POLYCHAR 23
PROGRAM & ABSTRACTS
23rd World Forum on Advanced Materials
University of Nebraska-Lincoln
Lincoln , Nebraska U.S.A.
May 11-15 , 2015
Welcome to PolyChar 23
University of Nebraska-Licoln, Lincoln, Nebraska
May 11-15, 2015
It is a pleasure to welcome you to PolyChar 23, the 23rd World Forum on Advanced Materials. The local
organizing committee with the help and support of members of the PolyChar executive committee, international partners, and local supporters has arranged a program of activities that we hope you enjoy. I would
like to thank all the presenters for their contribution, without which there could not be a scientiﬁc program.
Particular thanks goes to the plenary speakers, the keynote speakers, and the invited speakers that have
agreed to give direction to the program.
I would like to take this opportunity to thank our sponsors:
• The National Science Foundation,
• The International Union of Pure and Applied Chemistry (IUPAC),
• The IUPAC/Samsung fund,
• The John A. Woollam Company,
• The University of Nebraska-Lincoln (UNL),
• The UNL Oﬃce for Research and Economic Development,
• The UNL College of Engineering,
• The UNL Department of Mechanical & Materials Engineering,
• The City of Lincoln Convention and Visitors Bureau
Dr. Jeﬀ Shield, Chair of the Department of Mechanical & Materials Engineering, and Dr. Tim Wei, Dean
of the College of Engineering, have been kind enough to provided the needed staﬀ, support and expertise to
host this conference. Without their help it would not be possible to arrange the conference.
Special thanks goes to Dr. Prem Paul, Vice Chancellor for Research & Economic Development at UNL,
that has been a strong supporter of the activities of the Advanced Mechanics and Materials Engineering
International Laboratory (AMME-International) and the eﬀort to bring PolyChar to UNL. He also provided
substantial ﬁnancial support for the conference.
Finally, special thanks goes to Mrs. Cherie Crist and Mrs. Mary Ramsier, that have worked tirelessly
to arrange all the activities, and to all the students that have been helping with the conference.
I hope you enjoy the program and your visit.
Sincerely,
Mehrdad Negahban, Local Organizations Chair
PolyChar 23
Local Organizing Committee
• Dr. Mehrdad Negahban, Local Chair, Mechanical & Materials Engineering
• Dr. Christopher Cornelius, Chemical & Biomolecular Engineering
• Dr. Stephen Ducharme, Physics And Astronomy
• Dr. Yuris Dzenis, Mechanical & Materials Engineering
• Dr. Lucia Fernandez-Ballester, Mechanical & Materials Engineering
• Dr. Jinsong Huang, Mechanical & Materials Engineering
• Dr. Carl Nelson, Mechanical & Materials Engineering
• Dr. Jeﬀ Shield, Mechanical & Materials Engineering
• Dr. Li Tan, Mechanical & Materials Engineering
• Dr. Joseph Turner, Mechanical & Materials Engineering
• Mrs. Cherie Crist, Conference Secretary, Mechanical & Materials Engineering
• Mrs. Mary Ramsier, Mechanical & Materials Engineering
International Organizers
• Dr. Jean-Marc Saiter,AMME-LECAP, University of Rouen, France
• Dr. Michael Hess, Chosun University, Korea
• Dr. Jean-Jacques Pireaux, University of Namur, Belgium
• Dr. Rameshwar Adhikari, Tribhuvan University, Nepal
• Dr. Witold Brostow, University of North Texas, USA
• Dr. Eric Dargent, AMME-LECAP, University of Rouen, France
• Dr. Allisson Saiter, AMME-LECAP, University of Rouen, France
• Dr. Laurent Delbrelh, AMME-LECAP, University of Rouen, France
• Dr. Antonella Esposito, AMME-LECAP, University of Rouen, France
• Dr. Nicolas Delpouve, AMME-LECAP, University of Rouen, France
PolyChar 23 Symposia
• GP- General Papers, Organizers: Jean-Marc Saiter, Carl A Nelson, Mehrdad Negahban.
• CMSP- Characterization Methods and Structure-Properties Relations, Organizers: Mehrdad
Negahban, Christopher Cornelius, Jean-Marc Saiter.
• PMMS- Predictive Methods, Modelling, and Simulation, Organizers: Mehrdad Negahban.
• GEEN- Green Polymers, Green Engineering and Recycling, Organizers: Jean-Marc Saiter,
Joseph Turner.
• BIOT- Biomaterials, Drug Delivery and Tissue Engineering, Organizers: Yuris Dzenis, Joseph
Turner, Carl A Nelson.
• FIC- Fibers, Interfaces and Composite Materials, Organizers: Yuris Dzenis, Antonella Esposito.
• NANO- Nanomaterials and Smart Materials, Organizers: Li Tan.
• DEMO- Dielectric, Electrical, Magnetic, Optical and Optoelectronic Properties, Organizers: Stephen Ducharme, Laurent Delbreilh.
• PEOD- Polymers in Electronics and Optoelectronics Devices, Organizers: Jinsong Huang.
• PS- Progress in Polymer Synthesis, Organizers: Nicolas Delpouve, Rameshwar Adhikari.
• MPP- Mechanical Properties and Performance, Organizers: Mehrdad Negahban, Joseph Turner.
• CSPM- Characterization with Scanning Probe Microscopes, Organizers: Joseph Turner,
Rameshwar Adhikari.
• RSP- Rheology, Solutions and Processing, Organizers: Mehrdad Negahban, Lucia FernandezBallester, Antonella Esposito.
• PPSC- Processing and Properties of Semicrystalline Polymers, Organizers: Lucia FernandezBallester, Eric Dargent.
TIME
EVENT (LOCATION)
Monday, May 11
8:00 AM 8:30 AM 12:00 PM 1:00 PM 6:00 PM Registration
M1: Short Course (Auditorium, NU)
Lunch (Ballroom, NU)
M2: Short Course (Auditorium, NU)
Reception (Sheldon Art Gallery)
Tuesday, May 12
8:00 AM
8:20 AM 9:40 AM 10:00 AM
12:00 PM
12:50 PM 1:40 PM 2:40 PM 3:05 PM Registration
Opening/Plenary (Auditorium, NU)
Coffee Break
T2_1: CMSP (Heritage Room, NU)
Lunch (Ballroom, NU)
T_3: Young Plenary (Auditorium, NU)
T4_1: CMSP (Heritage Room, NU)
Coffee Break
T5_1 CMSP (Heritage Room, NU)
Wednesday, May 13
8:00 AM
8:30 AM 9:25 AM
9:45 AM
12:00 PM
1:00 PM 1:50 PM Registration
Plenary (Auditorium, NU)
Coffee Break
W2_1: NANO (Auditorium, NU)
Lunch (Ballroom, NU)
W_3: Young Plenary (Auditorium, NU)
W4: Posters (Ballroom, NU)
Thursday, May 14
8:30 AM 9:25 AM
9:45 AM
12:00 PM
1:00 PM 2:00 PM 3:40 PM 4:00 PM 6:00 PM Plenary (Henzlik 124)
Coffee Break
TH2_1: FIC (Henzlik 124)
Lunch (Ballroom, NU)
TH_3: Flory Medal Talk (Henzlik 124)
TH4_1: CSPM (Henzlik 124)
Coffee Break
TH5_1: BIOT (Henzlik 124)
Social Hour & Banquet (Ballroom, NU)
Friday, May 15
SCHEDULE
8:30 AM 9:25 AM
9:40 AM
12:00 PM
1:00 PM Plenary (Auditorium, NU)
Coffee Break
F2_1: PS (Auditorium, NU)
Lunch (Ballroom, NU)
F_3: Awards and Closing (Auditorium, NU)
EVENT (LOCATION)
T2_2: PEOD (Auditorium, NU)
T4_2: DEMO (Auditorium, NU)
T5_2: DEMO (Auditorium, NU)
W2_2: BIOT (Heritage Room, NU)
TH2_2: PPSC (Henzlik 53)
TH4_2: NANO (Henzlik 53)
TH5_2: PMMS (Henzlik 53)
F2_2: RSP/MPP (Heritage Room, NU)
nebraska union - city campus
Heritage Room
Auditorium
POLYCHAR 23 Technical Program
University of Nebraska-Licoln, Lincoln, Nebraska
May 11-15, 2015
Monday, May 11, 2015 Starting: 8:30 AM
M1: Short Course (Auditorium)
Session Chairs: Michael Hess, Brett Fors (Assistants: Wenlong Li, Jase Kaser )
1. (8:30 AM, Short Course) Menard: DYNAMIC MECHANICAL ANALYSIS
2. (9:25 AM, Short Course) Schubert: RHEOLOGY AND PROCESSING
3. (10:20 AM, Short Course) Schönherr: CHARACTERIZATION OF POLYMERIC NANOSTRUCTURES WITH COMBINED SCANNING PROBE AND FLUORESCENCE MICROSCOPIES
4. (11:15 AM, Short Course) Henning: MICROMECHANICS OF POLYMERS: MICRO- AND
NANOSCOPIC PROCESSES OF DEFORMATION AND FRACTURE
Monday, May 11, 2015 Starting: 1:00 PM
M2: Short Course (Auditorium)
Session Chairs: Kevin P. Menard, Sven Henning (Assistants: Marzieh Bakhtiary Noodeh, Mitchell
Schmidt)
1. (1:00 PM, Short Course) Saiter: GLASS TRANSITION AND GLASS TRANSITION TEMPERATURE
2. (1:55 PM, Short Course) Blümich: SOLID-STATE NMR
3. (2:50 PM, Short Course) Guenet: BASICS OF SCATTERING TECHNIQUES: X-RAY, NEUTRONS,
LIGHT
4. (3:45 PM, Short Course) Fors: PHOTOCHEMISTRY IN POLYMER SCIENCE
5. (4:40 PM, Short Course) Hnatchuk: FRICTION, WEAR AND SCRATCH RESISTANCE OF POLYMERS
Tuesday, May 12, 2015 Starting: 8:20 AM
T0: Opening (Auditorium)
Session Chair: Mehrdad Negahban (Assistants: Wenlong Li, John J. Bowen)
Tuesday, May 12, 2015 Starting: 8:45 AM
T1: Plenary (Auditorium)
Session Chair: Jinsong Huang (Assistants: Wenlong Li, John J. Bowen)
1. (8:45 AM, Plenary) Ade: SOFT X-RAY CHARACTERIZATION METHODS: UTILITY AND OPPORTUNITY
Tuesday, May 12, 2015 Starting: 10:00 AM
T2_1: CMSP (Heritage Room)
Session Chair: Bernhard Blümich (Assistant: John J. Bowen)
1. (10:00 AM, Keynote) Guenet: CHARACTERIZATION AND PROPERTIES OF HYBRID MATERIALS FROM POLYMERS AND SELF-ASSEMBLED SYSTEMS
2. (10:40 AM, Oral) Dargent: RELAXATION PROCESSES AND COOPERATIVITY IN COPOLYMERS WITH A SIMILAR BACKBONE FLEXIBILITY
3. (11:00 AM, Oral) Pireaux: UNDERSTANDING (INDUCING, REPAIRING) ION BEAM DAMAGES
IN POLYMERS - A POLYCHAR CONCERN
4. (11:20 AM, Oral) Delpouve: COUPLING APPROACHES FOR THE INVESTIGATION OF THE
ALPHA RELAXATION DYNAMICS IN INTERACTING NETWORKS
5. (11:40 AM, Oral) Adhikari: MORPHOLOGICAL, THERMAL AND ELECTRICAL PROPERTIES
OF STYRENIC BLOCK COPOLYMER COMPOSITES WITH NANOCARBONS
Tuesday, May 12, 2015 Starting: 10:00 AM
T2_2: PEOD (Auditorium)
Session Chair: Jinsong Huang (Assistant: Wenlong Li)
1. (10:00 AM, Invited) Ouyang: PEDOT:PSS FOR PEROVSKITE SOLAR CELLS
2. (10:20 AM, Invited) Xiao: UNDERSTANDING THE EFFECT OF DEUTERATED CONDUCTING POLYMER AND SOLVENT ADDITIVE ON THE PERFORMANCE OF ORGANIC PHOTOVOLTAICS
3. (10:40 AM, Oral) Ulanski: OTFTS WITH ULTRATHIN LAYERS OF POLY(3-HEXYLTIOPHENE)
4. (11:00 AM, Oral) Xiao: UNIVERSAL FORMATION OF COMPOSITIONALLY GRADED BULK
HETEROJUNCTION FOR EFFICIENCY ENHANCEMENT IN ORGANIC PHOTOVOLTAICS
5. (11:20 AM, Oral) Jo: CONDUCTING POLYMER/GRAPHENE COMPOSITE FOR SUPERCAPACITOR
Tuesday, May 12, 2015 Starting: 12:50 PM
T3: Young Pleanary (Auditorium)
Session Chair: Lucia Fernandez-Ballester (Assistants: Ramin Hosseinabad, Mitchell Schmidt)
1. (12:50 PM, Young Plenary) Stein: GRAZING INCIDENCE SMALL-ANGLE X-RAY SCATTERING:
PRINCIPLES, MODELS, AND APPLICATIONS FOR NANOSTRUCTURED THIN FILMS
Tuesday, May 12, 2015 Starting: 1:40 PM
T4_1: CMSP (Heritage Room)
Session Chair: Christopher Cornelius (Assistant: Ramin Hosseinabad )
1. (1:40 PM, Invited) Blümich: NMR-SPECTROSCOPY AND NONDESTRUCTIVE TESTING BY
COMPACT NMR
2. (2:00 PM, Oral) Tashiro: STRUCTURE FORMATION PROCESS OF POLY(VINYL ALCOHOL)IODINE COMPLEX REVEALED BY IN-SITU TIME-DEPENDENT X-RAY DIFFRACTION MEASUREMENT
3. (2:20 PM, Oral) Salim: THERMAL DEGRADATION IN THE MELT REACTION BETWEEN
POLY(3-HYDROXYBUTYATE-CO-3-HYDROXYHEXANOATE) AND EPOXIDIZED NATURAL
RUBBER
Tuesday, May 12, 2015 Starting: 1:40 PM
T4_2: DEMO (Auditorium)
Session Chair: Stephen Ducharme (Assistant: Mitchell Schmidt)
1. (1:40 PM, Invited) Xu: ENHANCED SENSITIVITY OF PRESSURE SENSOR USING ELECTROACTIVE POLYMERS
2. (2:00 PM, Oral) Poddar: FLEXOELECTRIC EFFECT IN FERROELECTRIC AND RELAXOR
POLYMERS OF VDF
3. (2:20 PM, Oral) Chan: RESPONSE OF SOLID POLYMER ELECTROLYTES TO ELECTRIC
FIELDS
2
Tuesday, May 12, 2015 Starting: 3:05 PM
T5_1: CMSP (Heritage Room)
Session Chair: Yong-Rak Kim (Assistant: Ramin Hosseinabad )
1. (3:05 PM, Oral) Sun: INVESTIGATING ORGANIC MATERIALS USING SPECTROSCOPIC ELLIPSOMETRY
2. (3:25 PM, Oral) Manhart: DESIGN OF ELASTOMER SURFACES WITH SPATIALLY CONTROLLED TRIBOLOGICAL PROPERTIES APPLYING PHOTOLITHOGRAPHIC TECHNIQUES
3. (3:45 PM, Oral) Desai: ROLE OF EXTERNAL DONOR AND CO-CATALYST - ZIEGLER NATTA
CATALYST USING SPECTROSCOPY TECHNIQUE
4. (4:05 PM, Oral) Schamme: ROLE OF MOLECULAR MOBILITY AND FRAGILITY ON PHYSICAL STABILITY OF TWO AMORPHOUS PHARMACEUTICALS IN THE SUPERCOOLED AND
GLASSY STATES
5. (4:25 PM, Oral) Viel: MOLECULAR MOBILITY VS POLYMORPHISM OF CHIRAL PHARMACEUTICAL COMPOUNDS: CASE OF DIPROPHYLLINE
6. (4:45 PM, Oral) Denchev: STRUCTURE GRADIENTS BY MICROFOCUS SYNCHROTRON XRAY DIFFRACTION IN SHELL-CORE POLYAMIDE MICROCAPSULES AND MOLDED COMPOSITES THEREOF
7. (5:05 PM, Oral) You: CHARACTERIZATION OF VISCOELASTIC-VISCOPLASTIC BEHAVIOR
OF POLYMERIC MATERIALS CONTAINING ALIPHATIC AND AROMATIC HYDROCARBONS
DERIVATIVES
Tuesday, May 12, 2015 Starting: 3:05 PM
T5_2: DEMO (Auditorium)
Session Chair: Chinhan Chan (Assistant: Mitchell Schmidt)
1. (3:05 PM, Invited) Jonas: NANOIMPRINTED FERROELECTRIC/SEMICONDUCTING POLYMER DEVICES
2. (3:25 PM, Oral) Sangoro: CHARGE TRANSPORT AND STRUCTURAL DYNAMICS IN POLYMERIZED IONIC LIQUIDS
3. (3:45 PM, Oral) Dencheva: FROM LOADED SHELL-CORE MICROCAPSULES TO THERMOPLASTIC HYBRID COMPOSITES: A NEW PATHWAY FOR THE PREPARATION OF CONDUCTIVE AND MAGNETIC POLYAMIDE COMPOSITES
4. (4:05 PM, Oral) Anada: DIVERSITY OF MICROSTRUCTURE OF POLYMER SOLID INVESTIGATED BY MOTION OF IMPURITY IONS
5. (4:25 PM, Oral) Hagg Lobland: THERMOELECTRIC GENERATORS (TEGS) WITH LONG SERVICE LIVES
Wednesday, May 13, 2015 Starting: 8:30 AM
W1: Plenary (Auditorium)
Session Chair: Li Tan (Assistants: Marzieh Bakhtiary Noodeh, Yan Zou)
1. (8:30 AM, Plenary) Laine: SYNTHESIS, PROCESSING AND PROPERTIES OF SILSESQUIOXANE MACROMONOMERS AND POLYMERS
3
Wednesday, May 13, 2015 Starting: 9:45 AM
W2_1: NANO (Auditorium)
Session Chair: Li Tan (Assistant: Marzieh Bakhtiary Noodeh)
1. (9:45 AM, Keynote) Dzenis: SIMULTANEOUSLY STRONG AND TOUGH CONTINUOUS POLYMER NANOFIBERS AND NANOCOMPOSITES
2. (10:25 AM, Invited) Serpe: STIMULI RESPONSIVE POLYMER-BASED SENSORS, MUSCLES,
AND DRUG DELIVERY PLATFORMS
3. (10:45 AM, Oral) Li: POLYMER-BASED MATERIALS FOR BUILDING ARTIFICIAL MUSCLES
AND THREE DIMENSIONAL STRUCTURES BY SELF-ROLLING
4. (11:05 AM, Oral) Alarifi: MECHANICAL AND THERMAL PROPERTIES OF CARBONIZED PAN
NANOFIBERS COHESIVELY ATTACHED TO SURFACE OF CARBON FIBER REINFORCED
COMPOSITES
5. (11:25 AM, Oral) Goponenko: ELECTROSPUN NANOFIBROUS MATERIALS AS STIMULI-RESPONSIVE POLYMERIZED HYDROGELS
Wednesday, May 13, 2015 Starting: 9:45 AM
W2_2: BIOT (Heritage Room)
Session Chairs: Linxia Gu, Dimitry Papkov (Assistant: Yan Zou)
1. (9:45 AM, Keynote) Causin: NANOCELLULOSE-REINFORCED GELS FOR BIOMEDICAL APPLICATIONS
2. (10:25 AM, Invited) Schönherr: INFECTION DIAGNOSTICS WITH POLYMERIC VESICLES
AND HYDROGELS FOR APPLICATION IN ADVANCED WOUND DRESSINGS AND BEYOND
3. (10:45 AM, Oral) Saunier: HOW ADDITIVE EXUDATION CAN AFFECT THE BIOCOMPATIBILITY OF A POLYMERIC MEDICAL DEVICE: THE CASE OF A POLYURETHANE USED IN
IMPLANTABLE CATHETERS
4. (11:05 AM, Oral) Ding: ELECTROSPUN PHB/PCL/FUMED SILICA FIBROUS STRUCTURE
FOR BONE TISSUE ENGINEERING
5. (11:25 AM, Oral) Andalib: BIOMIMETIC NANOFILAMENTARY POLYMER SCAFFOLDS AND
THE MECHANISMS OF CELL-SCAFFOLD INTERACTION
6. (11:45 AM, Oral) Maleckis: ULTRAHIGH-PERFORMANCE NANOFIBERS FROM DNA AND
PROTEINS
7. (12:05 PM, Oral) Lyu: INVESTIGATION OF RUBBER FLOW DURING SHAPING OF AUTOMOBILE TIRES
Wednesday, May 13, 2015 Starting: 1:00 PM
W3: Young Plenary (Auditorium)
Session Chair: Christopher Cornelius (Assistants: Trevor Gnuse, Yan Zou)
1. (1:00 PM, Young Plenary) Whittington: POLYMER CHARACTERIZATION OF MEDICAL DEVICES FOR USE IN CANCER PATIENTS
Wednesday, May 13, 2015 Starting: 1:50 PM
W4: Poster (Ballroom)
Session Chairs: Michael Hess, Jean-Jacques Pireaux (Assistant: Trevor Gnuse)
1. (1:50 PM, Poster) Jayasinghe: INVESTIGATION OF SWELLING BEHAVIOR OF POLY(HEMACO-DMAEMA) HYDROGELS CONFINED IN AN ELASTOMERIC MOLD
4
2. (1:50 PM, Poster) Schwahn: CONTROLLED CURING OF ACRYLATE: SYSTEM MODELING
AND APPLICATIONS IN STEREOLITHOGRAPHY
3. (1:50 PM, Poster) Adhikari: CHARACTERIZATION OF BAMBOO FLOURS REINFORCED
EPOXY RESIN COMPOSITES
4. (1:50 PM, Poster) Li: CHARACTERIZATION OF THE INFLUENCE OF DEPTH IN PHOTO CURING OF ACRYLATE: A METHOD BASED ON RAPID-SCAN FTIR DURING LASER CURING ON
AN ATR
5. (1:50 PM, Poster) Furgal: HIGH SURFACE AREA METHYLSILSESQUIOXANE POLYMER GELS
BY FLUORIDE CATALYSIS
6. (1:50 PM, Poster) Stockdale:
NANOCOMPOSITES
MANUFACTURING OF POLYIMIDE FIBER-REINFORCED
7. (1:50 PM, Poster) Zou: EFFECT OF CONSTRAINT ON STRUCTURE AND MECHANICAL
PROPERTIES OF CONTINUOUS POLYACRYLONITRILE-BASED STABILIZED AND CARBONIZED NANOFIBERS
8. (1:50 PM, Poster) Jasa: USING MOLECULAR DYNAMICS SIMULATIONS FOR CHARACTERIZING MACROSCOPIC RESPONSE IN POLYCARBONATE
9. (1:50 PM, Poster) Hnatchuk: MODIFICATION OF POLY(VINYL CHLORIDE)
10. (1:50 PM, Poster) Hnatchuk: PROPERTIES OF EPOXY FILMS BASED ON MODIFIED PHENOLFORMALDEHYDE OLIGOMERS
11. (1:50 PM, Poster) Chan: FTIR STRUCTURAL ANALYSIS OF EPOXY PAINTS ON STEEL
STRUCTURE FOR COATING FINGERPRINTING CERTIFICATE FOR PAINT INDUSTRY
12. (1:50 PM, Poster) Viel: IMPACT OF COVER SLIDE ON RECRYSTALLIZATION FROM THE
AMORPHOUS STATE OF CHIRAL PHARMACEUTICAL COMPOUNDS: CASE OF DIPROPHYLLINE
13. (1:50 PM, Poster) Cosby: CHARGE TRANSPORT AND STRUCTURAL DYNAMICS OF POLYMERIZED IONIC LIQUIDS
14. (1:50 PM, Poster) Jiao: INTERPLAY BETWEEN ABSORPTION BROADENING AND MORPHOLOGY DETERIORATION IN TERNARY BULK HETEROJUNCTION SOLAR CELLS RESOLVED
BY SOFT X-RAY SCATTERING
15. (1:50 PM, Poster) Chen: OPTIMIZATION OF THE DISTRIBUTION OF PROPERTIES: USING
ACRYLATE/EPOXY MIXTURES IN THE EXTENSION OF AN FGM PLATE WITH A HOLE
16. (1:50 PM, Poster) Daily: DIELECTRIC PROPERTIES AND KINETIC STUDY ON THE DEGRADATION OF BISMALEIMIDE RESIN
17. (1:50 PM, Poster) Jamil: MECHANISM OF MOLECULAR INTERACTION OF SUPERPLASTICIZER OLIGOMERS WITH HYDRATED CEMENT PHASES
18. (1:50 PM, Poster) Piorkowska: COMPARISON OF PROPERTIES OF STAR AND LINEAR
POLY(L-LACTIDE)
19. (1:50 PM, Poster) Frazier: CHEMICAL MODIFICATION OF PROTEIN-BASED ADHESIVES FOR
CONSTRUCTION APPLICATIONS
20. (1:50 PM, Poster) Dargent: MOLECULAR DYNAMICS IN ELECTROSPUN FIBERS OF PLASTICIZED POLYLACTIDE
5
21. (1:50 PM, Poster) Gakhutishvili: TRIBOLOGICAL PROPERTIES OF ANTIBACTERIAL POLYMER COMPOSITES
22. (1:50 PM, Poster) Delpouve: LENGTH SCALE AT THE GLASS TRANSITION IN SEMI-CRYSTALLINE COMPATIBILIZED POLYLACTIDE/CLAY NANOCOMPOSITES
23. (1:50 PM, Poster) Lin: HYDROGEN BONDING INDUCED NANOPHASE SEPARATION OF GIANT SURFACTANTS TOWARD SUB-10-NM HYBRID ORDER NANOSTRUCTURES
24. (1:50 PM, Poster) Liu: TWO-DIMENSIONAL NANO-CRYSTALS OF MOLECULAR JANUS PARTICLES
25. (1:50 PM, Poster) Alarifi: EFFECTS OF UV EXPOSURE ON PHYSICAL PROPERTIES OF CARBON FIBER/PPS THERMOPLASTIC COMPOSITES
26. (1:50 PM, Poster) Kaser:
YARNS
NANOMANUFACTURING POLYACRYLONITRILE NANOFIBER
27. (1:50 PM, Poster) Alharbi: INTEGRATING C60 NANOPARTICLES INTO TIO2 NANOFIBERS
VIA ELECTROSPINNING PROCESS FOR ENHANCED ENERGY CONVERSTION EFFICIENCIES
28. (1:50 PM, Poster) Loubeau: AGEING OF A THREE-LAYER PAPER USED IN THE INSULATION
OF AN ELECTRICAL MOTOR FOR THE AUTOMOTIVE TRACTION
29. (1:50 PM, Poster) Schmidt: A STUDY OF THE EFFECTS OF SPIN COATING ON PVDF FILMS
30. (1:50 PM, Poster) Schönherr: INVESTIGATION OF ELECTRONIC PROPERTIES OF A
GRAPHENE FIELD EFFECT TRANSISTOR
31. (1:50 PM, Poster) Ding: BROADBAND DIELECTRIC RELAXATION ANALYSIS ON THE REINFORCEMENT OF ANTHRACENE-FUNCTIONALIZED EPOXY COMPOSITES
32. (1:50 PM, Poster) Lobland: SYNTHESIS AND PROPERTIES OF REACTIVE OLIGOMERS
BASED ON A PEROXY DERIVATIVE OF AN EPOXY RESIN AND 1,4- BUTANEDIOL
33. (1:50 PM, Poster) Ospina: SYNTHESIS AND CHARACTERIZATION OF POLYMERS WITH ANTIBACTERIAL PROPERTIES BASE ON TRICLOSAN ACRYLATE
34. (1:50 PM, Poster) Bakhtiary Noodeh: USING CURING KINETICS TO CONTROL THE MECHANICAL PROPERTIES OF SIMULTANEOUS ACRYLATE/EPOXY IPNS DURING PHOTO
CURING OF GRADED MATERIALS
35. (1:50 PM, Poster) Gafurov: MOLECULAR STRUCTURE PARAMETERS INFLUENCE ON DEFORMATION MECHANICS OF AN ORIENTED CRYSTALLINE POLYMER
36. (1:50 PM, Poster) Lanyi: NOVEL CHART FOR REPRESENTATION OF MATERIAL PERFORMANCE AND RELIABILITY
37. (1:50 PM, Poster) Rezaei: U-SHAPED PROBES FOR CHARACTERIZATION OF POLYMERS
USING CONTACT RESONANCE ATOMIC FORCE MICROSCOPY
38. (1:50 PM, Poster) Dargent: STUDY OF AMORPHOUS AND CRYSTALLINE PHASES IN BIOBASED NANOCOMPOSITE FILMS
39. (1:50 PM, Poster) Delpouve: MICROSTRUCTURE, AMORPHOUS PHASE DYNAMICS AND
BARRIER PROPERTIES IN MULTILAYER COEXTRUDED POLYLACTIDE
6
40. (1:50 PM, Poster) Schamme:
POLY(LACTIC ACID)
RELAXATION OF SHEAR-INDUCED PRECURSORS IN
41. (1:50 PM, Poster) Hosseinabad: EFFECT OF COPOLYMER CONTENT ON FLOW-INDUCED
CRYSTALLIZATION
42. (1:50 PM, Poster) Sterzynski: THE POSS AND MWCNT MODIFIED GLASS TRANSITION TEMPERATURE TG OF POLY(VINYL CHLORIDE)
43. (1:50 PM, Poster) Saiter: INFLUENCE OF STRUCTURAL FEATURES OF POROGEN
MOLECULES ON THERMAL PROPERTIES AND POROSITY OF NANOPOROUS POLYCYANURATE-BASED FILM MATERIALS
44. (1:50 PM, Poster) Zare Rami: INVESTIGATION OF FRACTURE BEHAVIOR OF HETEROGENEOUS POLYMER MIXTURES SUBJECTED TO VISCOELASTIC DEFORMATION USING
MICROSTRUCTURAL MODELING
45. (1:50 PM, Poster) Ding: POLAR PHASE GENERATION IN PVDF, THROUGH AMPHIPHILIC
IONIC LIQUID MODIFIED MULTIWALLED CARBON NANOTUBES: EFFECT OF ANION
Thursday, May 14, 2015 Starting: 8:30 AM
TH1: Plenary (Henzlik 124)
Session Chair: Yuris Dzenis (Assistants: Kaspars Maleckis, Zesheng Zhang)
1. (8:30 AM, Plenary) Cheng: GIANT POLYHEDRA AND GIANT SURFACTANTS BASED ON
NANO-ATOMS: TUNING FROM CRYSTALS, TO QUASICRYSTALS, TO FRANK-KASPER
PHASES: AN INTERCONNECTION BETWEEN SOFT AND HARD MATTER
Thursday, May 14, 2015 Starting: 9:45 AM
TH2_1: FIC (Henzlik 124)
Session Chair: Yuris Dzenis (Assistant: Kaspars Maleckis)
1. (9:45 AM, Keynote) Galeski:
CRYSTALLIZATION AND MELTING PHENOMENA IN
NANOFIBER REINFORCED POLYMER NANOCOMPOSITES
2. (10:25 AM, Invited) Papkov: POLYMER CRYSTALLINITY AND TOUGHNESS: INCREASING
PLASTICITY OF CONTINUOUS POLYACRYLONITRILE NANOFIBERS THROUGH CRYSTALLIZATION SUPPRESSION
3. (10:45 AM, Oral) Sterzynski: ECOLOGICALLY FRIENDLY MULTILAYER WPC/SRC CONSTRUCTION MATERIALS; PRODUCTION, STRUCTURE AND PROPERTIES
4. (11:05 AM, Oral) Gonçalves: XANTHAM GUM AND CHITOSAN AS NATURAL ADHESIVES
FOR CORK
5. (11:25 AM, Oral) Bin: TRANSCRYSTALLIZATION IN CARBON FIBRE FILLED POLY (L-LACTIC ACID) COMPOSITES UNDER TEMPERATURE GRADIENT
6. (11:45 AM, Oral) Alharbi: SYNTHESIS AND ANALYSIS OF ELECTROSPUN SRTIO3
NANOFIBERS WITH NIOX NANOPARTICLES SHELLS AS PHOTOCATALYSTS FOR WATER
SPLITTING
Thursday, May 14, 2015 Starting: 9:45 AM
TH2_2: PPSC (Henzlik 53)
Session Chairs: Eric Dargent, Lucia Fernandez-Ballester (Assistant: Zesheng Zhang)
1. (9:45 AM, Keynote) Lefebvre: IN-SITU SAXS/WAXS INVESTIGATIONS ON DEFORMATION
INDUCED STRUCTURAL EVOLUTIONS IN AMORPHOUS AND SEMI-CRYSTALLINE POLYMERS
7
2. (10:25 AM, Oral) Mokni: EFFECT OF THE SUBLIMATION TEMPERATURE ON THE MORPHOLOGY AND CRYSTALLINITY OF PARYLENE D DEPOSITED BY CVD
3. (10:45 AM, Oral) Piorkowska: NUCLEATION OF HIGH-PRESSURE-INDUCED GAMMA FORM
IN ISOTACTIC POLYPROPYLENE IN NONISOTHERMAL CONDITIONS
4. (11:05 AM, Oral) Fernandez-Ballester: EFFECT OF COPOLYMER CONTENT ON FLOW-INDUCED CRYSTALLIZATION
5. (11:25 AM, Oral) Lugito: NOVEL APPROACHES TO ADVANCE UNDERSTANDING OF POLYMER CRYSTALLIZATION
6. (11:45 AM, Oral) Ding: EFFECT OF TRI-ARM STAR-SHAPED IMIDAZOLIUM IONIC LIQUID
OLIGOMER WITH PEG SEGMENT ON THE CRYSTALLIZATION BEHAVIORS OF POLY(LLACTIC ACID)
Thursday, May 14, 2015 Starting: 1:00 PM
TH3: Flory Medal Talk (Henzlik 124)
Session Chair: Jean-Jacques Pireaux (Assistants: John Jasa, Taylor Stockdale)
1. (1:00 PM, Prize Talk) Tashiro: CLARIFICATION OF MICROSCOPICALLY-VIEWED STRUCTURE-PROPERTY RELATIONSHIP OF POLYMER MATERIALS
Thursday, May 14, 2015 Starting: 2:00 PM
TH4_1: CSPM (Henzlik 124)
Session Chairs: Joseph Alan Turner, Philip Yuya (Assistant: John Jasa)
1. (2:00 PM, Keynote) Yablon: ADVANCES IN ATOMIC FORCE MICROSCOPY (AFM) BASED
METHODS TO CHARACTERIZE POLYMER MATERIALS ON THE NANOSCALE
2. (2:40 PM, Invited) Yuya: EFFECT OF GOLD NANOPARTICLE ENHANCEMENT ON NANOMECHANICAL PROPERTIES OF CHITOSAN FILMS
3. (3:00 PM, Oral) Desyatova: CHARACTERIZATION OF THERMOMECHANICAL PROPERTIES
OF RECOMBINANT RESILIN USING ATOMIC FORCE MICROSCOPY
4. (3:20 PM, Oral) Turner: SIMULTANEOUS QUANTIFICATION OF THE IN-PLANE AND OUTOF-PLANE LOSS TANGENT OF POLYMERS USING CONTACT RESONANCE ATOMIC FORCE
MICROSCOPY
Thursday, May 14, 2015 Starting: 2:00 PM
TH4_2: NANO (Henzlik 53)
Session Chair: Michael J. Serpe (Assistant: Taylor Stockdale)
1. (2:00 PM, Invited) Okamoto: EFFECT OF PARTICLE DISTORTION ON SAXS FROM OBDD
STUDIED USING PARACRYSTALLINE THEORY AND SELF-CONSISTENT FIELD THEORY
2. (2:20 PM, Invited) Matsuo: MECHANICAL AND DIELECTRIC PROPERTY OF POLYMERFILLER COMPOSITES IN TERMS OF THERMAL FLUCTUATION-INDUCED TUNNELING EFFECT
3. (2:40 PM, Oral) Song: REVERSAL NANOIMPRINTING AND FERROELECTRIC PROPERTIES
OF P(VDF-TRFE) COPOLYMER NANOSTRUCTURES ON FLEXIBLE PET SUBSTRATE
4. (3:00 PM, Oral) Hnatchuk: POLYCARBONATE AND POLYURETHANE NANO AND MICROHYBRID FOAMS
5. (3:20 PM, Oral) Park: CHARACTERIZATION OF CRYSTALLINE THERMOSETTING UREAFORMALDEHYDE RESINS
8
Thursday, May 14, 2015 Starting: 4:00 PM
TH5_1: BIOT (Henzlik 124)
Session Chair: Holger Schönherr (Assistant: John Jasa)
1. (4:00 PM, Keynote) Castano: ADVANCED NATURAL MATERIALS: FROM RICE HUSK TO
AEROSPACE SYSTEMS
2. (4:40 PM, Invited) Thomas: ROLE OF NANOPARTICLES IN COMPATIBILIZING IMMISCIBLE
POLYMER BLENDS
3. (5:00 PM, Oral) Gnuse: MECHANICALLY ACCURATE NANOFIBROUS VASCULAR GRAFT
MATERIALS
4. (5:20 PM, Oral) Laskar: EVALUATION OF POTENTIAL APPLICATION OF UNUSUAL POLYMERSOMES PREPARED FROM PH-RESPONSIVE DUAL HYDROPHILIC BIOCOMPATIBLE
RANDOM COPOLYMERS
Thursday, May 14, 2015 Starting: 4:00 PM
TH5_2: PMMS (Henzlik 53)
Session Chair: Zheng Li (Assistant: Taylor Stockdale)
1. (4:00 PM, Keynote) Saiter:
GLASSY POLYMERS
PHYSICAL AGEING AND COOPERATIVE RELAXATION IN
2. (4:40 PM, Oral) Hagg Lobland: BRITTLENESS OF POLYMERS AND THE RELATION TO
TOUGHNESS
3. (5:00 PM, Oral) Li: CHARACTERIZATION OF STRAIN-INDUCED ELASTIC ANISOTROPY,
EQUILIBRIUM STRESS, AND MODELING OF THE THERMAL-MECHANICAL RESPONSE OF
PEEK
4. (5:20 PM, Oral) Xu: VISUALIZED POLYMER PROCESSING: FAST COLLOIDAL PARTICLE
REDISTRIBUTION AT NON-PLANAR SOLIDIFICATION INTERFACE
Friday, May 15, 2015 Starting: 8:30 AM
F1: Plenary (Auditorium)
Session Chair: Lucia Fernandez-Ballester (Assistants: Marzieh Bakhtiary Noodeh, Mohammad Nahid
Andalib)
1. (8:30 AM, Plenary) Segalman: USING BIOINSPIRED POLYMERS TO EXPLORE THE ROLE OF
SEQUENCE ON CONTROLLING POLYMER PROPERTIES
Friday, May 15, 2015 Starting: 9:40 AM
F2_1: PS (Auditorium)
Session Chairs: Jean-Marc Saiter, Nicolas Delpouve (Assistant: Mohammad Nahid Andalib)
1. (9:40 AM, Keynote) Grande: DESIGN, SYNTHESIS, AND CHARACTERIZATION OF FUNCTIONAL DOUBLY POROUS CROSSLINKED POLYMERS
2. (10:20 AM, Keynote) López: A NEW METHOD TO MODIFY POLY(ARYLENE ETHERS) WITH
A MILD SULFONATION AGENT
3. (11:00 AM, Invited) Fors: DETERMINISTIC CONTROL OF POLYMER MOLECULAR WEIGHT
DISTRIBUTION
4. (11:20 AM, Oral) Neupane: CONVERSION OF PAPER WASTE INTO BIOPLASTICS (POLYLACTIC ACID)
9
5. (11:40 AM, Oral) Bhajiwala: MORPHOLOGICAL STUDY OF SPHERICAL MAGNESIUM
DICHLORIDE SUPPORTED TI BASED ZIEGLER NATTA CATALYST SYSTEM
Friday, May 15, 2015 Starting: 9:40 AM
F2_2: RSP/MPP (Heritage Room)
Session Chairs: Joseph Turner, Lucia Fernandez-Ballester (Assistant: Ehsan Rezaei)
1. (9:40 AM, Invited) Schubert: BINARY AND TERNARY BLENDS OF POLYPROPYLENE TYPESINFLUENCE ON THE HOMOGENEITY OF BIAXIAL ORIENTED FILMS
2. (10:00 AM, Oral) Chaganti: PLASTICIZED POLY (3-HYDROXYBUTYRATE): BIOBASED OLEGOMERIC DIISOCYANATE AS A TOUGHENER
3. (10:20 AM, Oral) Li: THE DYNAMIC FRACTURE BEHAVIOR OF PMMA
4. (10:40 AM, Oral) Wojtczak: ALL-POLYMER FIBRILLAR NANOCOMPOSITES
5. (11:00 AM, Oral) Akram: SOL-GEL DERIVED ORGANIC/INORGANIC HYBRID NANOCOMPOSITES FROM VEGETABLE OILS AS SURFACE COATING MATERIALS
6. (11:20 AM, Oral) Lin: CONTRIBUTION OF COLLAGEN FIBER UNDULATION TO MECHANICAL PROPERTIES OF TYPE I COLLAGEN GEL
Friday, May 15, 2015 Starting: 1:00 PM
F3: Awards and Closing Session
Session Chairs: Michael Hess, Jean-Marc Saiter, Jean-Jacques Pireaux, Mehrdad Negahban (Assistants: Wenlong Li, Ramin Hosseinabad, Marzieh Bakhtiary Noodeh)
10
Monday, May 11, 2015 Starting: 8:30 AM
M1: Short Course (Auditorium)
Session Chairs: Michael Hess, Brett Fors
Assistants: Wenlong Li, Jase Kaser
Talks:
1. (8:30 AM, Short Course) Menard: DYNAMIC MECHANICAL ANALYSIS
2. (9:25 AM, Short Course) Schubert: RHEOLOGY AND PROCESSING
3. (10:20 AM, Short Course) Schönherr: CHARACTERIZATION OF POLYMERIC NANOSTRUCTURES WITH COMBINED SCANNING PROBE AND FLUORESCENCE MICROSCOPIES
4. (11:15 AM, Short Course) Henning: MICROMECHANICS OF POLYMERS: MICRO- AND
NANOSCOPIC PROCESSES OF DEFORMATION AND FRACTURE
11
Talk Number: 1 (Short Course)
Time: Monday, May 11, 2015 8:30 AM
Session: M1: Short Course (Auditorium)
DYNAMIC MECHANICAL ANALYSIS
Kevin P. Menard1
1
Thermal Analysis, PerkinElmer, USA
Dynamic Mechanical Analysis is one of the most powerful tools for understanding materials. This class
will cover the basics of the technique and it’s applications to polymers. After discussing the basics of the
technique and its most common use in the polymer industry, we will move on to more complex applications.
The effects of frequency and strain on temperature scan, methods of kinetics, humidity, UV irradiation, and
immersion testing will be discussed.
Kevin P Menard recieved his PhD from the Wesleyan University and did post doctoral research at
Rensselaer Polytechnic Institute. He has worked for Fina Oil and Chemical, General Dynamics, and
PerkinElmer EH, where he is the Product Manager for Thermal Analysis. He has over 125 publications, 17
patents, and authored the book "Dynamic Mechanical Analysis: A Practical Introduction."
12
Talk Number: 2 (Short Course)
Time: Monday, May 11, 2015 9:25 AM
Session: M1: Short Course (Auditorium)
RHEOLOGY AND PROCESSING
Dirk W. Schubert1
1
Material Science, Institute for Polymer Materials, Germany
An overview from fundamental point of view will be given describing materials flow behavior. Corresponding
simple differential equations will be derived and solved for special cases. Aspects on linearity will be
explained to answer the question “What is a linear material behavior?” Shear thinning and relevant
equations will be discussed to understand viscosity. Selected processed will be discussed where viscosity
plays the main role.
13
Talk Number: 3 (Short Course)
Time: Monday, May 11, 2015 10:20 AM
Session: M1: Short Course (Auditorium)
CHARACTERIZATION OF POLYMERIC NANOSTRUCTURES WITH COMBINED
SCANNING PROBE AND FLUORESCENCE MICROSCOPIES
Holger Schönherr1
1
Department of Chemistry & Biology, Physical Chemistry I, University of Siegen, Germany
This short course module will introduce scanning probe microscopy for studying polymer morphologies. In
particular, I will focus on the fundamental principles and the basic modes of atomic force microscopy (AFM),
the differentiation of different phases present in polymers (amorphous vs. crystalline) and the determination
of local mechanical properties. The probing of polymeric nanostructures, such as tubes, particles and hollow
vesicular containers, by AFM will be complemented by simultaneous fluorescence microscopic approaches,
which shed light onto the local nanoscale surroundings of incorporated tracer dye molecules.
Holger Schönherr studied chemistry and polymer chemistry & physics at the Universities of Mainz
and Toronto and finished his diploma thesis with Helmut Ringsdorf in 1995. He obtained his Ph.D. at the
University of Twente, The Netherlands in 1999, working with G. Julius Vancso. Following a postdoctoral stay
at Stanford University with Curtis W. Frank he joined the MESA+ Institute for Nanotechnology in Twente
as assistant (later associate) professor before joining the University of Siegen in 2008 as a tenured University
Professor in Physical Chemistry. He was awarded among others with the Raphael-Eduard-Liesegang award
of the German Colloid Society (2011), the International POLYCHAR Materials Science Prize (2013) and
the Research Prize of the Faculty of Science and Engineering of the University of Siegen (2013). His research
interests comprise the chemistry and physics of biointerfaces, self-assembled and nanostructured polymer
systems, and surface analysis with atomic force microscopy. He is author of more than 170 papers in peer
reviewed journals and published in the Springer Laboratory series a book on “Scanning Force Microscopy of
Polymers” (Holger Schönherr, G. Julius Vancso, 2010, Springer, Vienna).
14
Talk Number: 4 (Short Course)
Time: Monday, May 11, 2015 11:15 AM
Session: M1: Short Course (Auditorium)
MICROMECHANICS OF POLYMERS: MICRO- AND NANOSCOPIC PROCESSES
OF DEFORMATION AND FRACTURE
Sven Henning1
1
Biological and Macromolecular Materials, Fraunhofer Institute for Mechanics of Materials, Germany
The main aims of micromechanical analyses are the identification of property determining micro- and
nanostructures and the description of the principal deformation phenomena that occur when mechanical
load is applied to the material, as there are, for instance, crazing, homogeneous deformation, shear
band formation, micro- and nanovoid formation, fibrillation, etc. These processes can be correlated to
a brittle, semiductile or ductile material behavior on the macroscopic scale. In that sense, the description of micromechanical phenomena can contribute to the formulation of material laws predicting the
response of a material to mechanical load. Micromechanical processes are the link between the morphology
(predicted by synthesis, composition, and processing), loading conditions and resulting mechanical properties.
There are a number of different micromechanical techniques that can be adapted with respect to the
actual problem. First of all, there are micromechanical in situ methods characterized by the application of
tensile load, compressive or bending force using miniaturized testing devices inside the TEM, (E)SEM or
AFM. Alternatively, microscopic analyses of deformation zones can be performed after mechanical testing ex
situ with correlation to actual states of deformation. That approach also includes the inspection of fracture
surfaces and, to some extent, problems of failure analysis. Thirdly, micromechanical techniques also include
the application of miniaturized mechanical testing devices for small samples (e.g., micro-parts, biological
samples, nanofibers) or for mechanical testing of small amounts of materials from new syntheses. Finally,
the micromechanical approach allows the measurement of local mechanical properties in microscopic regions
of interest.
The presentation also covers different preparation routes with a special emphasis on preparation by
means of (cryo-)ultramicrotomy. The advantages of the different techniques are illustrated by a number of
examples covering semicrystalline polymers, block copolymers, composites and nanocomposites with different
filler geometries (particles, layered structures, carbon nanotubes) and biological/biomedical materials (bone,
electrospun nanofibers).
15
Monday, May 11, 2015 Starting: 1:00 PM
M2: Short Course (Auditorium)
Session Chairs: Kevin P. Menard, Sven Henning
Assistants: Marzieh Bakhtiary Noodeh, Mitchell Schmidt
Talks:
1. (1:00 PM, Short Course) Saiter: GLASS TRANSITION AND GLASS TRANSITION TEMPERATURE
2. (1:55 PM, Short Course) Blümich: SOLID-STATE NMR
3. (2:50 PM, Short Course) Guenet: BASICS OF SCATTERING TECHNIQUES: X-RAY, NEUTRONS,
LIGHT
4. (3:45 PM, Short Course) Fors: PHOTOCHEMISTRY IN POLYMER SCIENCE
5. (4:40 PM, Short Course) Hnatchuk: FRICTION, WEAR AND SCRATCH RESISTANCE OF POLYMERS
16
Talk Number: 1 (Short Course)
Time: Monday, May 11, 2015 1:00 PM
Session: M2: Short Course (Auditorium)
GLASS TRANSITION AND GLASS TRANSITION TEMPERATURE
Jean-Marc Saiter1
1
Institut des Matériaux de Rouen, Universite de Rouen, France
We will look at the glass transition. When a liquid is cooled, a vitreous structure can be obtained if the
cooling conditions (mainly the value of the cooling rate) are not compatible with the kinetic conditions to
get a crystal. The temperature for which a transition between the liquid and the glassy materials occurs
is called the glass transition temperature. This glass transition temperature is not a material constant,
because the glass transition does not separate two steady states that the material could reach by changing
only the temperature or the pressure. In other words the glass transition is not a thermodynamic transition.
This particularity is also associated with the structural disorder that is frozen in at Tg.
We will consider the conditions that result in a glass, and then provide a description of a disordered
structure, considering the consequence of structural disorder on the physical behavior of such materials. We
will look at how the glass transition temperature can be correctly determined, what method can be used for
this evaluation, and the common errors that are generally made. We will conclude by looking at examples
of signals obtained by means of calorimetry so that students can have an idea of what to expect when doing
such measurements.
Professor Saiter is Professor Exceptional Class and the Director of the Institute of Materials Research at the University of Rouen, Rouen, France. He has over 200 journal publications, and has been
one of the active members of the PolyChar Conference. He also is the founding member of the Advanced
Mechanics and Materials Engineering International Laboratory and the first French Director.
17
Talk Number: 2 (Short Course)
Time: Monday, May 11, 2015 1:55 PM
Session: M2: Short Course (Auditorium)
SOLID-STATE NMR
Bernhard Blümich1
1
Institut fuer Technische und Makromolekulare Chemie, RWTH Aachen University, Germany
Nuclear Magnetic Resonance (NMR) is one of the most powerful techniques to characterize materials and
molecules. While most other forms of spectroscopy probe electrons, NMR probes nuclei and takes a look
at matter from the inside of molecules. Since molecular motion in solids is slow, the chemical information
is obscured by anisotropic magnetic interactions between nuclei, leaving NMR relaxation and molecular
diffusion as the most simple NMR tools to characterize the physical properties of polymers. These quantities
can be measured with far more simple instrumentation than needed for chemical analysis. The course gives
an introduction to NMR with special emphasis on relaxation and diffusion measurements with compact
instrumentation drawing on applications to polymer morphology and aging. It will conclude with an outlook
on desktop NMR spectroscopy for chemical analysis of polymer solutions.
Reference
B. Blümich, S. Haber-Pohlmeier, W. Zia, Compact NMR, de Gruyter, Berlin, 2014
Prof. Blümich is Chair of Macromolecular Chemistry at RWTH Aachen University. He received his
education in Physics at the Technical University in Berlin and at Rensselaer Polytechnic Institute in Troy,
N.Y. His research activities aim at understanding the macroscopic properties of advanced polymer and
functional porous materials by NMR on a microscopic and molecular basis. To this end he develops and
applies NMR methods for NMR spectroscopy of liquids and solids, NMR imaging of heterogeneous materials
and fluid flow, and measurements of NMR relaxation and diffusion. Bernhard Blümich has pioneered a
number of methodical innovations concerning multidimensional NMR spectroscopy with noise excitation,
1D and 2D methods of studying molecular motion in solids, solid sate imaging, and flow NMR. A growing
focus in his recent work is the development of magnets for compact NMR such as the NMR-MOUSE for
non-destructive materials testing and permanent magnets with homogeneous fields for chemical analysis by
1H NMR spectroscopy under the fume hood. His publication record includes over 400 papers, 3 monographs
and number of patents.
18
Talk Number: 3 (Short Course)
Time: Monday, May 11, 2015 2:50 PM
Session: M2: Short Course (Auditorium)
BASICS OF SCATTERING TECHNIQUES: X-RAY, NEUTRONS, LIGHT
Jean-Michel Guenet1
1
Institut Charles Sadron, CNRS-Université de Strasbourg, France
In this short lecture we will present some basic knowledge about small-angle scattering techniques used in
the study of the structure of matter. Three types of radiations will be discussed as the basic principles for
describing molecular structures are the same. They, however, do not necessarily interact with matter in the
same way. X-ray and light are both composed of photons and interact therefore with the electron clouds,
yet the 3-order of magnitude discrepancy in wavelength makes that the correlations investigated, namely
distances explored in a sample, range from 1000-100 nm in the case of light down to 10-1 nm in the case of
X-rays. Conversely, neutron is a quantum particle with a given wavelength so that it behaves as X-ray and
light but interacts with the atomic nucleus instead. This allows one to toy with the so-called “contrast factor”
in order to differentiate the various molecular structures present in a sample. Typical scattering sets-up
will be presented so as to provide some details about the experimental aspects. Various models of structures of polymers and self-assembled systems will be described together with available experimental examples.
Professor Jean-Michel Guenet is the Director of ICS and the Head of Institute Charles Sadron (200
employees) at CNR-University of Strasbourg. Dr. Guenet received his master from Paris XIII University
and his Ph.D. from Strasbourg University. He is the author of over 170 peer-reviewed journal articles and
three books. He received the Dillon medal of the American Physical Society in 1990. Dr. Guenet has
given over 70 invited talked at international symposia and has been a visiting professor at Mons-Hainaut
University, Belgium, and Shizuoka University, Japan.
19
Talk Number: 4 (Short Course)
Time: Monday, May 11, 2015 3:45 PM
Session: M2: Short Course (Auditorium)
PHOTOCHEMISTRY IN POLYMER SCIENCE
Brett Fors1
1
Department of Chemistry and Chemical Biology, Cornell University, USA
Having precise control over a polymer’s architecture and composition enables tuning of its function and
allows the development of new technologies. Light has proven to be a highly unique reagent in polymer
synthesis that can give both spatial and temporal control over polymerization and give rise to the formation
of a diverse set of structures. On this basis, photochemistry in polymer science has seen significant attention
and been used for an array of applications. This short course will look at some of the important advances
in photomediated polymerizations over the last two decades, examine new developments in this field, and
assess its future promise in materials science.
Brett P. Fors was born in Polson, Montana and carried out his undergraduate studies in chemistry
at Montana State University (B.S., 2006). He went on to do his Ph.D. (2011) at the Massachusetts Institute
of Technology with Professor Stephen L. Buchwald, where he worked on the development and applications
of Pd catalysts for C-N cross-coupling reactions. After his doctoral studies he became an Elings Fellow at
the University of California, Santa Barbara working with Professor Craig J. Hawker on new polymerization
techniques that can be effectively regulated with light. In the summer of 2014 he joined the faculty at Cornell University and is currently an Assistant Professor in the Department of Chemistry and Chemical Biology.
20
Talk Number: 5 (Short Course)
Time: Monday, May 11, 2015 4:40 PM
Session: M2: Short Course (Auditorium)
FRICTION, WEAR AND SCRATCH RESISTANCE OF POLYMERS
Witold Brostow1,2 , Nathalie Hnatchuk1,2
1
Department of Materials Science and Engineering and Department of Physics, University of North Texas,
USA
2 International Council on Materials Education, University of North Texas, USA
Industry worldwide suffers huge losses every year because of a need to replace moving parts and elements
of structure as a consequence of wear. In this respect wear is similar to corrosion, but wear concerns all
moving parts while corrosion ‘attacks’ only some metals. The first step to mitigating wear is understanding
tribology = the science and engineering of interacting surfaces in relative motion.
Important experimental techniques of determination of tribological properties include: determination
of static and dynamic friction with a ‘universal’ mechanical testing machine; determination of scratch
resistance and sliding wear; pin-on-disk tribometry and profilometry for determination of dynamic friction
and wear and also of roughness.
Methods of mitigating wear used for metals cannot be used for polymers and polymer-based materials (PBMs). For metal parts one uses external lubricants; such lubricants are likely to be absorbed by
polymers, resulting in swelling and jamming of moving parts. However, methods of mitigating wear in
PBMs exist and will be discussed also.
Recommended reading: W. Brostow, V. Kovacevic, D. Vrsaljko & J. Whitworth, Tribology of polymers and polymer-based composites, J. Mater. Ed. 2010, 32, 273.
21
Tuesday, May 12, 2015 Starting: 8:20 AM
T0: Opening (Auditorium)
Session Chair: Mehrdad Negahban
Assistants: Wenlong Li, John J. Bowen
22
Tuesday, May 12, 2015 Starting: 8:45 AM
T1: Plenary (Auditorium)
Session Chair: Jinsong Huang
Assistants: Wenlong Li, John J. Bowen
Talk:
1. (8:45 AM, Plenary) Ade: SOFT X-RAY CHARACTERIZATION METHODS: UTILITY AND OPPORTUNITY
Dr. Harald Ade, Distinguished Professor of Physics, North Carolina State University
23
Talk Number: 1 (Plenary)
Time: Tuesday, May 12, 2015 8:45 AM
Session: T1: Plenary (Auditorium)
SOFT X-RAY CHARACTERIZATION METHODS: UTILITY AND OPPORTUNITY
Harald Ade1
1
Physics, North Carolina State University, U.S.A
Soft X-rays provide unique advantages to characterize systems with high spatial resolution, high compositional and bond-orientation sensitivity, with relatively little radiation damage. We will trace key development
steps in microscopy and scattering and exemplify the applications in a broad range of fields with a focus
on application to characterize bulk heterojunction (BHJ) organic photovoltaics (OPVs). In these devices
electron donating and electron accepting materials form a complex network of discrete and distributed
heterointerfaces and charge transport pathways in the photoactive layer where critical photo-physical
processes occur. However, we have insufficient knowledge about the structural properties of these interfaces
due to their 3-dimensional arrangement and the paucity of techniques to measure local order and purity.
Synchrotron radiation based soft x-ray methods can uniquely measure critical structural parameters, which
includes molecular orientation correlations relative to donor/acceptor heterojunctions [1]. Using polarized
resonant soft X-ray scattering [2], the degree of molecular orientation, an order parameter that describes
face-on (+1) or edge-on orientation (-1) relative to these discrete heterointerfaces, can be determined. By
manipulating the degree of molecular orientation through choice of molecular chemistry and processing
solvent characteristics, the importance of this structural parameter on the performance of BHJ OPV devices
and charge transfer dynamics can be demonstrated. We will furthermore show how compositional variations
can be related to polymer crystal size [3] and how mobility and purity can relate to charge extraction and
thus in turn to device performance [4,5]. A complete description of actual morphologies and theoretical
modeling yet to be developed for OPVs will have to take these factors into account. Devices with efficiencies
up to 10.8% will be discussed [6]. Complementary applications to milk, helical nanofibrillar liquid crystals,
block copolymers and membranes will also be exemplified. Future plans and opportunities to improve environmental sample control, extend the energy range, and ptychography at the few nm level [7] will be discussed
1.
2.
3.
4.
5.
6.
7.
J. R. Tumbleston et al., Nature Photonics 8, 386 (2014).
B. A. Collins et al., Nat. Mater. 11, 536 (2012).
W. Ma at al, Advanced Materials 26, 4234 (2014)
S. Albrecht et al. J. Physical Chemistry Letters 5, 1131-1138 (2014).
W. Liu et al., J. Am. Chem. Soc. 136, 15566-15576 (2014).
Y. Liu et al., Nature Communications 5, 5293 (2014)
D. Shapiro et al., Nature Photonics 8, 765-769 (2014)
24
Tuesday, May 12, 2015 Starting: 10:00 AM
T2_1: CMSP (Heritage Room)
Session Chair: Bernhard Blümich
Assistant: John J. Bowen
Talks:
1. (10:00 AM, Keynote) Guenet: CHARACTERIZATION AND PROPERTIES OF HYBRID MATERIALS FROM POLYMERS AND SELF-ASSEMBLED SYSTEMS
2. (10:40 AM, Oral) Dargent: RELAXATION PROCESSES AND COOPERATIVITY IN COPOLYMERS WITH A SIMILAR BACKBONE FLEXIBILITY
3. (11:00 AM, Oral) Pireaux: UNDERSTANDING (INDUCING, REPAIRING) ION BEAM DAMAGES
IN POLYMERS - A POLYCHAR CONCERN
4. (11:20 AM, Oral) Delpouve: COUPLING APPROACHES FOR THE INVESTIGATION OF THE
ALPHA RELAXATION DYNAMICS IN INTERACTING NETWORKS
5. (11:40 AM, Oral) Adhikari: MORPHOLOGICAL, THERMAL AND ELECTRICAL PROPERTIES
OF STYRENIC BLOCK COPOLYMER COMPOSITES WITH NANOCARBONS
25
Talk Number: 1 (Keynote)
Time: Tuesday, May 12, 2015 10:00 AM
Session: T2_1: CMSP (Heritage Room)
CHARACTERIZATION AND PROPERTIES OF HYBRID MATERIALS FROM
POLYMERS AND SELF-ASSEMBLED SYSTEMS
Jean-Michel Guenet1
1
CNRS, Institut Charles Sadron, France
In this talk three types of hybrid materials made up from covalent polymers and self-assembling systems
will be presented. In all cases the formation of these hybrid materials is achieved through physical processes
(heterogeneous nucleation, gelation, self-assembling).
Three cases will be reviewed and discussed: encapsulation of self-assembled filaments in polymer fibrils, intermingled gels, sheathed of polymer fibrils with self-assembling molecules. The polymers used are
isotactic polystyrene and syndiotactic polystyrene, and the self-assembling materials are bicopper-2-éthyle
hexanoatecomplex, OPV (oligo phenylene vinylene)and (3,5-Bis-(5-hexylcarbamoylpentyloxy)-benzoic acid
decyl ester) together with its decyl ester fluorinated counterpart.
Results on the formation thermodynamics as observed by DSC, the morphology as determined by
AFM, some properties (magnetic) by SQUID, and the molecular structure as obtained by SANS, SAXS
and EXAFS will be presented and discussed. All the experimental results show that a high degree of
compatibility exists between all the components thus allowing one to prepare materials where one component
is finely dispersed within the other. The potential applications of these three systems will also be discussed.
26
Talk Number: 2 (Oral)
Time: Tuesday, May 12, 2015 10:40 AM
Session: T2_1: CMSP (Heritage Room)
RELAXATION PROCESSES AND COOPERATIVITY IN COPOLYMERS WITH A
SIMILAR BACKBONE FLEXIBILITY
Jorge A. Soto-Puente1,2 , Bidur Rijal1 , Laurent Delbreilh1 , Kateryna Fatyeyeva2 , Allison Saiter1 ,
Eric Dargent1
1
2
AMME-LECAP EA 4528 International Laboratory, Normandie Université, France
Laboratoire PBS, Normandie Université, France
The glass transition in polymeric materials is characterized by a temperature dependence of the segmental
relaxation time close to Tg. The deviation of this dependence from an Arrhenius behavior could be quantified
with fragility [1].
Several approaches have been proposed to explain the correlation between the fragility and the cooperative molecular mobility near to Tg [2,3]. Then, the concept of cooperative rearranging region (CRR) was
introduced by Donth and defined as the smallest amorphous domain where conformational rearrangement
phenomena can occur without causing rearrangements in the surrounding [4].
The poly (vinyl acetate) (PVAc) and its random ethylene copolymers, so-called poly (ethylene-covinyl acetate) (EVA) with a content of vinyl acetate (VAc) higher than 40 wt.% are completely amorphous
materials [5]. As a consequence of the ethylene content increasing, the dipole-dipole interactions between
the polymer chains are expected to decrease. Generally, the published works correlate the fragility with
the chemical backbone stiffness [6]. The aim of this work is to correlate the fragility with the amplitude of
cooperative motions, by decreasing the dipole-dipole interactions (through the VAc content modification)
and without changing the flexibility of the main chemical backbone. For this goal MT-DSC and broadband
dielectric spectroscopy measurements have been performed.
27
Talk Number: 3 (Oral)
Time: Tuesday, May 12, 2015 11:00 AM
Session: T2_1: CMSP (Heritage Room)
UNDERSTANDING (INDUCING, REPAIRING) ION BEAM DAMAGES IN POLYMERS - A POLYCHAR CONCERN
Jean-Jacques Pireaux1 , Laurent Nittler1
1
Research Center in Physics of Matter and Radiation (PMR), University of Namur, Belgium
Different spectroscopies are available to characterize the elemental, chemical and molecular composition
of polymer materials in the bulk or micrometer range (IR, NMR...) and other ones to study surfaces and
interfaces in the nanometer range (XPS, ToF-SIMS...). For the latter subject, when it comes to analyze
and remove extreme surface contamination -as this may become extremely relevant for adhesion studies or
biocompatibilization properties-, one is generally using a soft ion beam or a plasma process to etch away the
contamination layer. In order to study thicker layers, Ar+ monoatomic ion beam etching appeared as the
best method to be used up to now , even if it is known that such monoatomic ion beams are inducing a lot
of chemical and structural damages in the studied layer.
In the last few years, Argon ion cluster beams (Arn+) have been proven a very efficient method to
etch away almost any kind of organic/polymer layer, practically without inducing any defect in the studied
layer. In the present work, we propose to study with X-Ray Photoelectron Spectroscopy (XPS) and SRIM
modelling the use of such Arn+ beams in order to: (a) clean the surface of a PMMA layer, (b) to study the
damages induced by a monoatomic Ar+ beam (depending on the beam energy), and
(c) remove those Ar+ -induced damages.
At the end, it will appear that Argon ion cluster beams (Arn+) are a good tool for healing a polymer surface of chemical and structural defects. We will show that, for a given cluster energy, there is a
quite natural linear relation between the monoatomic ion beam damaged volume, and the fluence of ion
clusters necessary to remove these damages. This suggests that the Arn+ erosion mechanism is in a first
approximation mechanically driven.
28
Talk Number: 4 (Oral)
Time: Tuesday, May 12, 2015 11:20 AM
Session: T2_1: CMSP (Heritage Room)
COUPLING APPROACHES FOR THE INVESTIGATION OF THE ALPHA RELAXATION DYNAMICS IN INTERACTING NETWORKS
Nicolas Delpouve1 , Steven Araujo1 , Wenlong Li2 , Florian Batteux1 , Li Tan2 , Mehrdad Negahban2 , Jean-Marc
Saiter1
1
AMME-LECAP EA 4528 International Lab., Normandie University, Université and INSA Rouen, France
AMME-A-TEAM, Department of Mechanical &Materials Engineering, University of Nebraska-Lincoln,
Lincoln NE, USA
2
To date a wide number of models and theories have been developed in attempt to describe the molecular
dynamics around the glass transition temperature and all assume that the molecular motions at the
alpha-relaxation process are cooperative. Adam and Gibbs [1] first proposed the concept of cooperative
rearranging region (CRR) defined as the smallest subsystem which, upon a sufficient thermal fluctuation,
can undergo a conformational rearrangement independently of its environment. One of the challenges
associated to the relaxation investigation is to calculate the CRR size by means of experimental techniques.
The approach of Donth [2] is a powerful empiric approach to investigate the CRR size since it relates
the cooperativity volume to the fluctuation of the glass transition temperature directly obtained from
calorimetric techniques. Many works refer to this approach to describe the molecular dynamics of the
amorphous phase in polymeric systems at the glass transition [3,4] and in the liquid like state [5]. It is
moreover assumed that the cooperativity calculated from the equation of Donth depicts the level of weak
interactions in a material [6,7]. For some systems however, especially those exhibiting a very broad glass
transition, the strict use of Donth’s equation can lead to dramatically low values for the cooperativity
length. Another issue lies in the arbitrary determination of “the relaxing unit” which is particularly complex
in crosslinked materials. In this work we propose to investigate a particular case combining these two
major drawbacks: the reciprocal influence between two networks in terms of molecular dynamics in an
interpenetrating system. We will present our current challenges and the opportunities offered from coupling
approaches.
(1) Adam, G.; Gibbs, J. H. J. Chem. Phys. 2004, 43, 139-146.
(2) Donth, E. J. Non-Cryst. Solids 1982, 53, 325-330.
(3) Furushima, Y.; Ishikiriyama, K.; Higashioji, T. Polymer 2013, 54, 4078-4084.
(4) Delpouve, N.; Delbreilh, L.; Stoclet, G.; Saiter, A.; Dargent, E. Macromolecules 2014, 47, 5186-5197.
(5) Saiter, A.; Delbreilh, L.; Couderc, H.; Arabeche, K.; Schönhals, A.; Saiter, J.-M. Phys. Rev. E 2010, 81,
041805.
(6) Nakanishi, M.; Nozaki, R. Phys. Rev. E 2011, 84.
(7) Paluch, M.; Pawlus, S.; Grzybowski, A.; Grzybowska, K.; Włodarczyk, P.; Zioło, J. Phys. Rev. E 2011,
84, 052501.
29
Talk Number: 5 (Oral)
Time: Tuesday, May 12, 2015 11:40 AM
Session: T2_1: CMSP (Heritage Room)
MORPHOLOGICAL, THERMAL AND ELECTRICAL PROPERTIES OF STYRENIC
BLOCK COPOLYMER COMPOSITES WITH NANOCARBONS
Rameshwar Adhikari1 , Surendra Kumar Gautam2 , Marco Liebscher3 , Sven Henning4 , Hai Hong Le3 , Ralf
Lach5 , Wolfgang Grellmann5 , Amit Das3 , Gert Heinrich3
1
2
3
4
5
Central Department of Chemistry, Tribhuvan University, Nepal
Department of Chemistry, Tri-Chandra Campus, Tribhuvan University, Kathmandu, Nepal
Leibnitz Institute of Polymer Research, Dresden, Germany
Fraunhofer Institute for Mechanics of Materials, Halle/Saale, Germany
Center of Engineering, Martin Luther University Halle-Wittenberg, Germany
Styrenic block copolymers having different molecular architectures were compounded with multiwalled
carbon nanotubes and nanodiamond with the objectives of preparing composites with desired electrical
and thermal conductivities. Melt mixing using microcompounder followed by compression molding allowed
the formation of nanocomopostes with well disperse nanofillers into the polymer matrix. The materials
were characterized with different microscopic, techniques, X-ray diffraction, microindentation hardness
measurement, and tensile testing, It was found that the matrix with co-continuous morphology is favors the
formation electrically conducting polymers. The composites showed significant improvement in mechanical
properties at low filler content. The observed properties of nanocomposites will be discussed in correlation
with block copolymer architecture, processing methods and observed morphology.
Keywords: block copolymer, polymer nanocompostes, electron microscopy, microhardness
30
Tuesday, May 12, 2015 Starting: 10:00 AM
T2_2: PEOD (Auditorium)
Session Chair: Jinsong Huang
Assistant: Wenlong Li
Talks:
1. (10:00 AM, Invited) Ouyang: PEDOT:PSS FOR PEROVSKITE SOLAR CELLS
2. (10:20 AM, Invited) Xiao: UNDERSTANDING THE EFFECT OF DEUTERATED CONDUCTING POLYMER AND SOLVENT ADDITIVE ON THE PERFORMANCE OF ORGANIC PHOTOVOLTAICS
3. (10:40 AM, Oral) Ulanski: OTFTS WITH ULTRATHIN LAYERS OF POLY(3-HEXYLTIOPHENE)
4. (11:00 AM, Oral) Xiao: UNIVERSAL FORMATION OF COMPOSITIONALLY GRADED BULK
HETEROJUNCTION FOR EFFICIENCY ENHANCEMENT IN ORGANIC PHOTOVOLTAICS
5. (11:20 AM, Oral) Jo: CONDUCTING POLYMER/GRAPHENE COMPOSITE FOR SUPERCAPACITOR
31
Talk Number: 1 (Invited)
Time: Tuesday, May 12, 2015 10:00 AM
Session: T2_2: PEOD (Auditorium)
PEDOT:PSS FOR PEROVSKITE SOLAR CELLS
Kuan Sun1 , Yijie Xia1 , Jianyong Ouyang1
1
Department of Materials Science & Engineering, National University of Singapore, Singapore
Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is the most successful conducting
polymer in terms of practical application. PEDOT:PSS can be dispersed in water and some polar organic
solvents. High-quality PEDOT:PSS films can be readily prepared by solution processing techniques, such as
coating and printing. PEDOT:PSS has high transparency in visible range and good thermal stability. Highly
conductive PEDOT:PSS can replace transparent conductive oxide as the transparent electrode of optoelectronic devices, while less conductive PEDOT:PSS can be used as the buffer layer. Here, I will present our
study on the application of highly conductive PEDOT:PSS as the transparent electrode of perovskite solar
cells and the effects of perovskite precursors and solvents on the properties of PEDOT:PSS.
32
Talk Number: 2 (Invited)
Time: Tuesday, May 12, 2015 10:20 AM
Session: T2_2: PEOD (Auditorium)
UNDERSTANDING THE EFFECT OF DEUTERATED CONDUCTING POLYMER
AND SOLVENT ADDITIVE ON THE PERFORMANCE OF ORGANIC PHOTOVOLTAICS
Kai Xiao1 , Ming Shao1 , Jong Keum1 , Kunlun Hong1 , Jim Browning2 , Jihua Chen1 , Wei Chen3 , Jacek
Jakowski1 , Bobby Sumpter1 , David Geohegan1
1
2
3
Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, USA
Neutron Scattering Science Divisions, Oak Ridge National Laboratory, USA
Material Sciences Division, Argonne National Laboratory, USA
The desired physical and optoelectronic properties of conjugated polymers strongly depend on the molecular
structure and film morphology. Therefore, understanding the structure-property-performance relationship
is crucial to the development of high performance organic electronic devices. Here, I will first report
a systematic study of the isotopic effects of deuterium substitution on the structure, morphology and
optoelectronic properties of regioregular poly(3-hexylthiophene)s (P3HT) with an integrated approach
that combines the synthesis of deuterated materials, optoelectronic properties measurements, theoretical
simulation and neutron scattering. Interestingly, selective substitution of deuterium on the backbone or side
chains of P3HT contributes differently to the photovoltaic characteristic. Secondly, adding solvent additive
has been demonstrated to be an effective method to optimize the bulk heterojunction morphology, and
improve the efficiency of OPV. However, the key information of the nano-structural evolution occurring in
the transformation from casting solution to thin photoactive film is still lacking. We investigate the effects of
the processing additive diiodooctane (DIO) on the morphology of high efficient PBDTTT-C-T:PCBM OPV,
starting in the casting solution and tracing the effects in the spun-cast thin films. Our results reveal that DIO
has no observable effect on the structure of polymer donor and aggregation of fullerene acceptors in solution,
however in the spun-cast films, it significantly promotes their molecular ordering and phase separation.
Moreover, thermodynamic analysis provides a rationale for the effects of DIO on different characteristics
of phase segregation. Such information will guide the design of ternary blends to improved efficiency for OPVs.
This research was conducted at the Center for Nanophase Materials Sciences and the Spallation Neutron Source, which are sponsored at Oak Ridge National Laboratory by the Division of Scientific User
Facilities, U.S. Department of Energy.
[1] M. Shao, J. Keum, J. Chen, Y. He, W. Chen, J. F. Browning, J. Jakowski, B. G. Sumpter, I. N.
Ivanov, Y. Ma, C. M. Rouleau, S. C. Smith, D. B. Geohegan, K. Hong, K. Xiao, Nature Comm. 5, 4180
(2014).
[2] M. Shao, J. K. Keum, R. Kumar, J. Chen, J. F. Browning, S. Das, W. Chen, J. Hou, C. Do, K. C.
Littrell, A. Rondinone, D. B. Geohegan, B. G. Sumpter, K. Xiao, Adv. Funct. Mater., 24, 6467 (2014)
33
Talk Number: 3 (Oral)
Time: Tuesday, May 12, 2015 10:40 AM
Session: T2_2: PEOD (Auditorium)
OTFTS WITH ULTRATHIN LAYERS OF POLY(3-HEXYLTIOPHENE)
Izabela Tszydel1 , Lukasz Janasz1 , Remigiusz Grykien1 , Beata Luszczynska1 , Tomasz Makowski2 ,
Jacek Ulanski1
1
Department of Molecular Physics, Technical University of Lodz, Poland
Department of Polymer Physics, Centre of Molecular and Macromolecular Studies of Polish Academy of
Sciences, Poland
2
Flexible Organic Large Area Electronics (FOLAE) is quickly emerging technology offering possibility of
mass production of cheap and flexible electronic devices by using different printing techniques. Solution
processable conjugated polymers are main class of organic semiconductors suitable for FOLAE applications
and Organic Thin Film Transistors (OTFTs) are basic building units of any electronic devices, therefore transistors based on conjugated polymers are subjects of intensive investigations since many years. It is known,
that in the OTFT the charge carrier transport occurs in few monolayers near the semiconductor/dielectric
interface, however there are only scares published data for OTFTs with ultra-thin semiconducting polymer
layers obtained by solution-based methods.
In our studies we have focused on determination of relationship between morphology of the very first
layers of the conjugated polymer and performance of the OTFT. As a model conjugated polymer we have
chosen the regioregular poly(3-hexyltiophene) (P3HT) with different molecular weights and with narrow
molecular weight distributions. Regioregular P3HT is well known p-type semi-crystalline polymer consisting
of a π-conjugated backbone with head-to-tail arrangement of the thiophene units bearing pendent alkyl
side groups. We have found that by changing the conditions of processing (type of solvent, concentration
of the solution, speed of spin-coating, post-treatment annealing) one can get ultrathin layers with different
morphology. These differences are reflected in different performances of the OTFTs, and in particular the
charge carrier mobility, as determined from the transistor characteristics, is very sensitive to morphology of
the few first monolayers of P3HT.
Acknowledgements: This work was supported by grant 2013/08/M/ST5/00914 of the Polish National
Science Centre and by grant Master9./2014 of the Foundation for Polish Science.
34
Talk Number: 4 (Oral)
Time: Tuesday, May 12, 2015 11:00 AM
Session: T2_2: PEOD (Auditorium)
UNIVERSAL FORMATION OF COMPOSITIONALLY GRADED BULK HETEROJUNCTION FOR EFFICIENCY ENHANCEMENT IN ORGANIC PHOTOVOLTAICS
Zhengguo Xiao1 , Jinsong Huang1
1
Mechanical and Materials Engineering, University of Nebraska-Lincoln, USA
All of the current efficient organic photovoltaic devices have a bulk heterojunction (BHJ) structure. Regular
BHJ films, formed from randomly mixed donors and acceptors in solution, inevitably have many breaks
and dead ends, and have uniform distribution of donors and acceptors along the vertical direction which
does not match the gradient electron and hole current across the films. The nonideal morphologies inevitably cause the charge recombination both in the BHJ films and at the metal/organic interface, in forms
of geminate recombination, or bimolecular recombination. Compositionally graded BHJ films, donor enriched at the anode and acceptor enriched at the cathode side, were proposed to facilitate the charge extraction and to reduce charge recombination in several highly efficient OPVs. However, the graded BHJs
with preferred composition profiles were only observed in a few high efficiency material systems which require special substrate surfaces and suitable surface energy differences between donors and acceptors for
its formation. Here we report a universal method to form the compositionally graded BHJ using a simple solvent-fluxing treatment of the wet BHJ films, in which the fluxing solvent brings the additives, as
well as fullerene-derivatives, toward the film surface. The graded BHJ significantly reduces bimolecular charge recombination. The fluxing process also resulted in more uniform nanodomain distribution in
the plane of the films and higher charge carrier mobilities. An efficiency enhancement of 15∼50%, with
highest efficiency of 8.6% for poly[4,8-bis-(2-ethyl-hexyl-thiophene-5-yl)-benzo[1,2-b:4,5-b’]dithiophene-2,6diyl]-alt-[2-(2’-ethyl-hexanoyl)-thieno[3,4-b]thiophen-4,6-diyl] (PBDTTT-C-T):C71-butyric acid methyl ester
(PC70BM) system, was achieved for all of the solution-processed BHJ systems studied compared to those
devices with regular BHJ films.
35
Talk Number: 5 (Oral)
Time: Tuesday, May 12, 2015 11:20 AM
Session: T2_2: PEOD (Auditorium)
CONDUCTING POLYMER/GRAPHENE COMPOSITE FOR SUPERCAPACITOR
Won Ho Jo1 , Kyung Tae Kim1 , Jin Woo Lee1
1
Dept of Materials Science and Engineering, Seoul National University, Korea
A water-soluble conducting polymer, poly(styrene sulfonic acid)-graft-polyaniline (PSSA-g-PANI), was synthesized and used to directly exfoliate graphite into graphene layers in aqueous media, because PANI in
PSSA-g-PANI is strongly physisorbed onto graphene surface via strong interaction while PSSA in PSSA-gPANI enhances water solubility. Hence, PSSA-g-PANI is expected to exfoliate directly graphite into graphene
layers and thus to disperse effectively the layers in aqueous media. As a consequence, PSSA-g-PANI/graphene
composite films are easily fabricated by a solution process and used for supercapacitor electrode. The capacitances of the composites depend upon the length and composition of PANI in PSSA-g-PANI. When the
capacitances of the composites with different PSSA-g-PANIs (different ratio of aniline (ANI) to styrene sulfonic acid (SSA) in polymer) were measured by cyclic voltammetry, the composite with the ratio of ANI/SSA
(50/50) in PSSA-g-PANI exhibits the highest specific capacitance of 480 F/g and 1449 F/g when the capacitance was measured by cyclic voltammetry at a scan rate of 50 mV/s and Galvano curves at a current
density of 1 A/g, respectively, which are among the highest values of EDLC type supercapacitor, and the
composite also shows superior cycle life with 90% retention of the initial specific capacitance after 1000 cycles
as compared to pseudo supercapacitor.
36
Tuesday, May 12, 2015 Starting: 12:50 PM
T3: Young Pleanary (Auditorium)
Session Chair: Lucia Fernandez-Ballester
Assistants: Ramin Hosseinabad, Mitchell Schmidt
Talk:
1. (12:50 PM, Young Plenary) Stein: GRAZING INCIDENCE SMALL-ANGLE X-RAY SCATTERING:
PRINCIPLES, MODELS, AND APPLICATIONS FOR NANOSTRUCTURED THIN FILMS
Dr. Gila Stein, Ernest J. and Barbara M. Henley Assistant Professor of Chemical and Biomolecular
Engineering, University of Houston
37
Talk Number: 1 (Young Plenary)
Time: Tuesday, May 12, 2015 12:50 PM
Session: T3: Young Pleanary (Auditorium)
GRAZING INCIDENCE SMALL-ANGLE X-RAY SCATTERING: PRINCIPLES,
MODELS, AND APPLICATIONS FOR NANOSTRUCTURED THIN FILMS
Gila Stein1
1
Chemical and Biomolecular Engineering, University of Houston, USA
Grazing incidence small-angle X-ray scattering (GISAXS) is an emerging method for quantitative characterization of nanostructured polymer films. This reflection-mode technique illuminates the sample with a shallow
incidence angle and records off-specular scattering with an area detector. Analyzing these data is non-trivial,
as models must include refraction corrections and account for multiple scattering events. In this talk, I will
provide an overview of the GISAXS experiment, and then discuss qualitative and quantitative approaches
for interpreting the data. I will present two case studies that illustrate how GISAXS measurements can
detect confinement-induced behavior in block copolymer thin films: First, I will show that GISAXS detects
complex symmetry transitions in thin films of spherical-domain block copolymers. These transitions (from
hexagonal to face-centered orthorhombic to body-centered cubic) are driven by packing frustration in the
confined geometry, and the equilibrium symmetry depends on the thickness of the film. Second, I will
discuss domain orientations in thin films of lamellar copolymers on “nearly-neutral” substrates. Through
detailed analysis of GISAXS data, we show that lamellae can bend near the bottom of the film. The extent
of these deformations is controlled by preferential interactions with the underlying substrate, as well as the
thickness of the film, and such defects have important implications for semiconductor manufacturing based
on block copolymer lithography.
About the speaker: Gila Stein earned her B.S. in Chemical Engineering at Drexel University (2002)
and completed a Ph.D. in Chemical Engineering at the University of California, Santa Barbara (2006). She
then moved to the National Institute of Standards and Technology, where she was a NRC postdoctoral fellow
in the Center for Nanoscale Science and Technology (2007-2008). Since 2009, she has been an Assistant
Professor in the Chemical and Biomolecular Engineering department at the University of Houston. Dr.
Stein’s research group studies the physics and chemistry of thin polymer films, emphasizing applications in
the microelectronics industry. She received a NSF CAREER award in 2012.
38
Tuesday, May 12, 2015 Starting: 1:40 PM
T4_1: CMSP (Heritage Room)
Session Chair: Christopher Cornelius
Assistant: Ramin Hosseinabad
Talks:
1. (1:40 PM, Invited) Blümich: NMR-SPECTROSCOPY AND NONDESTRUCTIVE TESTING BY
COMPACT NMR
2. (2:00 PM, Oral) Tashiro: STRUCTURE FORMATION PROCESS OF POLY(VINYL ALCOHOL)IODINE COMPLEX REVEALED BY IN-SITU TIME-DEPENDENT X-RAY DIFFRACTION MEASUREMENT
3. (2:20 PM, Oral) Salim: THERMAL DEGRADATION IN THE MELT REACTION BETWEEN
POLY(3-HYDROXYBUTYATE-CO-3-HYDROXYHEXANOATE) AND EPOXIDIZED NATURAL
RUBBER
39
Talk Number: 1 (Invited)
Time: Tuesday, May 12, 2015 1:40 PM
Session: T4_1: CMSP (Heritage Room)
NMR-SPECTROSCOPY AND NONDESTRUCTIVE TESTING BY COMPACT
NMR
Bernhard Blümich1 , Alina Adams1 , Ernesto Danieli1 , Tylor Meldrum2 , Dirk Oligschlaeger1 , Kawarpal
Singh1 , Wasif Zia1
1
2
Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Germany
Department of Chemistry, The College of William & Mary, USA
An introduction to compact NMR will be given with the focus on polymer analysis. Most NMR instruments
are bulky and expensive. This is not so for compact NMR instruments, which employ small permanent
magnets instead of large superconducting magnets. Despite their low field strength they are useful for
a variety of different investigations of macromolecules and macromolecular materials. For instance, highresolution 1H and 13C NMR spectra of polymer solutions can be acquired within a few minutes with a
compact desktop spectrometer directly in the chemical laboratory and even under the fume hood. The
sensitivity is good enough to monitor chemical reactions in real time and to distinguish raw rubber from
different plantations (NR), different manufacturing processes. With stray-field sensors like the NMR-MOUSE
extregistered only rubber products like tubes and tires could be characterized non-destructively in the past
in terms of depth profiles and local cross-link density. With the recent development of the MiniMOUSE, the
limiting instrument deadtime could be considerably reduced so that now not only the signal from amorphous
domains in semi-crystalline polymers can be detected but also the signal from crystalline domains. In
addition to thermal and physical aging, temperature and solvent induced crystallization have been studied.
Such investigations are closely related to studies of paint, paintings, and other objects of art and cultural
heritage relevant to conservation science.
40
Talk Number: 2 (Oral)
Time: Tuesday, May 12, 2015 2:00 PM
Session: T4_1: CMSP (Heritage Room)
STRUCTURE FORMATION PROCESS OF POLY(VINYL ALCOHOL)-IODINE
COMPLEX REVEALED BY IN-SITU TIME-DEPENDENT X-RAY DIFFRACTION
MEASUREMENT
Kohji Tashiro1 , Siti Munirah Saharin1
1
Department of Future Industry-oriented Basic Science and Materials, Toyota Technological Institute, Japan
Poly(vinyl alcohol) (PVA)-iodine complex is used for a optical polarizer for color display, sun glass etc. By
dipping PVA film into an iodine solution, the complex is formed not only in the amorphous region, as used
for polarizer but also in the crystal region. We have analyzed the crystal structures of complexes using
X-ray diffraction data, and investigated the factors governing the complex formation. In the present paper,
the structure changes in the formation process of the complexes have been investigated by performing the
in-situ time-resolved X-ray diffraction measurement using a doubly-oriented anisotropic PVA film. (1) In
the crystal structure of PVA itself, a couple of planar zigzag chains are linked together by intermolecular
hydrogen bonds. These PVA chains are linked also between the unit cells with strong hydrogen bonds.
(2) When the concentration of iodine solution is low (∼0.02M), the iodine ions invade into the amorphous
region and form the complex with PVA there.The iodine molecules exist as I5- ion. Most of the crystal
regions are still remained as the crystalline state of PVA itself. (3) The PVA sample is dipped into a KI/I2
aqueous solution of 0.05M∼1M concentration. As known from the Raman data, the I3- ions invade into the
crystalline region and form the complex with PVA chains. According to the X-ray sdiffraction analysis, the
structure consists basically of three layers: a layer of PVA chains connected by hydrogen bonds, and two
layers consisting of PVA-I3- complex. The occupancy of the iodine is about 0.3. The arrangement of these 3
layers indicates that the PVA-iodine complex is formed by shifting the PVA chains from the original position
and iodine molecules enter the spaces created by such a shift of PVA chains. However, the invasion of I3- ions
is not perfect but some of PVA chains still remain in the original structure. (4) By dipping the PVA sample
into more highly-concentrated iodine solution (∼3M), more perfectly-packed PVA-iodine complex is formed,
in which all the PVA chains form the complex with I3- at an occupancy of 0.7. The planar zigzag planes of
PVA chains are almost commonly parallel to the rolled plane in the two cases of PVA itself and the complex
of intermediate concentration. But, once the highly-concentrated PVA-I3- complex is formed, the a-axis is
oriented in parallel to the rolled plane and the molecules rotate by 38o around the chain axis.
41
Talk Number: 3 (Oral)
Time: Tuesday, May 12, 2015 2:20 PM
Session: T4_1: CMSP (Heritage Room)
THERMAL DEGRADATION IN THE MELT REACTION BETWEEN POLY(3HYDROXYBUTYATE-CO-3-HYDROXYHEXANOATE) AND EPOXIDIZED NATURAL RUBBER
Yoga Sugama Salim1,2,3 , Kumar Sudesh4 , Seng Neon Gan3 , Chin Han Chan2 , Jean-Marc Saiter1
1
AMME-LECAP, EA4528, International Laboratory, Institute des Materiaux de Rouen, Université et INSA
de Rouen, France
2 Polymer Blends Research Laboratory, Faculty of Applied Sciences, Universiti Teknologi MARA, 40450
Shah Alam, Malaysia
3 Department of Chemistry, Faculty of Applied Sciences, Universiti Malaya, 50603 Kuala Lumpur, Malaysia
4 Ecobiomaterial Research Laboratory, School of Biological Sciences, Universiti Sains Malaysia, 11800
Penang, Malaysia
Melt reaction between a member family of biodegradable copolyesters polyhydroxyalkanoate: poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(3HB-co-3HHx)] and epoxidized natural rubber (ENR) was investigated.
P(3HB-co-3HHx) is known to exhibit random chain scission at temperature above its melting point. This
random cleavage of P(3HB-co-3HHx) can be selectively grafted with natural rubber bearing a cyclic ether
group. The temperature of investigated melt reaction was conducted at 195 o C. During the melt reaction,
there is a time-dependence of mass loss as shown in thermogravimetric analysis. The plot of mass loss (in
percent, %) against weight fraction of ENR (wENR) exhibits an asymmetric bell curve. Highest mass loss at
5 × t0.5,rb (t0.5,rb = half-time of isothermal reactive blends) was observed in the blends containing wENR
= 30 wt% and wENR = 50 wt%, which was (14.1 ± 0.6)% and (13.0 ± 0.8)% respectively. The asymmetric
curve could be attributed to: (1) a heterogeneous reaction at the interface between P(3HB-co-3HHx) and
ENR. This means that in P(3HB-co-3HHx)-rich phase, there is a coexistence of dispersed ENR particles
with different size distribution and vice versa; and (2) further decomposition of P(3HB-co-3HHx) at prolong
reaction time. However at wENR = 40 wt%, there is a percolation pathway in which it forms a continuous
phase in both P(3HB-co-3HHx) and ENR (supported by SEM images). The mass loss for this particular
blend composition at 5 × t0.5,rb was (9.5 ± 0.1)%. FTIR investigation confirms the molecular interactions
during the course of melt reaction between P(3HB-co-3HHx) and ENR.
42
Tuesday, May 12, 2015 Starting: 1:40 PM
T4_2: DEMO (Auditorium)
Session Chair: Stephen Ducharme
Assistant: Mitchell Schmidt
Talks:
1. (1:40 PM, Invited) Xu: ENHANCED SENSITIVITY OF PRESSURE SENSOR USING ELECTROACTIVE POLYMERS
2. (2:00 PM, Oral) Poddar: FLEXOELECTRIC EFFECT IN FERROELECTRIC AND RELAXOR
POLYMERS OF VDF
3. (2:20 PM, Oral) Chan: RESPONSE OF SOLID POLYMER ELECTROLYTES TO ELECTRIC
FIELDS
43
Talk Number: 1 (Invited)
Time: Tuesday, May 12, 2015 1:40 PM
Session: T4_2: DEMO (Auditorium)
ENHANCED SENSITIVITY OF PRESSURE SENSOR USING ELECTROACTIVE
POLYMERS
Chunye Xu1
1
Department of Polymer Science and Engineering, School of Chemistry and Materials; Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, China
Electroactive polymers (EAPs) are smart materials that exhibit controllable response to external stimulus,
promising in application for actuators, sensors and electrochromic devices. We developed a highly sensitive
flexible pressure sensor based on piezopolymer and silver nanowire (Ag NWs) composite. The composite
nanofiber webs are made by electrospinning mixed solutions of poly(vinylidene fluoride) (PVDF) and Ag
NWs in the cosolvent of dimethyl formamide and acetone. FTIR and XRD results reveal that doping Ag
NWs into PVDF largely enhances the content of β phase in PVDF. The increase of β phase can be attributed
to interactions between Ag NWs and the PVDF matrix, which force the polymer chains to be embedded into
the β phase crystalline. The sensitivity of the pressure sensors agrees well with FTIR and XRD characteristics.
This study may provide a new method of fabricating high performance flexible sensors at relatively low cost
compared with sensors based on [P(VDF-TrFE), (77/23)].
44
Talk Number: 2 (Oral)
Time: Tuesday, May 12, 2015 2:00 PM
Session: T4_2: DEMO (Auditorium)
FLEXOELECTRIC EFFECT IN FERROELECTRIC AND RELAXOR POLYMERS
OF VDF
Shashi Poddar1 , Stephen Ducharme1
1
Physics and Astronomy, University of Nebraska Lincoln, United States of America
The flexoelectric effect yields a change in electrical polarization proportional to an inhomogeneous strain
gradient, and as such, is a more general phenomenon than the linear change in polarization due to stress,
the piezoelectric effect, which requires a non-centrosymmetric crystal structure. The inhomogeneous strain
gradient becomes appreciable at the nanoscale and behaves as an applied electric field, capable of poling,
switching, and rotation of polarization. The flexoelectric response is of practical interest, because it lifts
the symmetry restrictions that limit piezoelectric response, and therefore can be found in crystalline and
amorphous materials alike, allowing much greater flexibility in material and device design. The theoretical
background laid down by Kogan and Tagantsev supposes the flexoelectric coefficient µ to be to be of order
ke/a (∼ 0.1 nC/m), where k is the dielectric constant and a is the lattice constant of the material. The
predicted scalability of the flexoelectric response with dielectric constant indicates that the flexoelectric effect
should also exhibit a strong enhancement near the Curie transition temperature for normal ferroelectric
and near the dielectric relaxation temperature regimes. In our studies we investigated the flexoelectric
response in ferroelectric and relaxor polymers of vinylidene fluoride. By using a simple cantilever measurement
technique, while monitoring remanent polarization through the pyroelectric response, we are able to measure
the flexoelectric response in thin films as well as isolate and correct for piezoelectric contributions, which
would otherwise dominate the flexoelectric measurement. We also investigated the temperature dependence
of the flexoelectric response in thin films of these materials. The ferroelectric samples were depoled to
minimize piezoelectric response by heating them beyond their Curie temperature and then cooling in zero
applied electric field. In both the relaxor ferroelectric polymer and the paraelectric state of the ferroelectric
copolymer, the flexoelectric coefficient was proportional to the dielectric constant over a limited range of
temperatures. The enhancements in flexoelectric response were also observed near the phase transition
temperatures of both the forms. These organic polymer materials have a broader dielectric anomaly than
the ceramic perovskites and thus, provides greater temperature stability for these enhancements.
45
Talk Number: 3 (Oral)
Time: Tuesday, May 12, 2015 2:20 PM
Session: T4_2: DEMO (Auditorium)
RESPONSE OF SOLID POLYMER ELECTROLYTES TO ELECTRIC FIELDS
Chinhan Chan1 , Hans-Werner Kammer2 , Laihar Sim3 , Tan Winie1
1
2
3
Faculty of Applied Sciences, Universiti Teknologi MARA, Malaysia
Department of Chemistry and Physics, Martin-Luther University Halle-Wittenberg, Germany
Pusat Asasi, Universiti Teknologi MARA, Malaysia
The overview discusses in phenomenological way dielectric relaxation as a function of salt content in polymer
electrolytes with poly(ethylene oxide) (PEO) and epoxidized natural rubber (ENR). Impedance is seen as
key quantity which images relaxation properties of those systems. It follows Debye relaxation at low salt
concentration. With increasing salt content one observes dispersion of relaxation time. The spectrum of
imaginary part of impedance displays two extreme values: maximum and minimum. Accordingly, one has to
distinguish between low- and high-frequency branches. The maximum reflects chain relaxation. It shifts with
increasing salt content to higher frequencies, which is consistent with increase in glass transition temperature
(Tg) under the same conditions. The minimum characterizes electrode polarization or formation of double
layer at the electrode/electrolyte interface. The frequency where the minimum occurs might be seen as
diffusion frequency. It governs transport of charge carriers in the limit of low frequencies. Consequently,
diffusion coefficient (Dion) changes as frequency omega (min) in dependence on salt content. Impedance
spectrum of PEO displays two extreme values whereas the minimum in spectra of ENRs shifts to very low
frequencies and is not experimentally accessible. As a consequence, relaxations in PEO can be discussed in
the DC range whereas those in ENRs are only approachable in the high-frequency region where frequency
omega >> omega (max). In any branch, the concentration of electrically active charge carriers is quite low
and changes only weakly with added salt content; the diffusion coefficient on the other hand, is high and
increases with salt content.
46
Tuesday, May 12, 2015 Starting: 3:05 PM
T5_1: CMSP (Heritage Room)
Session Chair: Yong-Rak Kim
Assistant: Ramin Hosseinabad
Talks:
1. (3:05 PM, Oral) Sun: INVESTIGATING ORGANIC MATERIALS USING SPECTROSCOPIC ELLIPSOMETRY
2. (3:25 PM, Oral) Manhart: DESIGN OF ELASTOMER SURFACES WITH SPATIALLY CONTROLLED TRIBOLOGICAL PROPERTIES APPLYING PHOTOLITHOGRAPHIC TECHNIQUES
3. (3:45 PM, Oral) Desai: ROLE OF EXTERNAL DONOR AND CO-CATALYST - ZIEGLER NATTA
CATALYST USING SPECTROSCOPY TECHNIQUE
4. (4:05 PM, Oral) Schamme: ROLE OF MOLECULAR MOBILITY AND FRAGILITY ON PHYSICAL STABILITY OF TWO AMORPHOUS PHARMACEUTICALS IN THE SUPERCOOLED AND
GLASSY STATES
5. (4:25 PM, Oral) Viel: MOLECULAR MOBILITY VS POLYMORPHISM OF CHIRAL PHARMACEUTICAL COMPOUNDS: CASE OF DIPROPHYLLINE
6. (4:45 PM, Oral) Denchev: STRUCTURE GRADIENTS BY MICROFOCUS SYNCHROTRON XRAY DIFFRACTION IN SHELL-CORE POLYAMIDE MICROCAPSULES AND MOLDED COMPOSITES THEREOF
7. (5:05 PM, Oral) You: CHARACTERIZATION OF VISCOELASTIC-VISCOPLASTIC BEHAVIOR
OF POLYMERIC MATERIALS CONTAINING ALIPHATIC AND AROMATIC HYDROCARBONS
DERIVATIVES
47
Talk Number: 1 (Oral)
Time: Tuesday, May 12, 2015 3:05 PM
Session: T5_1: CMSP (Heritage Room)
INVESTIGATING ORGANIC MATERIALS USING SPECTROSCOPIC ELLIPSOMETRY
Jianing Sun1 , Greg Pribil1 , James Hilfiker1 , John Woollam1
1
Applications, J. A. Woollam Co., Inc, USA
Spectroscopic Elipsometry (SE) provides accurate film thickness (from sub-nanometers to microns), refractive indices as well as structural conformation and anisotropy. The technique has been routinely used in
getting thickness of organic films in single layer or multiple-layer stack. SE determines the optical behaviors
of thin films in organic light emitting diodes (OLED) and organic photovoltaic (OPV). Such films present
anisotropy resulting from their conjugated molecular structure and conformation. The sensitivity to sub-nm
film makes it an idea technique to monitor thin film absorption and desorption in bio- or surface chemistry
applications. Thermal behaviors of thin organic films are important for their mechanical, electrical or
biological applications. SE provides fast and non-destructive way to dynamically monitor their temperature
dependent behaviors. Applications in understanding temperature effects on glass transition and anisotropy
will be demonstrated. Thermal responses of ultra-thin (below 20nm) free-standing films will for the first
time be discussed.
Key Words: Spectroscopic ellipsometry, Refractive index, thickness, anisotropy, glass transition temperature
48
Talk Number: 2 (Oral)
Time: Tuesday, May 12, 2015 3:25 PM
Session: T5_1: CMSP (Heritage Room)
DESIGN OF ELASTOMER SURFACES WITH SPATIALLY CONTROLLED TRIBOLOGICAL PROPERTIES APPLYING PHOTOLITHOGRAPHIC TECHNIQUES
Jakob Manhart1 , Andreas Hausberger1 , Inge Mühlbacher1 , Raimund Schaller2 , Armin Holzner2 , Wolfgang
Kern1,3 , Sandra Schlögl1
1
2
3
Polymer Competence Center Leoben , GmbH, Austria
Semperit Technische Produkte GmbH, GmbH, Austria
Chair of Chemistry of Polymeric Materials, University of Leoben, Austria
Tribological properties of elastomer-based materials have gained increased attention in numerous fields of
application, ranging from the automotive industry to the health-care sector. In recent years, various routes
have been pursued towards the development of elastomer materials with improved tribological characteristics. The present contribution highlights a new approach for the preparation of functionalized and patterned
natural rubber (NR) elements with tailored friction properties.
By using versatile UV-induced thiol-ene chemistry, a two-step surface modification strategy has been developed which enables controlled and patterned immobilization of micro-scaled inorganic particles onto diene-rubber surfaces, causing a tremendous change of chemical and physical surface properties. The chemical
composition of the modified surfaces was characterized by XPS, FTIR, zeta potential and water contact angle
measurements. Physical transformation was monitored by means of optical, scanning electron and confocal
microscopy in order to gauge surface topology and roughness whilst tribological studies were performed to
characterize the friction properties in two dimensions.
The results reveal that the attachment of selected micro-scaled particles provides a distinctive increase in
surface roughness and a considerable decrease in the coefficient of friction. Both can be conveniently adjusted
through the amount of particles immobilized onto the elastomer surface. The application of photolithographic
techniques further promotes elastomer materials with precisely and spatially controlled tribological properties. Whilst elastomer surfaces with randomly attached particles exhibit isotropic coefficients of friction,
anisotropic friction properties can be accomplished by surface patterning. It is clearly evidenced that this
photochemical modification route enables the well-defined production of surface textures and thus allows the
design of elastomer surfaces with tailored friction properties.
49
Talk Number: 3 (Oral)
Time: Tuesday, May 12, 2015 3:45 PM
Session: T5_1: CMSP (Heritage Room)
ROLE OF EXTERNAL DONOR AND CO-CATALYST - ZIEGLER NATTA CATALYST USING SPECTROSCOPY TECHNIQUE
Bhavesh Kiritbhai Desai1
1
Reliance Research & Development center, Reliance Industries Ltd, Hazira, India
The roles of internal and external electron donors have been often discussed in abundant studies on MgCl2
supported TiCl4 catalysts for propylene polymerization. Since Z-N catalyst and its polymerization is highly
complex system and it is quite difficult to identify experimentally active species of polymerization in a
heterogeneous MgCl2 support. The interaction of the electron donors with a central titanium atom of
the active species is not well-understood. Due to heterogeneous nature of catalyst and also very complex
polymerization and catalyst reaction mechanism some advanced tool required to understand role of electron
donors (Lewis Base), supports, co-catalyst (Aluminum Alkyl) and also TiCl4 (Lewis Acid). In propylene
polymerization the interactions are very much important and are need to be understood for understanding
the polymerization mechanism in details.
External donor (p-isopropoxy methyl benzoate; PIPMB) & co catalyst (Triethylaluminium-TEAl)
were interacted in 1:3 molar ratio. The resultant complexes formed by the interaction of ED and co catalyst
were studied by spectroscopy at room temperature. 1H, 13C 1H & DEPT45, 90 & 135 NMR spectra of
were recorded. The resultant complexes were also studied at 70o C to mimic the polymerization conditions
at slurry phase process. The strength of coordination bond (degree of coordination) was co related by
measuring the chemical shift of carbonyl functionality through NMR spectra.
50
Talk Number: 4 (Oral)
Time: Tuesday, May 12, 2015 4:05 PM
Session: T5_1: CMSP (Heritage Room)
ROLE OF MOLECULAR MOBILITY AND FRAGILITY ON PHYSICAL STABILITY OF TWO AMORPHOUS PHARMACEUTICALS IN THE SUPERCOOLED AND
GLASSY STATES
Benjamin Schamme1,2 , Laurent Delbreilh1 , Valérie Dupray2 , Eric Dargent1 , Gérard Coquerel2
1
2
Advanced Materials and Mechanical Engineering, AMME-LECAP International Laboratory, France
Crystal Genesis Unit, SMS Laboratory, France
In the pharmaceutical industry, crystalline active pharmaceutical ingredients (API) and/or excipients have
been, so far, preferred for the formulation of drugs because of stability concerns [1]. However, a number of
pharmaceutical ingredients are prompt to get amorphized and it has been demonstrated that amorphous
API can result in significant improvements of the dissolution rate and bioavailability with reference to the
crystallized solid. However, preparation methods as well as thermal and mechanical treatments employed
during formulation of the drug have been shown to affect physical stability of the amorphous API [2].
Beside the inherent out of equilibrium state of amorphous material, the molecular mechanisms governing the kinetic stability of amorphous API remain unclear (as a large number of experimental factors
may impact the process of crystallization) but need to be clarified in order to design reliable formulation
processes [3]. Recent works have highlighted that molecular mobility could be a key factor to account for the
physical stability of amorphous substances. In particular the impact of glass fragility on physical stability
of amorphous systems has been considered [4].
In view to contribute to this challenging inquiry, we characterized the amorphous state of two APIs:
Biclotymol and Quinidine. Biclotymol possesses antiseptic properties and is used for the treatment of
otolaryngology infections while Quinidine acts as an antiarrhythmic agent. Based on Broadband Dielectric
Spectroscopy measurements conducted on these two compounds, this study shows that fragility could be
a valuable parameter for understanding the mechanisms relating crystallization from amorphous state and
stability (life expectancy) of amorphous materials. Dynamics of primary and secondary relaxations processes
for the two compounds have been carefully investigated in a wide range of temperatures and frequencies.
Moreover, in situ crystallization mechanisms were explored through isothermal and non-isothermal cold
crystallization, within the framework of uncontrolled recrystallization processes from amorphous systems.
[1] Singhal, D; Curatolo, W. Adv. Drug Deliv. Rev. 2004, 56, 335-347.
[2] Patterson, J; James, M; Forster, A; Lancaster, R; Butler, J; Rades, T. J. Pharm. Sci. 2005, 94,
1998-2012.
[3] Morris, K; Griesser, U; Eckhardt, C; Stowell, J. Adv. Drug Deliv. Rev. 2001, 48, 91-114.
[4] Gupta, P; Chawla, G; Bansal, A. Mol. Pharmaceutics. 2004, 1, 406-413.
51
Talk Number: 5 (Oral)
Time: Tuesday, May 12, 2015 4:25 PM
Session: T5_1: CMSP (Heritage Room)
MOLECULAR MOBILITY VS POLYMORPHISM OF CHIRAL PHARMACEUTICAL COMPOUNDS: CASE OF DIPROPHYLLINE
Quentin Viel1,2 , Clement Brandel2 , Yohann Cartigny2 , Gerard Coquerel2 , Eric Dargent1 , Samuel Petit2
1
2
LECAP, University of Rouen, France
Crystal Genesis SMS, University of Rouen, France
Compared to the crystalline state, the amorphous state is an attractive solution for the pharmaceutical
industry since the capacity of the molecule to be dissolved in liquids (not to be confused with “solubility”)
is increased. Thus, a higher bioavailability of a targeted Active Pharmaceutical Ingredient (API) [1] can
be reached by amorphization of a crude product. However, physical instabilities related to the amorphous
state represent a significant limitation to the development of an amorphous drug product and for its
subsequent formulation. Consequently, the scientific and industrial communities try to understand the
factors affecting the crystallization route from the amorphous state [2]. There is a particular scientific
interest in understanding the role of molecular mobility in glass-forming materials during the process of
crystallization [3]. The chiral drug Diprophylline (DPL) is used as a racemic solid (a 50/50 mixture of both
enantiomers) in oral dosage forms for treatment of pulmonary diseases. The molecule itself consists of a rigid
heterocyclic group theophylline attached to a flexible propanediol moiety. Although the stable state of DPL
enantiomeric mixtures consists of an usual equilibrium between a racemic compound (RI) and an enantiopure
form (EI), we have found that annealing DPL glasses with various enantiomeric compositions (Xs) above the
DPL glass transition (Tg = 37 o C) can induce the crystallization of two distinct metastable solid solutions
labelled ssRII and ssEII. The aim of the present study is to elucidate the impact of enantiomeric composition
in supercooled melts on the outcomes of DPL recrystallization from the amorphous state. Calorimetric
measurements (DSC) and Broadband Dielectric Spectroscopy (BDS) analyzes have been used to characterize
the path/route of the molecules from the amorphous state (molecular mobility) until recrystallization at
distinct enantiomeric compositions.
[1] Baird A.J., Taylor L., Ad Drug Rev, 64, 396-421, 2012
[2] Bhugra C., Shmeis R., Pikal M., Journal of Pharmaceutical Sciences, 97, 10, 2008
[3] Rodrigues A.C., Viviosa M.T., Affouard F, Correia T., Molecular Pharmaceutics, 11, 112-130, 2014
52
Talk Number: 6 (Oral)
Time: Tuesday, May 12, 2015 4:45 PM
Session: T5_1: CMSP (Heritage Room)
STRUCTURE GRADIENTS BY MICROFOCUS SYNCHROTRON X-RAY
DIFFRACTION IN SHELL-CORE POLYAMIDE MICROCAPSULES AND MOLDED
COMPOSITES THEREOF
Zlatan Zlatev Denchev1 , Nadya Vassileva Dencheva1 , Stephan V. Roth2
1
2
Polymer Engineering, I3N - Institute for Polymers and Composites, Portugal
Photon Science at DESY, DESY, Germany
Polyamide microcapsules are of demand in many industries e.g., compression-and rotational molding, selective
laser sintering, cosmetics etc. In bioengineering, polyamide-microcapsules can be attractive carriers for
protein or enzyme immobilization. The distribution of the solid filler in microcapsules is a function of the
manufacturing conditions and is often of decisive importance for certain applications. Such measurements
are not possible by means of conventional X-ray techniques or electron microscopy due to the large size of
the X-ray beam or sample preparation difficulties, respectively. This work reports on the measurements of
the structure and composition gradients in novel microcapsules with polyamide 6 (PA6) porous shells and
diameters in the 25-50 angstrom range obtained by emulsion anionic polymerization. The microcapsules
were loaded in situ with various amounts and types of inorganic, finely dispersed materials: nanoclays,
carbon allotropes, and metal particles. Thin layers of the respective microcapsule samples were scanned
along two perpendicular axes with a 5x5 angstrom synchrotron beam in WAXS mode covering areas of
3025 angstrom2. The microfocos WAXS results obtained showed irregular distribution of the filler within
the PA6 microcapsules causing changes in the content of Î±- and ÎPA6 polymorphs in 121 shell sections of
25 angstrom2 each. Similar measurements were performed with composite plates obtained by compression
molding of certain amounts of the respective microcapsules. These unique WAXS studies helped characterize
the core nanostructure of the loaded PA6 microcapsules and how it transits into the molded part. In such a
way a direct relation was made between the reaction parameters of the microcapsule-forming polymerization
process and the nanostructure of the molded samples.
53
Talk Number: 7 (Oral)
Time: Tuesday, May 12, 2015 5:05 PM
Session: T5_1: CMSP (Heritage Room)
CHARACTERIZATION OF VISCOELASTIC-VISCOPLASTIC BEHAVIOR OF
POLYMERIC MATERIALS CONTAINING ALIPHATIC AND AROMATIC HYDROCARBONS DERIVATIVES
Taesun You1 , Soohyok Im2 , Yong-Rak Kim1
1
2
Civil Engineering, University of Nebraska-Lincoln, USA
Civil Engineering, Texas A&M Transportation Institute, USA
Bitumen is a black or dark polymer, being composed of high molecular weight hydrocarbons and nonmetallic
derivatives. Fine aggregate matrix (FAM) consisting of bitumen, air voids, fine aggregates, and fillers plays
a significant role in evaluating the damage and deformation of entire bituminous mixtures. The simplicity,
repeatability, and efficiency of the FAM testing make it a very attractive specification-type approach for evaluating the performance characteristics of the entire bituminous mixtures. This study explores a linkage in the
deformation characteristics between the two length scales: bituminous mixture scale and its corresponding
FAM scale. To that end, a simple creep-recovery test was conducted for both mixtures (i.e., bituminous mixture and its corresponding FAM phase) at various stress levels. Test results were compared and analyzed using
Schapery’s single integral viscoelastic theory and Perzyna-type viscoplasticity with a generalized DruckerPrager yield surface. In particular, stress-dependent nonlinear viscoelastic and viscoplastic behaviors were
characterized in addition to linear viscoelastic deformation characteristics, because the nonlinear viscoelastic
and viscoplastic behaviors are considered significant in bituminous pavements that are subjected to heavy
vehicle loads and elevated service temperatures. With a limited scope and test-analysis results at this stage,
it was found that there is a strong link between the FAM and bituminous mixture in (linear and nonlinear)
viscoelastic and viscoplastic deformation characteristics. This implies that the viscoelastic stiffness characteristics and viscoplastic hardening of typical bituminous mixtures could be estimated or predicted from the
simple FAM-based testing-analysis method, which can significantly reduce the experimental-analytical efforts
required for bituminous mixtures.
54
Tuesday, May 12, 2015 Starting: 3:05 PM
T5_2: DEMO (Auditorium)
Session Chair: Chinhan Chan
Assistant: Mitchell Schmidt
Talks:
1. (3:05 PM, Invited) Jonas: NANOIMPRINTED FERROELECTRIC/SEMICONDUCTING POLYMER DEVICES
2. (3:25 PM, Oral) Sangoro: CHARGE TRANSPORT AND STRUCTURAL DYNAMICS IN POLYMERIZED IONIC LIQUIDS
3. (3:45 PM, Oral) Dencheva: FROM LOADED SHELL-CORE MICROCAPSULES TO THERMOPLASTIC HYBRID COMPOSITES: A NEW PATHWAY FOR THE PREPARATION OF CONDUCTIVE AND MAGNETIC POLYAMIDE COMPOSITES
4. (4:05 PM, Oral) Anada: DIVERSITY OF MICROSTRUCTURE OF POLYMER SOLID INVESTIGATED BY MOTION OF IMPURITY IONS
5. (4:25 PM, Oral) Hagg Lobland: THERMOELECTRIC GENERATORS (TEGS) WITH LONG SERVICE LIVES
55
Talk Number: 1 (Invited)
Time: Tuesday, May 12, 2015 3:05 PM
NANOIMPRINTED
VICES
Session: T5_2: DEMO (Auditorium)
FERROELECTRIC/SEMICONDUCTING
POLYMER
DE-
Ronggang Cai1 , Tilia Patois1 , Laurianne Nougaret1 , Alain M. Jonas1
1
Bio & Soft Matter, University of Louvain, Belgium
For the fabrication of efficient organic devices, it is desirable to develop methodologies able to shape
functional polymers into nanostructures, while simultaneously controlling essential attributes such as crystal
orientation and size. In this context, nanoimprint lithography (NIL), initially developed as a nanolithography
technique applied to amorphous polymers, proved to be well-suited to shape and control the structure of a
range of liquid crystalline and semicrystalline polymers [1-3], such as semiconducting [4], electroluminescent,
or ferroelectric polymers [5-7]. The reasons for this control stem from perturbed nucleation, confinement
during crystallization, and grapho-epitaxy.
As a side benefit of this process, the polymer is also shaped in an array of nanoobjects separated by
regularly spaced cavities. This provides a unique opportunity to fabricate hybrid multifunctional layers, by
filling the so-created cavities by another material synergetically interacting with the first one. By using a
semiconducting polymer as second component, we fabricated a series of memory devices, such as ferroelectric/semiconducting diodes [8], ferroelectric field effect transistors with a nanoimprinted top ferroelectric
layer [9], or a new type of ferroelectric transistor including a mixed semiconducting/ferroelectric active layer;
we also realized organic solar cells containing nanoimprinted ferroelectric layers. In this communication, we
present the specificities of the coupling between the ferroelectric polymer and the semiconducting polymer
in the nanostructured bifunctional layers, and show how this may be used to develop new device architectures.
References
[1] Nano Letters 2005, 5, 1738-1743;
[2] Soft Matter 2010, 6, 21-28;
[3] Handbook of Nanophysics. Nanoelectronics and Nanophotonics, Sattler, K. D., Ed. CRC: Boca Raton,
2011; Vol. 6, pp 18.1-18.8;
[4] Nano Letters 2007, 7, 3639-3644;
[5] Nature Materials 2009, 8, 62-67;
[6] Macromolecules 2013, 46, 8569-8579;
[7] Macromolecules 2014, 47, 4711-4717;
[8] ACS Nano 2014, 8, 3498-3505;
[9] Appl. Phys. Lett. 2014, 105, 113113.
56
Talk Number: 2 (Oral)
Time: Tuesday, May 12, 2015 3:25 PM
Session: T5_2: DEMO (Auditorium)
CHARGE TRANSPORT AND STRUCTURAL DYNAMICS IN POLYMERIZED
IONIC LIQUIDS
Joshua Sangoro1
1
Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, USA
Polymerized ionic liquids (PolyILs) are a novel class of functional polymers that combine the unique physicochemical properties of molecular ionic liquids with the outstanding mechanical characteristics of polymers
[1-2]. This special mix of features might help to circumvent the key limitations of low molecular weight ionic
liquids, namely, leakage and poor mechanical properties while utilizing their outstanding characteristics
such as low vapor pressures, wide liquidus ranges, high thermal stability, high ionic conductivity, and wide
electrochemical windows. PolyILs have shown remarkable advantages when employed in electrochemical
devices such as dye-sensitized solar cells, lithium batteries, actuators, field-effect transistors, light emitting
electrochemical cells, and electrochromic devices, among others. Despite their promising prospects as
ideal polymer electrolytes, the role of molecular structure, morphology, and polymer dynamics on charge
transport in PolyILs remains poorly understood.
According to classical theories, the self-diffusion and ion transport in electrolytes are controlled by structural
relaxation. These approaches predict similar temperature dependence for the dc conductivity and structural
dynamics. Although this prediction has been shown to hold reasonably well for low molecular weight aprotic
ionic liquids [3], it fails for PolyILs [2]. In addition, the impact of morphology charge transport is not
considered within the framework of these theories.
In this talk, new insights obtained from both experimental studies employing broadband dielectric spectroscopy, temperature-modulated differential scanning calorimetry, and scattering techniques along with
multiscale modeling investigations to elucidate charge transport and structural dynamics in a systematic
series of polymerized ammonium- and imidazolium- based ionic liquids will be presented. Detailed analyses
reveal strong decoupling of these processes in the PolyILs, implying failure of the classical theories in
describing charge transport and molecular dynamics in these materials. In addition, the strong correlation
observed between ionic conductivity from dielectric experiments and morphologies from scattering studies
will be discussed.
References
[1] Mecerreyes, D. Progress in Polymer Science 2011, 36, 1629.
[2] Sangoro, J. R. et al., Soft Matter 2014, 10, 3536.
[3] Sangoro, J. R.; Kremer, F. Accounts of Chemical Research 2012, 45, 525.
57
Talk Number: 3 (Oral)
Time: Tuesday, May 12, 2015 3:45 PM
Session: T5_2: DEMO (Auditorium)
FROM LOADED SHELL-CORE MICROCAPSULES TO THERMOPLASTIC HYBRID COMPOSITES: A NEW PATHWAY FOR THE PREPARATION OF CONDUCTIVE AND MAGNETIC POLYAMIDE COMPOSITES
Nadya Vassileva Dencheva1 , Zlatan Zlatev Denchev1 , Senentxu Lanceros-Méndez2 , José Carlos Brêda1 , Filipa
Matos Oliveira1
1
2
Polymer Engineering, i3N - Institute for Polymers and Composites, Portugal
ESM - Electroactive Smart Materials, University of Minho, Department of Physics, Portugal
Polyamide 6 microcapsules find various applications in biotechnology for protein and enzyme immobilization
to produce drug delivery systems, in solid-phase diagnostics, biosensors, biocatalysts, extracorporeal therapy,
and bio-separation. Also, they have direct and potential applications in fields of industrial materials for laser
sintering, electro-conductive and magnetic composites, etc. This work presents an original one-pot synthesis
of polyamide 6 microcapsules containing in their cores finely dispersed inorganic payloads. The microcapsules
were synthesized by suspension anionic polymerization of ε-caprolactam in non-polar hydrocarbon solvents
carried out in the presence of metal micron-sized powders (Al, Cu, Zn or Fe) or carbon allotropes (carbon
black, carbon nanotubes, graphite and carbon nanofibers). Various composite materials were prepared by
compression molding of the resultant microcapsules. The morphology and crystalline structure of the microcapsules and that of the respective composites were studied by SEM, light microscopy and thermal analyses
(DSC and TGA). The mechanical properties in tension of the composites were evaluated as well as their electromagnetic properties: volume conductivity, dielectric permeability and magnetic susceptibility. The results
obtained suggest that loaded microcapsules can be obtained in high yields, with excellent dispersion of the
conductive material and reaching electrical conductivities of semiconductors (in the case of carbon allotropes)
or high dielectric constants (for metal loads) without any functionalization or compatibilization procedures.
All this allowed the conclusion about the significant application potential of the suggested pathway.
58
Talk Number: 4 (Oral)
Time: Tuesday, May 12, 2015 4:05 PM
Session: T5_2: DEMO (Auditorium)
DIVERSITY OF MICROSTRUCTURE OF POLYMER SOLID INVESTIGATED BY
MOTION OF IMPURITY IONS
Yuichi Anada1
1
Business Administration and Information Science, Hokkaido Information University, Japan
A relatively large amount of non-crystalline part exists between crystallites in polymer solid generally. In
the non-crystalline part, there are free spaces with various sizes. This inhomogeneity of free spaces results
from a thermal motion of the polymer molecules with amorphous conformation under the spatial restriction
made by crystallite morphology. The impurity ions mixed in processing in the crystalline polymers move
through these inhomogeneous free spaces. Consequently, this motion of ions reflects the inhomogeneous
micro-structure of non-crystalline part. Actually, in previous study of our laboratory, plural kinds of
motion of impurity ions is observed for the electric modulus as a function of frequency in low frequency
region below 10 Hz. These plural motions reflect the inhomogeneity of non-crystalline part. Furthermore,
the conductivity relaxation time of the ion motion analyzed for poly(vinyl chloride) plasticized with
dioctyl phthalate (p-PVC), isotactic polypropylene (iPP) and low density polyethylene (LDPE) reflects the
difference of the micro-structure of non-crystalline part among these polymers. In the present study, the
ionic motion of impurity ions in poly(ethylene telephlalate) (PET) is investigated as continuation of this study.
Electrical measurement was made by the apparatus of Schlumberger SI1260 Impedance/Gain-Phase
Analyzer with an amplifier of Keithley428. At the frequencies lower than 10Hz, the amplifier of Keithley428
was used with the impedance analyzer. On the other hand, the amplifier was not used at frequencies higher
than 10 Hz. The three-Terminal-Configuration Electrodes were used. The thickness of the film of PET is
0.1mm.
Frequency dependence of the loss permittivity of PET shows the characteristic of dc conduction below about 1Hz in frequency. The electric modulus-frequency curve shows the characteristic of single
conductivity relaxation, which is the Debye type dispersion. The conductivity relaxation time analyzed
from this curve is 0.53 at 100o C. This value is similar to those of LDPE and plasticized poly(vinyl chloride)
(p-PVC) but smaller than those of iPP. However, in a plot of conductivity relaxation time vs. permittivity,
the location of PET is near p-PVC. This result suggests that the inhomogeneity of PET is similar to that
p-PVC.
59
Talk Number: 5 (Oral)
Time: Tuesday, May 12, 2015 4:25 PM
Session: T5_2: DEMO (Auditorium)
THERMOELECTRIC GENERATORS (TEGS) WITH LONG SERVICE LIVES
Witold Brostow1 , Gregory Granowski1 , Haley E. Hagg Lobland1 , Gerald Hu1 , Nathalie Hnatchuk1 , Sanchit
Sachdeva1,2 , Susmitha Sayana1,2 , John B. White1,3
1
2
3
Dept. of Materials Science & Engineering and Dept. of Physics, University of North Texas, USA
Texas Academy of Mathematics and Science, Texas, USA
Marlow Industries, Inc., Dallas, USA
In 1821 the Estonian-German physicist Thomas Johann Seebeck discovered in the city now called Tallinn
an effect later named after him. Namely, a temperature difference ∆T between two dissimilar electrical
conductors or semiconductors in contact with each other produces a voltage V. Devices based on the
Seebeck effect are called thermo-electric generators (TEGs). There is a very large ∆T between the ambient
temperature and the temperature of the car exhausts. This in principle makes possible creation of a new
type of hybrid cars, without heavy batteries and the need of frequent recharging these batteries. However,
TE materials at temperatures such as 600o C undergo thermal degradation (oxidation, sublimation of some
components) fast. It is for this reason that hybrid cars based on the Seebeck effect do not exist.
Our solution to this problem consists in covering TEGs with high temperature polymers (HTPs)
that survive without degradation 600o C. The coatings protect the devices from thermal degradation: oxygen
cannot penetrate inside, nothing can escape. This eliminates most polymers as candidates for HTPs;
polyethylenes have melting temperatures at most at 130o C, other widely used polymers are not better.
We do have HTPs that ‘survive’ temperature cycling up to 550o C or 600o C. Selection of HTPs is based
on determination of several characteristics: wettability of molten HTPs on TEGs determined by contact
angles; HTP dehydration and curing cycles; differential scanning calorimetry (DSC); thermogravimetric
analysis (TGA); electrical resistivity (ER); energy-dispersive X-ray spectroscopy (EDS); Raman spectroscopy.
60
Wednesday, May 13, 2015 Starting: 8:30 AM
W1: Plenary (Auditorium)
Session Chair: Li Tan
Assistants: Marzieh Bakhtiary Noodeh, Yan Zou
Talk:
1. (8:30 AM, Plenary) Laine: SYNTHESIS, PROCESSING AND PROPERTIES OF SILSESQUIOXANE MACROMONOMERS AND POLYMERS
Dr. Richard Laine, Professor and Director, Materials Science and Engineering, University of Michigan
61
Talk Number: 1 (Plenary)
Time: Wednesday, May 13, 2015 8:30 AM
Session: W1: Plenary (Auditorium)
SYNTHESIS, PROCESSING AND PROPERTIES
MACROMONOMERS AND POLYMERS
OF
SILSESQUIOXANE
Richard M. Laine2,1 , Joesph C Furgal3 , Mozghan Bahrami1 , David Pan2
1
2
3
Materials Science and Engineering, University of Michigan, U.S.
Macromolecular Science and Engineering, University of Michigan, U.S.
Chemistry, University of Michigan, U.S.
Synthesis, Processing and Properties of Silsesquioxane Macromonomers and Polymers
Cage compounds of the type [RSiO1.5]8,10,12 can be synthesized with a variety of functional groups
including systems with mixed functional groups. The cage, originally thought to be innocuous and insulating
can now be shown to greatly influence the reactivity and photophysical properties of appended R groups.
Trace amounts of fluoride anion can be used to catalyze the exchange or RSiO1.5 units between cages and
the introduction of RR’SiO units into the cage and/or the formation of polymeric materials. The judicious
choice of reactants, reaction conditions and R groups provide access to polymers for coatings, very high
surface area microporous and hydrophobic materials as well as dendronizable beads on a chain polymers.
General methods and specific outcomes will be discussed.
62
Wednesday, May 13, 2015 Starting: 9:45 AM
W2_1: NANO (Auditorium)
Session Chair: Li Tan
Assistant: Marzieh Bakhtiary Noodeh
Talks:
1. (9:45 AM, Keynote) Dzenis: SIMULTANEOUSLY STRONG AND TOUGH CONTINUOUS POLYMER NANOFIBERS AND NANOCOMPOSITES
2. (10:25 AM, Invited) Serpe: STIMULI RESPONSIVE POLYMER-BASED SENSORS, MUSCLES,
AND DRUG DELIVERY PLATFORMS
3. (10:45 AM, Oral) Li: POLYMER-BASED MATERIALS FOR BUILDING ARTIFICIAL MUSCLES
AND THREE DIMENSIONAL STRUCTURES BY SELF-ROLLING
4. (11:05 AM, Oral) Alarifi: MECHANICAL AND THERMAL PROPERTIES OF CARBONIZED PAN
NANOFIBERS COHESIVELY ATTACHED TO SURFACE OF CARBON FIBER REINFORCED
COMPOSITES
5. (11:25 AM, Oral) Goponenko: ELECTROSPUN NANOFIBROUS MATERIALS AS STIMULI-RESPONSIVE POLYMERIZED HYDROGELS
63
Talk Number: 1 (Keynote)
Time: Wednesday, May 13, 2015 9:45 AM
Session: W2_1: NANO (Auditorium)
SIMULTANEOUSLY STRONG AND TOUGH
NANOFIBERS AND NANOCOMPOSITES
CONTINUOUS
POLYMER
Yuris Dzenis1
1
MME, UNL, USA
Simultaneously Strong and Tough Continuous Polymer Nanofibers and Nanocomposites
Yuris Dzenis
Department of Mechanical and Materials Engineering
Nebraska Center for Materials and Nanoscience
University of Nebraska-Lincoln
Lincoln, NE 68588-0526
[email protected]
The bulk of nanomaterials research to date focused on nanoparticles. Nanofibers are becoming increasingly
available thanks to emerging nanomanufacturing technologies such as electrospinning. This presentation
reviews recent theoretical and experimental breakthroughs on ultra-high-performance continuous nanofibers
and nanocomposites, conducted by the author’s group. Nanomanufacturing, nanofiber characterization,
modeling, and design issues are covered. Examples of novel synthetic and natural polymer nanofibers, their
assemblies, and nanocomposites are presented. Unique simultaneous increases in strength and toughness
of nanofibers with their diameter decrease are demonstrated for the first time and explained. Recent
breakthroughs on and prospects of nanofiber-reinforced supernanocomposites (defined as nanocomposites
exceeding the properties of conventional advanced composites [3]) are presented. Recommendations on the
cost-effective nanofiber manufacturing scale-up and macroscopic nanocomposite designs for near-to-medium
term applications are formulated.
1. Dzenis Y. “Spinning Continuous Nanofibers for Nanotechnology”, Science, 304, 2004, 1917-1919
2. Dzenis, Y., "Structural Nanocomposites", Science, 2008, 319, 419-420
3. Ritchie, R.O.; and Dzenis, Y., "The Quest for Stronger, Tougher Materials", Science, 2008, 320, 448
4. Papkov, D., Zou, Y., Andalib, M.N., Goponenko, A., Cheng, S.Z.D., Dzenis, Y., "Simultaneously Strong
and Tough Ultrafine Continuous Nanofibers,” ACS Nano, 2013, 7, 3324-3331 (cover feature ACS Nano,
April, 2013; highlighted in Nature, 2013, 495, 284)
64
Talk Number: 2 (Invited)
Time: Wednesday, May 13, 2015 10:25 AM
Session: W2_1: NANO (Auditorium)
STIMULI RESPONSIVE POLYMER-BASED SENSORS, MUSCLES, AND DRUG
DELIVERY PLATFORMS
Michael J. Serpe1
1
Department of Chemistry, University of Alberta, Canada
The group’s research is focused on the development of novel polymer-based materials for solving environmental and health-related problems. To solve these problems, the group primarily employs poly (N-isopropylacrylamide) (pNIPAm)-based spherical particles as the active component in our technologies. PNIPAm-based
particles (nano or microgels, depending on their diameter) are extremely porous, and are fully water soluble and swellable. Additionally, pNIPAm-based nano/microgels are responsive to temperature, shrinking in
diameter as the temperature is increased to >32 o C and reswelling when they are cooled to < 32 o C. Our
group has exploited these properties for numerous applications. Today’s talk will highlight the group’s work
on the development of these devices for sensing and biosensing, as muscles, and for controlled/triggered drug
delivery.
65
Talk Number: 3 (Oral)
Time: Wednesday, May 13, 2015 10:45 AM
Session: W2_1: NANO (Auditorium)
POLYMER-BASED MATERIALS FOR BUILDING ARTIFICIAL MUSCLES AND
THREE DIMENSIONAL STRUCTURES BY SELF-ROLLING
Xue Li1 , Michael J Serpe1
1
Chemistry, University of Alberta, Canada
Poly (N-isopropylacrylamide) (pNIPAm) microgel-based materials can be made, which self-fold into threedimensional structures in response to changes in the humidity of their environment. This material is composed
of a semi-rigid polymer substrate coated with a thin layer of Au; the Au layer is subsequently coated with a
pNIPAm-based microgel layer and finally covered with a solution of polydiallyldimethylammonium chloride
(pDADMAC). When the pDADMAC dries, it causes the material to deform, which is completely reversible
over many cycles as the environmental humidity is systematically varied. In this study, we found this material
was able to do work and lift masses many times the mass of the material in response to changes in the humidity
of its environment. We further investigated how the size and aspect ratio of the polymer substrate affected
the self-folding behavior of the materials. From experimental observations, a set of empirical rules were
developed that can be applied to predict the folding behavior of such materials. Furthermore, these rules
have allowed us to direct the folding of these materials into discrete three-dimensional objects, which are
fully capable of unfolding and folding in response to humidity.
66
Talk Number: 4 (Oral)
Time: Wednesday, May 13, 2015 11:05 AM
Session: W2_1: NANO (Auditorium)
MECHANICAL AND THERMAL PROPERTIES OF CARBONIZED PAN
NANOFIBERS COHESIVELY ATTACHED TO SURFACE OF CARBON FIBER
REINFORCED COMPOSITES
Ibrahim Alarifi1 , Dr. Ramazan Asmatulu1 , Abdulaziz Alharbi1 , Waseem S. Khan1
1
ME, Wichita State University, United States
Pre-preg carbon fibers of 10 peel plies were laid up at 0, 45, -45 and 45 stacking sequences on flat and
smooth Al plate, and then carbonized electrospun polyacrylonitrile (PAN) nanofibers were placed on top
of the last ply prior to the vacuum curing in a vacuum oven. The PAN electrospun fibers were oxidized
at 280o C in an ambient condition for one hour, and then carbonized at 850o C for one hourr in Ar gas
atmosphere. The resultant composite panels were cut into small pieces, and subjected to a number of
different characterization techniques. Thermal Mechanical Analysis (TMA) measurements clearly showed
that a significant reinforcement was achieved for the pre-preg / carbonized PAN fiber composites because
of the enhanced interfacial bonding between the PAN nanofibers and the matrix. Dynamic mechanical
analysis (DMA) tests exhibited that glass transition temperature of carbonized PAN nanofiber/composite
was shifted, which may be helpful for the high-temperature applications of the present composites. Raman
spectroscopy peak around 897 cm-1 indicated the formation of the γ-phase of the carbonized PAN fibers.
The highest stretching peak of CH2 group was recognized within the range of 185-200 cm-1 for the
carbonized fibers. The group of CâĽąN vibration peak also appeared at 1452 cm-1 spectrum. Thermal
Mechanical Expansion (TME) determined the coefficient of thermal expansion, indicating an improvement
in stability of the composite material, which can be useful for the structural health monitoring, lightning strikes and electromagnetic interference (EMI) shielding applications of the new carbon fiber composites.
Keywords: Electrospun PAN Nanofibers, Carbonization, Carbon Fiber Composites, Thermal and
Mechanical Properties.
67
Talk Number: 5 (Oral)
Time: Wednesday, May 13, 2015 11:25 AM
Session: W2_1: NANO (Auditorium)
ELECTROSPUN NANOFIBROUS MATERIALS AS STIMULI-RESPONSIVE POLYMERIZED HYDROGELS
Kazi I Jahan1 , Alexander Goponenko1 , Yuris A Dzenis1
1
Mechanical and Materials Engineering, University of Nebraska-Lincoln, USA
Hydrogels are three-dimensional polymeric networks swollen in aqueous media without dissolution. There
is a growing interest in hydrogel materials, especially in stimuli-responsive polymerized hydrogels (SRPH).
These “smart” hydrogels respond to a change in their environment by increasing or decreasing their
volume and dimensions, changing their mechanical properties, generating substantial force, etc. SRPHs
are increasingly being used, for instance, as sensor-actuator systems for automatic regulation of a liquid flow, where the flow rate can be controlled by the fluid properties, like pH, temperature, and composition.
The main disadvantages of the bulk/film hydrogels are slow speed of response to stimuli and poor
mechanical properties. Therefore, SRPHs in a nanofibrous form are of high interest, because this form will
provide improved mechanical properties and fast response as well as developed porous structure. These
SRPH can be achieved by the electrospinning process. Electrospinning is known to be a versatile and
efficient tool for preparing fibrous materials with fiber diameters ranging from several micrometers down to
tens of nanometers.
In this study, both poly vinyl alcohol (PVA) - poly acrylic acid (PAA) and Dextran (Dex) - PAA
nanofilamentary hydrogel (NFG) are fabricated by electrospinning and crosslinked thermally through ester
formation between a hydroxyl group on one polymer chain and a carboxylic acid on the other. Swelling
kinetics of NFG membranes in different pH solution were compared with bulk hydrogels. These studies
demonstrate a higher degree of swelling and lower water retention abilities in NFG than bulk gels, because
of easier diffusion of water molecules in NFGs. The response speed becomes very fast by reducing the
critical dimension of hydrogel to nano-scale. Also the mechanical properties of conventional bulk gels
were compared to the properties of aligned NFGs. Bulk gels from PVA-PAA and Dex-PAA demonstrated
a similar mechanical behavior, while NFGs from these two polymer systems demonstrated a significant
difference in behavior and exhibit unusual size effect on mechanical properties at smaller diameters. These
hydrogels with nanofilamentary structure and useful features, such as unusual volume phase transition,
size-dependent mechanical properties, and sensitivity to environmental stimuli, reveal unique possibilities
for applications in smart actuator system and biochemical fields.
68
Wednesday, May 13, 2015 Starting: 9:45 AM
W2_2: BIOT (Heritage Room)
Session Chairs: Linxia Gu, Dimitry Papkov
Assistant: Yan Zou
Talks:
1. (9:45 AM, Keynote) Causin: NANOCELLULOSE-REINFORCED GELS FOR BIOMEDICAL APPLICATIONS
2. (10:25 AM, Invited) Schönherr: INFECTION DIAGNOSTICS WITH POLYMERIC VESICLES
AND HYDROGELS FOR APPLICATION IN ADVANCED WOUND DRESSINGS AND BEYOND
3. (10:45 AM, Oral) Saunier: HOW ADDITIVE EXUDATION CAN AFFECT THE BIOCOMPATIBILITY OF A POLYMERIC MEDICAL DEVICE: THE CASE OF A POLYURETHANE USED IN
IMPLANTABLE CATHETERS
4. (11:05 AM, Oral) Ding: ELECTROSPUN PHB/PCL/FUMED SILICA FIBROUS STRUCTURE
FOR BONE TISSUE ENGINEERING
5. (11:25 AM, Oral) Andalib: BIOMIMETIC NANOFILAMENTARY POLYMER SCAFFOLDS AND
THE MECHANISMS OF CELL-SCAFFOLD INTERACTION
6. (11:45 AM, Oral) Maleckis: ULTRAHIGH-PERFORMANCE NANOFIBERS FROM DNA AND
PROTEINS
7. (12:05 PM, Oral) Lyu: INVESTIGATION OF RUBBER FLOW DURING SHAPING OF AUTOMOBILE TIRES
69
Talk Number: 1 (Keynote)
Time: Wednesday, May 13, 2015 9:45 AM
Session: W2_2: BIOT (Heritage Room)
NANOCELLULOSE-REINFORCED GELS FOR BIOMEDICAL APPLICATIONS
Valerio Causin1 , Edmondo Maria Benetti2 , Byungdae Park3 , Nanang Masruchin3
1
2
3
Dipartimento di Scienze Chimiche, Università di Padova, Italy
Department of Materials, ETH Zürich, Switzerland
Department of Wood Science and Technology, Kyungpook National University, Republic of Korea
Drug delivery and tissue engineering pose great challenges for polymer scientists. Polymers have ideal
properties under a number of aspects, but the multiple, and often contradictory, requirements of such
applications involve a precise control over the several steps involved in the manufacturing of the final
material, from the monomer to the finished item. This is vital in particular for the applications where
features such as biodegradation behavior, biocompatibility, size and surface morphology critically govern
the biological activity of the material.
In this communication, the development of polymer-based materials for drug delivery and tissue engineering
applications will be reported.
Poly(oxazoline)s, polymers which display biodegradability, biocompatibility, antifouling properties and
a relatively easy tunability of the chemical structure, were used. These materials were explored for
preparing degradable gels for drug delivery applications and for functionalizing polymeric scaffolds with
brush coatings acting as “first contact layers”. The mechanical properties of these gels were tuned by addition of nanocellulose. The effect of such filler on the performance and on the drug release rate was evaluated.
Acknowledgement: This work was carried out in the framework of the executive programme for scientific and
technological cooperation between the Italian Republic and the Republic of Korea. The contribution of Ministero degli Affari Esteri, Direzione Generale per la Promozione del Sistema Paese, is gratefully acknowledged.
70
Talk Number: 2 (Invited)
Time: Wednesday, May 13, 2015 10:25 AM
Session: W2_2: BIOT (Heritage Room)
INFECTION DIAGNOSTICS WITH POLYMERIC VESICLES AND HYDROGELS
FOR APPLICATION IN ADVANCED WOUND DRESSINGS AND BEYOND
Katrin-Stephanie Tücking1 , Simon Haas1 , Mir Mortzea Sadat Ebrahimi1 , Holger Schönherr1
1
Department of Chemistry & Biology, Physical Chemistry I, University of Siegen, Germany
The development of in situ approaches for point of care infection diagnostics receives currently considerable
attention. In this context we investigate and develop polymer-based infection diagnostics for application in,
among others, wound dressings and in food safety.
Our core strategy is the implementation of selective trigger mechanisms that signal the presence of pathogenic
bacteria via an easily discernible colorimetric signal. In our work we exploit bacterial enzymes as the trigger
to break down reporter dye-filled capsules [1], to enzymatically release indicator species conjugated covalently
to hydrogel materials [2] or digest polymers in nanoporous sensor membranes [3].
The bacteria-sensing capsules are composed of amphiphilic block copolymers, which are assembled into
polymeric vesicles [1]. The enzymatic degradation of the vesicle wall by the enzymes of the pathogenic bacteria
staphylococcus aureus and pseudomonas aeruginosa result in the release of encapsulated dye molecules, which
is detected due to the change in color and / or fluorescence intensity. The detailed characterization of the
polymeric vesicles and the degradation kinetics by confocal fluorescence lifetime imaging microscopy (FLIM)
is shown to provide the basis for the successful development of prototype dressings that respond to low levels
of enzymes in bacterial supernatants.
The strategy was recently expanded to chitosan hydrogel-based sensing platforms, which are compatible
with the implementation in infection-sensing wound dressings and food safety applications [2]. Thin films
of the established wound dressing biopolymer chitosan were functionalized with fluorogenic or chromogenic
substrates, which are released only upon selective enzymatic degradation, resulting in a pronounced increase
in fluorescence emission intensity or color change, respectively. By exploiting various substrates, the detection
of staphylococcus aureus, pseudomonas aeruginosa as well as E. coli (EHEC) is shown to be feasible with
our bacteria sensing hydrogels.
Finally, it will be discussed how novel photonic structures can be exploited to detect bacterial enzymes
without using dye molecules.
References:
1 K.-S. Tücking, S. Handschuh-Wang, H. Schönherr, Australian Journal of Chemistry, 2014, 67, 578-584.
2 M. M. S. Ebrahimi, H. Schönherr, Langmuir, 2014, 30, 7842-7850.
3 F. S. H. Krismastuti, H. Bayat, N. H. Voelcker, H. Schönherr, 2014, submitted.
71
Talk Number: 3 (Oral)
Time: Wednesday, May 13, 2015 10:45 AM
Session: W2_2: BIOT (Heritage Room)
HOW ADDITIVE EXUDATION CAN AFFECT THE BIOCOMPATIBILITY OF A
POLYMERIC MEDICAL DEVICE: THE CASE OF A POLYURETHANE USED IN
IMPLANTABLE CATHETERS
Johanna Saunier1 , Micheal Nouman1 , Emile Jubeli1 , Jean-Marie Herry2 , Christian Marlière3 , Alexandre
Dazzi4 , Margareth Renault2 , Marie-Noëlle Bellon-Fontaine2 , Najet Yagoubi1
1
2
3
4
EA 401 - UFR de pharmacie, Université Paris Sud, FRANCE
BHM - UMR 1319 MICALIS, INRA - AgroPArisTech, FRANCE
ISMO - UMR 8214, CNRS - Université Paris Sud, FRANCE
LCP - UMR 8000, CNRS - Université Paris Sud, FRANCE
An important part of the implantable catheters are made of polyurethane (PU). Moreover the catheters
contain additives such as antioxidants or lubricants. The repartition of additives in the polymer is governed
by thermodynamic and diffusion kinetic. As these molecules are small, they have indeed a high mobility and
they can migrate through the polymer matrix to the surface. Even if the concentration of these additives in
the bulk is commonly less than 0.5%, they can be present at very high concentration on the surface and they
can modify surface properties. In this communication we will present the case of a polyurethane catheter that
can present blooming of antioxidant and lubricant on its surface. After having characterized the blooming by
microscopy (AFM, AFM-IR), we worked on the catheter and on PU spincoated films and we showed how the
interactions of the material with biological media was modified by the blooming. The impact of the bacterial
adhesion was studied by using a versatile and virulent pathogen bacterium, staphylococcus aureus, often
implicated in nosocomial diseases. The adhesion ability and the viability of the adhered cells were evaluated
and we try to correlate these results to the physical properties of the surface (hydrophobicity, topography,
stiffness ...). Moreover the ability of the material to release additives at the solid or soluble state was studied
and correlated to cytotoxicity tests (MTT) realized after contact with endothelial cells (HUVECS).
72
Talk Number: 4 (Oral)
Time: Wednesday, May 13, 2015 11:05 AM
Session: W2_2: BIOT (Heritage Room)
ELECTROSPUN PHB/PCL/FUMED SILICA FIBROUS STRUCTURE FOR BONE
TISSUE ENGINEERING
Yaping Ding1 , Qingqing Yao2 , Wei Li3 , Judith Roether1 , Aldo Boccaccini3 , Dirk Schubert1
1
Department of Materials Science and Engineering, Institute of Polymer Materials, University of ErlangenNuremberg, Germany
2 School of Ophthalmology & Optometry, Institute of Advanced Materials for Nano-Bio Applications, Wenzhou Medical University, China
3 Department of Materials Science and Engineering, Institute of Biomaterials, University of Erlangen-Nuremberg, Germany
Bone tissue engineering is a novel approach to create bone graft in situ as alternative of autograft and
allograft for bone defect repair and restoration. In bone tissue engineering, as one of the key player,
scaffolds were designed to not only support the cell attachment, proliferation and differentiation, but also
were able to degrade by the time of new tissue regeneration and then discharged from the body. Among
the various scaffolds fabrication processes, with combining the dominant advantages of all components,
Electrospinning of polymer/inorganic composites was one of the intensively studied approaches for three
dimensional scaffolds fabrication owing to the fiber size down to nano level, the high porosity up to 95%, the
high surface volume ratio, the conveniences, etc [1]. Here in this study, polyhydroxybutyrate (PHB)/ poly
-ε-caprolactone (PCL)/fumed silica composite fibermeshes were prepared through electrospinning combined
with the ultrasonication since the biopolymer blend was able to integrate the high stiffness and strength of
PHB and high elasticity of PCL, and fumed silica was reported to not only reinforce the polymer matrix, but
also induce higher cell vitality and improved cytocompatibility [2]. In this report, the influence of 0∼50wt%
fumed silica addition on the composite fibrous scaffolds was investigated on the perspective of morphologies,
mechanical properties, chemical structure, wettability, thermal properties and biological properties. The
SEM graphs showed that no severe aggregation occurred until 20wt% particles addition, and the fiber
filaments were fully covered with nanoparticles in case of 50wt% addition. The tensile strength and elastic
modulus was enhanced 14% and 20% by 1wt% silica addition, but decreased with further incorporation.
All electrospun fiber meshes exhibited high hydrophobicity (all with WCA above 130o C); however, the
contact angles all reduced to different extent after 5 mins which is attributed to the hydrophilicity nature
of the fumed silica. FTIR spectra were used to confirm the incorporation of silica nanoparticles, and the
crystallinity changes were analyzed through DSC measurements. At last, the cell response and cytotoxicity
evaluation were conducted to testify the biological properties of the composite system.
Reference
[1] Y. Ding, et al, Eur. Polym. J. 2014, 55(1), 222-234.
[2] Y. Wu, et al, J. Appl. Polym. Sci. 2012, 123(3), 1612-1620.
73
Talk Number: 5 (Oral)
Time: Wednesday, May 13, 2015 11:25 AM
Session: W2_2: BIOT (Heritage Room)
BIOMIMETIC NANOFILAMENTARY POLYMER SCAFFOLDS AND THE MECHANISMS OF CELL-SCAFFOLD INTERACTION
Mohammad Nahid Andalib1 , Jeong Soon Lee1 , Ligyeom Ha1 , Yuris Dzenis1 , Jung Yul Lim1
1
Mechanical and Materials Engineering, University of Nebraska-Lincoln, USA
Tissue engineered scaffolding materials require certain minimum requirements including cellular biocompatibility, mechanical strength, degradation property, etc. to support successful regeneration of the damaged tissue. Electrospun nanofibrous scaffolds can fulfill many of these requirements, as they have advantages of biomimicking nanofilamentary architecture which can be tailored to match the mechanical compliance/strength of the target tissue, high surface area, controllable porous structure, and potential 3D
microenvironment for supporting cell-substrate and cell-cell interaction.
Although nanofiber-based tissue engineering applications have reported some successes, very little is revealed
regarding the molecular mechanism of cell-nanofiber interaction. We tested the hypothesis that cytoskeletal
tension signaling, such as RhoA kinase (ROCK), may play a mediatory role in mesenchymal stem cell (MSC)
alignment on nanofibers. To test this, we produced poly(L-lactic acid) nanofibers to have unidirectional and
random orientations with same diameter (about 130 nm). We cultured MSCs on these aligned and random
nanofibers and flat PLLA control film and assessed the ROCK expression in MSCs on the test substrata by
western immunoblotting. MSCs seeded on aligned nanofibers exhibited well-documented contact guidance
behavior by growing and aligning along the nanofibers. Importantly, we for the first time showed that ROCK
expression in MSCs was significantly increased for cells cultured on aligned nanofibers relative to cells on flat
control which suggested that ROCK is involved in MSC alignment on nanofibers. Furthermore, we demonstrated that if ROCK signaling in MSCs was interfered by molecular silencing (shRNA) or pharmacological
inhibitor (Y-27632), cells on nanofibrous cultures displayed significantly decreased cellular lengths, in both
major and minor axis lengths.
While cytoskeletal signaling such as ROCK may constitute one important regulatory mechanism, focal cell
adhesion signaling may form another vital mechanism for the nanofiber control of cells. Currently, we are
conducting experiments to reveal the role of focal adhesion kinase (FAK) in cell response to nanofibers. Obtained data on the role of ROCK and FAK, each representing key molecular mechanosensors of cytoskeletal
tension and focal adhesion, in MSC alignment and morphology on nanofibers will provide a new insight into
nanofiber-based tissue engineering and regenerative medicine.
74
Talk Number: 6 (Oral)
Time: Wednesday, May 13, 2015 11:45 AM
Session: W2_2: BIOT (Heritage Room)
ULTRAHIGH-PERFORMANCE NANOFIBERS FROM DNA AND PROTEINS
Kaspars Maleckis1 , Yuris Dzenis1
1
Mechanical and Materials Engineering, University of Nebraska-Lincoln, USA
Nucleic acids and polypeptides have several intriguing nanoscale properties which can be adapted in novel
nano-structured and nano-sized devices, sensors and materials. Development of one-dimensional, continuous
nanostructures of these polymers provide additional benefits, such as directionality of properties, easy manipulation and high surface area. Typically such structures have been produced by bottom-up nanofacturing
methods, which rely on biopolymer capability to self-assemble at the molecular scale. While bottom-up approach gives unprecedented control of the molecular structure, it has limitations in continuity and mechanical
integrity of the nanofilaments. Alternative top-down nanomanufacturing methods, like electrospinning, allow
one to overcome these limitations, however control of molecular structure and properties remains uncertain,
since traditional polymer characterization methods cannot be applied to individual nanofilaments.
Here we show a unique insight into structure and properties of individual electrospun DNA and other biological polymer nanofilaments. We also demonstrate specially developed protocols of different characterization methods that can be applied to individual polymer nanofilaments to study size-structure-property
relationships. Our results show that electrospinning enables production of continuous and uniform DNA
nanofilaments within wide range of diameters (10-500nm) and high throughput. Mechanical tests of individual DNA nanofilaments through failure show extraordinary strength and toughness. These properties
increase as nanofiber diameters decrease, exceeding bulk properties of some of the high-performance synthetic materials and fibers. Structural studies of individual DNA nanofibers with different methods indicate
pseudo-crystalline high orientation, but show no indication of crystalline packing. The resulting nanofibers
and their constructs attract high interest for use in drug and gene delivery, tissue engineering, and biomedical
devices.
75
Talk Number: 7 (Oral)
Time: Wednesday, May 13, 2015 12:05 PM
Session: W2_2: BIOT (Heritage Room)
INVESTIGATION OF RUBBER FLOW DURING SHAPING OF AUTOMOBILE
TIRES
Min-Young Lyu1 , Min-A Lee2 , Seong-Yeol Park2 , Sung-Hyun Choi3
1
Mechanical System Design Engineering, Seoul National University of Science and Technology, South Korea
Product Design and Manufacturing Engineering, Seoul National University of Science and Technology,
South Korea
3 Central R & D Center, Hoonkook Tire Co., South Korea
2
Automobile tires consist of more than ten layers, including the tread, carcass, and sidewall. The tread,
in direct contact with the road surface, has a significant effect on the performance of an automobile such
as breaking conditions, traction, noise and so on. It has grooves with a complex geometry that is molded
by a curing process. The short shot of the tread rubber in the mold affects the quality of the tire but,
simultaneously, can lead to problems with the automobile performance. Consequently, investigation of the
flow behavior of tread rubber during the curing process is important. This research undertakes a simulation
and experiment using white rubber to investigate the flow behavior of tread rubber in a mold. Flow of the
rubber across the grooves of the mold is not observed in either the simulation or experiment. The simulation
results are in good agreement with those of the experiment.
76
Wednesday, May 13, 2015 Starting: 1:00 PM
W3: Young Plenary (Auditorium)
Session Chair: Christopher Cornelius
Assistants: Trevor Gnuse, Yan Zou
Talk:
1. (1:00 PM, Young Plenary) Whittington: POLYMER CHARACTERIZATION OF MEDICAL DEVICES FOR USE IN CANCER PATIENTS
Dr. Abby Whittington, Assistant Professor of Biomedical Engineering and Sciences, Virginia Tech
77
Talk Number: 1 (Young Plenary)
Time: Wednesday, May 13, 2015 1:00 PM
Session: W3: Young Plenary (Auditorium)
POLYMER CHARACTERIZATION OF MEDICAL DEVICES FOR USE IN CANCER
PATIENTS
Abby R. Whittington1
1
Chemical Engineering & Materials Science and Engineering, Virginia Tech, USA
Polymeric medical devices are becoming commonplace in the treatment of cancer patients to provide fluids
and medications, to offer insight into diagnosis, and to fill the voids created by removal of the tumor.
Therefore there is a growing need to understand how the materials respond and are influenced by the hostile
environment of generated around the tumor during caner treatment. My research group has begun focusing
on the design and characterization of polyurethane devices for medical applications and how therapeutic
radiation commonly used in cancer therapy influences the critical properties of such materials. This talk will
focus on the two main areas where therapeutic radiation is utilized: imaging and radiotherapy. The doses for
imaging, while very low, pose a risk when repeated multiple times as in the case of placement and monitoring
of peripherally inserted central catheters (PICC) for neonates. In radiotherapy, the dose levels are sufficiently
high to cause cross-linking and/or degradation of many polymers when exposed in the aqueous environment
of the body. An example of both applications will be explored.
78
Wednesday, May 13, 2015 Starting: 1:50 PM
W4: Poster (Ballroom)
Session Chairs: Michael Hess, Jean-Jacques Pireaux
Assistant: Trevor Gnuse
Talks:
1. (1:50 PM, Poster) Jayasinghe: INVESTIGATION OF SWELLING BEHAVIOR OF POLY(HEMACO-DMAEMA) HYDROGELS CONFINED IN AN ELASTOMERIC MOLD
2. (1:50 PM, Poster) Schwahn: CONTROLLED CURING OF ACRYLATE: SYSTEM MODELING
AND APPLICATIONS IN STEREOLITHOGRAPHY
3. (1:50 PM, Poster) Adhikari: CHARACTERIZATION OF BAMBOO FLOURS REINFORCED
EPOXY RESIN COMPOSITES
4. (1:50 PM, Poster) Li: CHARACTERIZATION OF THE INFLUENCE OF DEPTH IN PHOTO CURING OF ACRYLATE: A METHOD BASED ON RAPID-SCAN FTIR DURING LASER CURING ON
AN ATR
5. (1:50 PM, Poster) Furgal: HIGH SURFACE AREA METHYLSILSESQUIOXANE POLYMER GELS
BY FLUORIDE CATALYSIS
6. (1:50 PM, Poster) Stockdale:
NANOCOMPOSITES
MANUFACTURING OF POLYIMIDE FIBER-REINFORCED
7. (1:50 PM, Poster) Zou: EFFECT OF CONSTRAINT ON STRUCTURE AND MECHANICAL
PROPERTIES OF CONTINUOUS POLYACRYLONITRILE-BASED STABILIZED AND CARBONIZED NANOFIBERS
8. (1:50 PM, Poster) Jasa: USING MOLECULAR DYNAMICS SIMULATIONS FOR CHARACTERIZING MACROSCOPIC RESPONSE IN POLYCARBONATE
9. (1:50 PM, Poster) Hnatchuk: MODIFICATION OF POLY(VINYL CHLORIDE)
10. (1:50 PM, Poster) Hnatchuk: PROPERTIES OF EPOXY FILMS BASED ON MODIFIED PHENOLFORMALDEHYDE OLIGOMERS
11. (1:50 PM, Poster) Chan: FTIR STRUCTURAL ANALYSIS OF EPOXY PAINTS ON STEEL
STRUCTURE FOR COATING FINGERPRINTING CERTIFICATE FOR PAINT INDUSTRY
12. (1:50 PM, Poster) Viel: IMPACT OF COVER SLIDE ON RECRYSTALLIZATION FROM THE
AMORPHOUS STATE OF CHIRAL PHARMACEUTICAL COMPOUNDS: CASE OF DIPROPHYLLINE
13. (1:50 PM, Poster) Cosby: CHARGE TRANSPORT AND STRUCTURAL DYNAMICS OF POLYMERIZED IONIC LIQUIDS
14. (1:50 PM, Poster) Jiao: INTERPLAY BETWEEN ABSORPTION BROADENING AND MORPHOLOGY DETERIORATION IN TERNARY BULK HETEROJUNCTION SOLAR CELLS RESOLVED
BY SOFT X-RAY SCATTERING
15. (1:50 PM, Poster) Chen: OPTIMIZATION OF THE DISTRIBUTION OF PROPERTIES: USING
ACRYLATE/EPOXY MIXTURES IN THE EXTENSION OF AN FGM PLATE WITH A HOLE
16. (1:50 PM, Poster) Daily: DIELECTRIC PROPERTIES AND KINETIC STUDY ON THE DEGRADATION OF BISMALEIMIDE RESIN
79
17. (1:50 PM, Poster) Jamil: MECHANISM OF MOLECULAR INTERACTION OF SUPERPLASTICIZER OLIGOMERS WITH HYDRATED CEMENT PHASES
18. (1:50 PM, Poster) Piorkowska: COMPARISON OF PROPERTIES OF STAR AND LINEAR
POLY(L-LACTIDE)
19. (1:50 PM, Poster) Frazier: CHEMICAL MODIFICATION OF PROTEIN-BASED ADHESIVES FOR
CONSTRUCTION APPLICATIONS
20. (1:50 PM, Poster) Dargent: MOLECULAR DYNAMICS IN ELECTROSPUN FIBERS OF PLASTICIZED POLYLACTIDE
21. (1:50 PM, Poster) Gakhutishvili: TRIBOLOGICAL PROPERTIES OF ANTIBACTERIAL POLYMER COMPOSITES
22. (1:50 PM, Poster) Delpouve: LENGTH SCALE AT THE GLASS TRANSITION IN SEMI-CRYSTALLINE COMPATIBILIZED POLYLACTIDE/CLAY NANOCOMPOSITES
23. (1:50 PM, Poster) Lin: HYDROGEN BONDING INDUCED NANOPHASE SEPARATION OF GIANT SURFACTANTS TOWARD SUB-10-NM HYBRID ORDER NANOSTRUCTURES
24. (1:50 PM, Poster) Liu: TWO-DIMENSIONAL NANO-CRYSTALS OF MOLECULAR JANUS PARTICLES
25. (1:50 PM, Poster) Alarifi: EFFECTS OF UV EXPOSURE ON PHYSICAL PROPERTIES OF CARBON FIBER/PPS THERMOPLASTIC COMPOSITES
26. (1:50 PM, Poster) Kaser:
YARNS
NANOMANUFACTURING POLYACRYLONITRILE NANOFIBER
27. (1:50 PM, Poster) Alharbi: INTEGRATING C60 NANOPARTICLES INTO TIO2 NANOFIBERS
VIA ELECTROSPINNING PROCESS FOR ENHANCED ENERGY CONVERSTION EFFICIENCIES
28. (1:50 PM, Poster) Loubeau: AGEING OF A THREE-LAYER PAPER USED IN THE INSULATION
OF AN ELECTRICAL MOTOR FOR THE AUTOMOTIVE TRACTION
29. (1:50 PM, Poster) Schmidt: A STUDY OF THE EFFECTS OF SPIN COATING ON PVDF FILMS
30. (1:50 PM, Poster) Schönherr: INVESTIGATION OF ELECTRONIC PROPERTIES OF A
GRAPHENE FIELD EFFECT TRANSISTOR
31. (1:50 PM, Poster) Ding: BROADBAND DIELECTRIC RELAXATION ANALYSIS ON THE REINFORCEMENT OF ANTHRACENE-FUNCTIONALIZED EPOXY COMPOSITES
32. (1:50 PM, Poster) Lobland: SYNTHESIS AND PROPERTIES OF REACTIVE OLIGOMERS
BASED ON A PEROXY DERIVATIVE OF AN EPOXY RESIN AND 1,4- BUTANEDIOL
33. (1:50 PM, Poster) Ospina: SYNTHESIS AND CHARACTERIZATION OF POLYMERS WITH ANTIBACTERIAL PROPERTIES BASE ON TRICLOSAN ACRYLATE
34. (1:50 PM, Poster) Bakhtiary Noodeh: USING CURING KINETICS TO CONTROL THE MECHANICAL PROPERTIES OF SIMULTANEOUS ACRYLATE/EPOXY IPNS DURING PHOTO
CURING OF GRADED MATERIALS
35. (1:50 PM, Poster) Gafurov: MOLECULAR STRUCTURE PARAMETERS INFLUENCE ON DEFORMATION MECHANICS OF AN ORIENTED CRYSTALLINE POLYMER
80
36. (1:50 PM, Poster) Lanyi: NOVEL CHART FOR REPRESENTATION OF MATERIAL PERFORMANCE AND RELIABILITY
37. (1:50 PM, Poster) Rezaei: U-SHAPED PROBES FOR CHARACTERIZATION OF POLYMERS
USING CONTACT RESONANCE ATOMIC FORCE MICROSCOPY
38. (1:50 PM, Poster) Dargent: STUDY OF AMORPHOUS AND CRYSTALLINE PHASES IN BIOBASED NANOCOMPOSITE FILMS
39. (1:50 PM, Poster) Delpouve: MICROSTRUCTURE, AMORPHOUS PHASE DYNAMICS AND
BARRIER PROPERTIES IN MULTILAYER COEXTRUDED POLYLACTIDE
40. (1:50 PM, Poster) Schamme:
POLY(LACTIC ACID)
RELAXATION OF SHEAR-INDUCED PRECURSORS IN
41. (1:50 PM, Poster) Hosseinabad: EFFECT OF COPOLYMER CONTENT ON FLOW-INDUCED
CRYSTALLIZATION
42. (1:50 PM, Poster) Sterzynski: THE POSS AND MWCNT MODIFIED GLASS TRANSITION TEMPERATURE TG OF POLY(VINYL CHLORIDE)
43. (1:50 PM, Poster) Saiter: INFLUENCE OF STRUCTURAL FEATURES OF POROGEN
MOLECULES ON THERMAL PROPERTIES AND POROSITY OF NANOPOROUS POLYCYANURATE-BASED FILM MATERIALS
44. (1:50 PM, Poster) Zare Rami: INVESTIGATION OF FRACTURE BEHAVIOR OF HETEROGENEOUS POLYMER MIXTURES SUBJECTED TO VISCOELASTIC DEFORMATION USING
MICROSTRUCTURAL MODELING
45. (1:50 PM, Poster) Ding: POLAR PHASE GENERATION IN PVDF, THROUGH AMPHIPHILIC
IONIC LIQUID MODIFIED MULTIWALLED CARBON NANOTUBES: EFFECT OF ANION
81
Talk Number: 1 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
INVESTIGATION OF SWELLING BEHAVIOR OF POLY(HEMA-CO-DMAEMA)
HYDROGELS CONFINED IN AN ELASTOMERIC MOLD
Hasani Gaya Jayasinghe1 , Yolanda Vasquez1
1
CHEMISTRY, OKLAHOMA STATE UNIVERSITY, USA
Hydrogels are versatile network polymeric materials that have a vast range of applications that includes scaffolds for tissue engineering, drug delivery systems, and as sensors and actuators due to properties such as high
retention of water, biocompatibility and ability to respond to external stimuli. The swelling of a hydrogel
depends on properties such as crosslinking density and the identity of the functional groups present in the
hydrogel as well as the interactions between the hydrogel and the solvent. In addition to the chemical parameters, swelling of the hydrogel can be significantly affected by confinement. In this study, we have prepared
a poly(HEMA-co-DMAEMA) [poly(2-hydroxyethylmethacrylate-co-2-dimethylaminoethylmethacrylate)] hydrogel and investigated the swelling of the hydrogel while confined by polydimethyl siloxane (PDMS), an
elastomeric material. Around two-fold decrease in the swelling ratio was observed when PDMS was used as
the confining surface as compared to the free, unconfined hydrogel and when 60% ethanol was used as the
swelling medium. We demonstrate that the swelling behavior of the confined hydrogel can be exploited to
successfully generate microscale patterns on to poly(HEMA-co-DMAEMA).
82
Talk Number: 2 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
CONTROLLED CURING OF ACRYLATE: SYSTEM MODELING AND APPLICATIONS IN STEREOLITHOGRAPHY
Evan Schwahn1 , Wenlong Li1 , Mehrdad Negahban1 , Nicolas Delpouve2 , Jean-Marc Saiter2 , Steven Araujo2 ,
Florian Batteux2
1
2
Mechanical and Materials Engineering, University of Nebraska-Lincoln, United States of America
Department of Physics, University of Rouen, France
Rapid prototyping (RP) is widely used in industry for its ability to construct parts and/or prototypes
quickly and affordably. Despite the recent advances in the field regarding part resolution and accuracy such
as that by Ruidong and Dichen [1], and also research into multi-material prototyping [2], there is still a need
for materials with properties that can be controlled and specified at any point within a part structure. This
control of properties within one material can eliminate the need for fasteners and other assembly practices
that could otherwise be costly to manufacturers. The goal of this work was to provide a model for controlled
curing of acrylate resin that would allow the manufacture of a graded structure at the molecular level. We
use the stereolithography rapid prototyping technique.
To achieve this, rapid-scan FTIR was employed to study the curing kinetics of the acrylate resin in order
to determine control variables for the RP machine. The study provided information the energy exposure
needed to reach any degree of conversion desired for the acrylate system and yielded information about the
dark cure effect (continued curing after termination of light exposure). Another control variable studied is
the laser beam profile overlap that results from successive linear scans. To achieve a uniform conversion
degree across the sample, it was determined that the energy profiles of successive scans over the same point
could not added and related to the extent of curing. Instead, when a second exposure was overlapped with
the first, the overlapped area yielded a conversion degree up to 25% higher than would be expected for a
single exposure at the total energy. Because of this behavior, a study was done and the optimal beam profile
overlap for sample uniformity was found to be 35% beam overlap for the acrylate system. With information gained from these studies, a model was developed to predict the curing extent in the beam overlap region.
[1] Xie, Ruidong, and Dichen Li. “Research on the Curing Performance of UV-LED Light Based Stereolithography.” Optics & Laser Technology 44, no. 4 (June 2012): 1163-71. doi: 10.1016/ j.optlastec.2011.09.019.
[2] Choi, Jae-Won, Ho-Chan Kim, and Ryan Wicker. “Multi-Material Stereolithography.” Journal of Materials Processing Technology 211, no. 3 (March 1, 2011): 318-28. doi: 10.1016/ j.jmatprotec.2010.10.003.
83
Talk Number: 3 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
CHARACTERIZATION OF BAMBOO FLOURS REINFORCED EPOXY RESIN
COMPOSITES
Rameshwar Adhikari1 , Surendra Kumar Gautam2 , Marco Liebscher3 , Ralf Lach4 , Wolfgang Grellmann4 ,
Hanna Brodowsky3 , Gert Heinrich3
1
2
3
4
Central Department of Chemistry, Tribhuvan University, Nepal
Department of Chemistry, Tri-Chandra Campus, Tribhuvan University, Kathmandu, Nepal
Leibnitz Institute of Polymer Research, Dresden, Germany
Center of Engineering, Martin Luther University Halle-Wittenberg, Germany
Bamboo flours were subjected to different chemical modifications and carbonization and incorporated
into epoxy resin with the aim of reinforcing the mechanical properties of the composite materials. The
composites were prepared by using amine hardened diglycidyl ether of bisphenol A (DGEBA) as polymer
matrix which were characterized by thermogravimetric analysis (TGA), dynamic mechanical analysis and
scanning electron microscopy (SEM).
Both neat and carbonized bamboo flour filled composites showed significant reinforcement in mechanical
properties. As shown by SEM investigations, the fillers were uniformly distributed in the matrix, the
distribution being much better in the composites with carbonized bamboo flour. This effect was reflected
also in the mechanical properties of the samples. A significant increase in the glass transition temperature
in the composites relative to the neat epoxy resin was observed. The observed properties of composites will
be discussed in correlation with the phase morphology.
Keywords: epoxy resin, polymer composites, electron microscopy, microhardness
84
Talk Number: 4 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
CHARACTERIZATION OF THE INFLUENCE OF DEPTH IN PHOTO CURING
OF ACRYLATE: A METHOD BASED ON RAPID-SCAN FTIR DURING LASER
CURING ON AN ATR
Wenlong Li1 , Mehrdad Negahban1 , Nicolas Delpouve2 , Jean-Marc Saiter2 , Florian Batteux2 , Steven Araujo2
1
2
Department of Mechanical and Materials Engineering, University of Nebraska-Lincoln, United States
AMME-LECAP EA 4528 International Lab., Normandie University, Université and INSA Rouen, France
When photo curing a polymer system one becomes immediately concerned with the depth of penetration of
light into the system and with the uniformity of curing process. Both of these are related to the Beer-Lambert
law of light penetration into the system. To use the Beer-Lambert law, which is given in an exponential
form for a homogeneous system, one needs to determine of the associated attenuation coefficient. This is
normally done by direct measurement of the light transmission using different thicknesses of the medium
using a power meter. We have used a Rapid-Scan FTIR equipped with an ATR to demonstrate that one can
get the Beer-Lambert attenuation coefficient directly while monitoring the curing kinetics. This also allows
to directly evaluate the validity of the one half power law used to model the effect of power on the curing
kinetics. The process was demonstrated for the photo curing of an acrylate system.
85
Talk Number: 5 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
HIGH SURFACE AREA METHYLSILSESQUIOXANE POLYMER GELS BY FLUORIDE CATALYSIS
Joseph Furgal1 , Honami Yamane2 , Timothy Odykirk3 , Eongyu Yi3 , Richard Laine3
1
2
3
Chemistry/Macromolecular Science and Engineering, University of Michigan, USA
Polymer Chemistry, Kyoto University, Japan
Materials Science and Engineering, University of Michigan, USA
High surface area materials are of considerable interest for gas storage/capture as well as for slow release drug
delivery systems. The hydrophobic methylsilsesquioxane polymer gels are made by a simple and fast fluoride
catalyzed rearrangement of methyltriethoxysilane and bis-triethoxysilylethane (BTSE) at room temperature.
These materials offer surface areas up to 1300 m2 /g, pore sizes of 0.8 nm and thermal stabilities above 200
o C. The gelation time and surface area can be controlled by adjusting the solvent volume (DCM), % fluoride
(TBAF) and amount of cross-linking agent (BTSE). Polymers with other corners and linkers are also explored.
86
Talk Number: 6 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
MANUFACTURING OF POLYIMIDE FIBER-REINFORCED NANOCOMPOSITES
Taylor Stockdale1 , Mohammad Nahid Andalib1 , Anastasia Desyatova1 , Stephen Cheng2 , Yuris Dzenis1
1
2
Mechanical and Materials Engineering, University of Nebraska-Lincoln, United States
Department of Polymer Science, University of Akron, United States
Continuous nanofibers are an emerging class of nanomaterials with property combinations unavailable in
other materials, offering a great opportunity for composite applications. Polyimide (PI) is an attractive
candidate for use in composites due to its versatility, good chemical resistance, and high service temperature.
Typical fabrication of PI fibers is completed in two steps. First a polyamic acid (PAA) solution is used to
spin PAA fibers. The fibers are then converted to polyimide through an imidization process. A single step
fabrication method is of great interest as it would simplify the fiber manufacturing process, and prevent the
fusion of fibers that can occur during imidization. Here we demonstrate the manufacturability of a thin,
flexible, nanofiber-reinforced composite material based on electrospun PI nanofibers, produced in a singlestep process from a soluble PI. PI nanofiber mats were used as reinforcement in two types of resins - epoxy
and PI. The epoxy-based nanocomposites were manufactured by applying an epoxy resin to as spun nanofiber
mats and then curing at elevated temperatures under pressure. For PI/PI nanocomposites, thin PI films
were first produced using a drawdown machine and another soluble PI. PI nanofiber mats were assembled
between PI thin films and cured under pressure at temperatures above the Tg of the thin films, but below the
Tg of the nanofibers. PI/PI nanocomposite thicknesses were an order of magnitude lower than thicknesses
of epoxy-matrix nanocomposites. SEM results confirmed that complete impregnation of nanofiber mats was
achieved and the resulting nanocomposites were optically transparent.
87
Talk Number: 7 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
EFFECT OF CONSTRAINT ON STRUCTURE AND MECHANICAL PROPERTIES OF CONTINUOUS POLYACRYLONITRILE-BASED STABILIZED AND CARBONIZED NANOFIBERS
Yan Zou1 , Dimitry Papkov1 , Alexander Goponenko1 , Yuris Dzenis1
1
Mechanical & Materials Engineering, UNL, USA
High-performance carbon fibers are the most commonly used reinforcements in structural advanced composites. Commercial high-strength carbon fibers are produced from polyacrylonitrile (PAN) by a two stage
process that includes oxidative stabilization and carbonization at high temperature under inert atmosphere.
Application of constraint and stretch of the precursor fibers during the stabilization stage is commonly
believed to be responsible for the superior properties of carbon fibers. Such treatment prevents entropic
shrinkage, and relaxation of the aligned polymer chains. Continuous carbon nanofibers (CNFs) can be produced from electrospun PAN nanofibers (NFs) by stabilizing and carbonizing them. Mechanical properties of
individual CNFs and NFs were not widely studied so far. Here we present a study of size effects in mechanical properties of individual stabilized and carbonized PAN NFs examined in a wide range of NF diameters,
showing significant improvements in strength and modulus with the decrease in CNF diameter. In addition,
graphitic structure, graphitic crystal orientation in CNFs was examined by Raman spectroscopy and electron
diffraction, showing significant improvements for smaller NF diameters, and as a result of physical constraint
of the CNFs during the nano-manufacturing process. Comparison of mechanical properties of NFs stabilized
with and without constraint show significant improvements in NF modulus for the constrained NFs. The
demonstrated results indicate the potential for the development of next generation advanced fibers.
88
Talk Number: 8 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
USING MOLECULAR DYNAMICS SIMULATIONS FOR CHARACTERIZING
MACROSCOPIC RESPONSE IN POLYCARBONATE
John Jasa1 , Lili Zhang3 , George Gazonas2 , Antoine Jérusalem3 , Zesheng Zhang1 , Mehrdad Negahban1
1
2
3
Mechanical and Materials Engineering, University of Nebraska-Lincoln, United States
U.S. Army Research Laboratory, Aberdeen Proving Ground, United States
Department of Engineering Science, University of Oxford, United Kingdom
Keywords: Molecular dynamics, continuum-level characterization, deformation gradient, Cauchy stress,
multi-scale
Recently, there has been a push to accurately characterize amorphous glassy polymers using molecular dynamics (MD) simulations. Our work uses MD to help bridge the gap between nanoscale simulations
and well-understood macroscale experiments. To do this, continuum parameters widely used in continuum
mechanics, such as deformation gradient and Cauchy stress, are constructed from MD simulations. These
methods are applicable to non-equilibrium and inhomogeneous systems, and can be used to evaluate any
part of a system, such as a molecule or particular region in the system. This information can be used to
create continuum-like models based on MD simulations.
These continuum-like methods have been applied to systems of polycarbonate at various temperatures and strain rates. In addition to polymers, KcsA potassium channels, carbon nanotubes, and aluminum
oxynitride have been investigated to show the versatility of the methods. The results from these simulations
and our analyses compare well with experimental results, especially in regards to stress-strain relationships.
With the proposed method, specific groups of atoms can be selected and analyzed in order to determine areas of stress concentrations or derive properties for a portion of the system. This can be especially
useful to examine the material around cracks or to characterize the microstructure after impact loading.
By using these methods on larger systems of 100,000s of atoms, the continuum properties are expected
to better mimic the expected continuum response. Additionally, the large systems allow focusing on local
events around, for example, cracks. Averaging of individual molecular response naturally provides a way to
study the difference between affine and non-affine motions in large systems.
89
Talk Number: 9 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
MODIFICATION OF POLY(VINYL CHLORIDE)
Witold Brostow1 , Olena Astakhova2 , Bogdana Bashta2 , Michael Bratychak2 , Gregory Granowski1 ,
Nathalie Hnatchuk1
1
2
Materials Science and Engineering, University of North Texas, USA
Polymer Chemistry and Technology, Lvivska Politechnika National University, Ukraine
Oligomer products with various functional groups are widely used as crosslinking and modified agents of
different polymer mixtures. The modification of Polyvinyl Chloride (PVC) based mixtures by oligomers
with carboxy and epoxy or peroxy functional groups have been studied.
The effect of incorporation of polyfunctional oligomers into the PVC material was investigated by
the weight loss. Samples were kept at 422 K during 7 days. Mixture IV is characterized by stable weight
during four days and the it starts losing weight, but still at a slower rate than other materials. This while
the unmodified PVC containing a plasticizer started losing weight from the first day. These results correlate
well with those from TGA.
90
Talk Number: 10 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
PROPERTIES OF EPOXY FILMS
FORMALDEHYDE OLIGOMERS
BASED
ON
MODIFIED
PHENOL-
Witold Brostow1 , Olena Astakhova2 , Michael Bratychak2 , Nathalie Hnatchuk1 , Halyna Zubyk1,2
1
2
Materials Science and Engineering, University of North Texas, USA
Polymer Chemistry and Technology, Lvivska Politechnika National University, Ukraine
The presence of different functional groups in the molecules of phenol-formaldehyde oligomers (PFOs)
should improve properties of the final products. This applies in particular to protective coatings containing
PFOs. We have synthesized PFOs which contain methacrylate or peroxide and hydroxyl groups based on
the Novolac PFO.
With oligomers so synthesized, we have created oligomeric epoxy films based on the ED-20 epoxy
resin and oligoesteracrylate at 403 K for 75 minutes. The original Novolac PFO was studied for comparison.
Films so obtained exhibit much stronger chemical resistance to aggressive environments and improved
properties than the Novolac. We have also determined scratch resistance, the technique is described in [1].
Much shallower residual depth is seen for an oligomer with methacrylic groups. Thus, such a material is a
good candidate for protective coatings when strong scratch resistance is required.
Reference:
1. W. Brostow, V. Kovacevic, D. Vrsaljko & J. Whitworth, Tribology of polymers and polymer-based
composites, J. Mater. Ed. 2010, 32, 273.
91
Talk Number: 11 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
FTIR STRUCTURAL ANALYSIS OF EPOXY PAINTS ON STEEL STRUCTURE
FOR COATING FINGERPRINTING CERTIFICATE FOR PAINT INDUSTRY
Chinhan Chan1 , Chonghup Ong2 , Tan Winie1 , Mk Harun1 , Mh Hidzir1 , Fi Saaid1 , Jiayin Lee3
1
2
3
Faculty of Applied Sciences, Universiti Teknologi MARA, Malaysia
, Norimax Sdn Bhd, Malaysia
, Research Instruments (M) Sdn Bhd, Malaysia
Most of the oil and gas companies in Malaysia are facing challenge to ensure the fabrication & construction
works are carried out in full compliance to the specifications. The general phenomenon is the jobs or projects
offered by the oil and gas companies are secured at rock-bottom prices by the suppliers. The question is:
has it been possible to maintain (or improve) the quality of the jobs despite the challenge of lower prices
or sometimes below the cost prices of suppliers. One of the identified and common challenges for the oil
and gas companies is the failure of polymeric coatings on steel structures, which has led to huge cost of
repainting jobs. This progressive study showcases the practicality and simplicity of the provision of Coating
Fingerprint Certificate for 2-component epoxy coatings for the supply of polymeric coatings from local paint
manufacturers as quality assurance requirement of the coatings supplied. This will reduce the possibility
of failures of the polymeric coatings and hence enhance the quality, integrity and safety. Fourier-transform
infrared (FTIR) is a simple and reliable tool for the study of reproducibility of the epoxies and hardeners as
well as to differentiate different types of epoxies and hardeners without any intrusion of paint formulations
when High Sensitivity Compare feature of the FTIR software is to be strictly followed. This algorithm
depends on x- (wavenumber) and y- (absorbance) vectors. This function is able to discriminate minute
difference of different components as well as the compositional change of the components among samples.
Simple (and software assisted) step-by-step guides are proposed in this work for the generation of reference
FTIR spectrum from one sample, which subsequently is used to estimate the degree of similarity (r) with the
FTIR spectra from other samples. Fingerprinting regions of FTIR for epoxy resin and hardener are proposed
and the confidence level of acceptance for quality assurance and quality control (QA & QC) is suggested at
more or same at 90.0%. We conclude that, the structural analysis by FTIR for complete Coating Fingerprint
Certificate for epoxy resin and hardener is reproducible. Besides, rejection or acceptance of the samples can
be easily done by setting the threshold value at 0.90 using High Sensitivity Compare feature of the FTIR
software.
92
Talk Number: 12 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
IMPACT OF COVER SLIDE ON RECRYSTALLIZATION FROM THE AMORPHOUS STATE OF CHIRAL PHARMACEUTICAL COMPOUNDS: CASE OF
DIPROPHYLLINE
Quentin Viel1,2 , Clement Brandel2 , Yohann Cartigny2 , Gerard Coquerel2 , Eric Dargent1 , Samuel Petit2
1
2
LECAP, University of Rouen, France
Crystal Genesis SMS, University of Rouen, France
Althought two enantiomers of an active pharmaceutical ingredient (API) share the same chemical composition, the spatial arrangement of atoms differs around the asymmetric center, which often results in
significantly different pharmacological properties. It is nowadays almost mandatory to commercialize only
enantiopure samples. For this purpose, crystallization processes are economically advantageous and are
often employed at the industrial scale. Thus, crystallization of chiral APIs has been the subject of intense
research, but these investigations are rather focused on crystallization in solution. Hence, the fundamental
mechanisms related to nucleation and growth of chiral APIs from glassy materials remain largely unexplored
as a consequence of our poor understanding of molecular arrangements, motions and interactions in
amorphous materials. Consequently, the scientific and industrial communities try to understand the
factors affecting the crystallization route from the amorphous state [1-2]. There is a scientific interest in
understanding the role of the confinement due to the cover slide in glass-forming materials during the
process of crystallization [3].
The aim of this study is to elucidate the impact of enantiomeric composition in supercooled melts on
the outcomes of DPL recrystallization from the amorphous state, with and without cover slide. Hot
Stage Microscopy (HSM) analyzes, Calorimetric measurements (DSC), X-Ray Powder Diffraction (XRPD)
and Raman spectroscopy have been used to characterize the polymorphism of the distinct enantiomeric
compositions promoted by the cover slide effect.
[1] Yu L., Advanced Drug Delivery Reviews, 48, 27-42, 2001
[2] Hancock B.C., Shamblin S.L., Zografi G., Pharmaceutical Research, 12, 6, 1995
[3] Bhugra C., Shmeis R., Pikal M., Journal of Pharmaceutical Sciences, 97, 10, 2008
93
Talk Number: 13 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
CHARGE TRANSPORT AND STRUCTURAL DYNAMICS OF POLYMERIZED
IONIC LIQUIDS
James Tyler Cosby1 , Maximilian Heres1 , Joseph Minutolo1 , Joshua Sangoro1
1
Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, United States
Charge transport and structural dynamics of polymerized imidazolium bis(trifluoromethylsulfonyl)imide ionic
liquids are investigated by broadband dielectric spectroscopy and differential scanning calorimetry. Unlike
non-polymerized ILs, DC conductivity and structural dynamics show significant decoupling, especially at
low temperatures, due to the high mobility of the anion relative to the rate of structural relaxation. A
homologous series of imidazolium based polymerized ionic liquids are investigated to determine the effect of
alkyl substitution of the polymer backbone on the physicochemical properties of these polyILs.
94
Talk Number: 14 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
INTERPLAY BETWEEN ABSORPTION BROADENING AND MORPHOLOGY DETERIORATION IN TERNARY BULK HETEROJUNCTION SOLAR CELLS RESOLVED BY SOFT X-RAY SCATTERING
Xuechen Jiao1 , Xiaoyan Du2 , Tayebeh Ameri3 , Rainer Fink2 , Harald Ade1
1
2
3
Physics, North Carolina State University, USA
PhysikalischeChemie II, FAU Erlangen-Nürnberg , Germany
I-MEET, FAU Erlangen-Nürnberg, Germany
In the past several years, P3HT:ICBA based ternary blends have been intensively investigated. Although
various sensitizers were used to broaden absorption range, ternary BHJs show few successful cases. Therefore, fundamental understanding why ternary cells fail to achieve high efficiency is indispensable for the
future development of ternary blend solar cells. Domain details inside active layers are considered crucial to
influence device performance. However, due to the low material contrast between polymer and fullerene in
conventional morphology characterization such as transmission electron microscope (TEM), unambiguous
and quantitative study of morphology impact of sensitizer is still lacking. Resonant soft x-ray scattering
technique(R-SoXS) has emerged as a powerful tool for morphology study in polymer:fullerene blends due
to the strong material contrast it utilizes[1]. R-SoXS can probe inter-domain details or mass-thickness
variation by tuning the incident photon energy to material contrast or vacuum contrast[2]. Here, we
sensitized P3HT:ICBA by Si-PCPDTBT/C-PCPDTBT to broaden the absorption range. The domain
spacing is quantitatively characterized by R-SoXS and reveals good correlation with device performance.
Interestingly, although Si-PCPDTBT and C-PCPDTBT are very similar in terms of chemical structure and
absorption, the influence of Si-PCPDTBT/C-PCPDTBT on morphology are quite different. By tracking the
domain spacing evolution of ternary blends along with different Si-PCPDTBT/C-PCPDTBT concentration,
it was found that incorporation of Si-PCPDTBT up to 20% does not influence active layer inter-domain
spacing, while the incorporation of C-PCPDTBT disturbs active layer morphology even at low C-PCPDTBT
concentration. Through this study, we observed experimentally and quantitatively the morphology evolution
along with different concentration of sensitizer and substantiated that in order to improve PCE of ternary
BHJs, at the moment of broadening the absorption range of active layer, it is also crucial to minimize the
negative influence of sensitizer on the active layer morphology.
[1] Collins, B. A., Z. Li, et al. (2013). Advanced Energy Materials 3(1): 65-74.
[2] Gann, E., A. T. Young, et al. (2012). Review of Scientific Instruments 83(4)
95
Talk Number: 15 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
OPTIMIZATION OF THE DISTRIBUTION OF PROPERTIES: USING ACRYLATE/EPOXY MIXTURES IN THE EXTENSION OF AN FGM PLATE WITH A
HOLE
Zhong Chen1 , Mehrdad Negahban1
1
Mechanical and Material Engineering, University of Nebraska Lincoln, USA
We looked at optimization of property distribution in parts. As it will be shown, by changing the distribution
of material properties, one can make an inhomogeneous part that is better than the best uniform part. To
demonstrate this, we looked at optimizing the distribution of properties in a plate with a hole that is under
uniaxial extension. In this problem, for a uniform plate the hole creates a stress concentration that limits the
maximum applied stress on the plate to one third the load carrying capacity of the material. We show that
for real materials one can select material distributions that allows applied stresses close to the maximum
capacity of the best material (i.e. 3 times the load carrying capacity of the best uniform plate with a hole).
An acrylate/epoxy IPN plate with a hole was selected for the investigated. We modeled, as a function of each components concentration, the real characterized values of the Young’s modulus, Poisson’s ratio
and fracture strength. A finite-element-method analysis based tool was developed to optimized the property
distribution for this problem. It is shown that by varying the content of epoxy from 70 to 100% in the
mixture, one can protect the hole, and thus use most of the material at 100% of its capacity, resulting in
over two fold increase of the load carrying capacity of the part relative to the best uniform part.
96
Talk Number: 16 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
DIELECTRIC PROPERTIES AND KINETIC STUDY ON THE DEGRADATION OF
BISMALEIMIDE RESIN
Connor Daily1 , Nicola Bowler1
1
Materials Science and Engineering, Iowa State University, USA
Bismaleimide, a thermosetting resin, is attracting interest in the aerospace industry due to its epoxy-like
processability, but better high-temperature performance than epoxy. As this industry shifts towards using
higher overall percentages of fiber-reinforced polymer-matrix composites, understanding how these systems
degrade, in particular the polymer matrix component, becomes increasingly important. Additionally, these
materials are now being exposed to a wider variety of environmental and physical conditions, as new areas
of usage, for both primary and secondary roles, are being explored. In this context, the thermo-oxidative
degradation kinetics of bismaleimide are explored. Two model-free isoconversional methods, the Friedman
and Ozawa-Flynn-Wall methods, are used to analyze results from thermogravimetric analysis at a variety
of heating rates (2, 5, 10, 20, and 50 o C/min) from room temperature to 800 o C. From these methods, the
activation energies associated with particular degradation mechanisms have been determined. Additionally,
the dielectric properties of the bismaleimide resin were measured as a function of frequency (0.10 Hz to 1
MHz) and temperature (-115 o C to 240 o C) using spectroscopic techniques. Two dielectric relaxations, beta
and gamma, were observed in the material, and their activation energies calculated.
97
Talk Number: 17 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
MECHANISM OF MOLECULAR INTERACTION OF
OLIGOMERS WITH HYDRATED CEMENT PHASES
SUPERPLASTICIZER
Tariq Jamil1 , Hendrik Heinz1
1
Polymer Engineering Department, University of Akron, United States
Understanding the action of organic additives on hydrated cement phases is essential to develop novel admixtures and alternative cements with low carbon footprint. Due to the indirect nature of available experimental
information the true nanoscale morphology of hydrated cement surface and its interaction with additives has
remained elusive. Atomistic simulations at with the thoroughly validated PCFF-INTERFACE force field
allow first quantitative insight into the interactions of polyacrylate oligomers containing polyethylene side
chains with tobermorite 14 A (h k l) surfaces in aqueous solution. The results show that the acrylate backbone is more attracted to the surface than the polyethylene oxide side chains. In particular, carbonate
ions approach calcium ions on the tobermorite surface to form ion pairs. The adsorption energy on (001)
tobermorite facets remains under -1 kcal per mol acrylate monomer. Detailed results for a range of different
polymers and tobermorite facets (001) will be presented.
98
Talk Number: 18 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
COMPARISON OF PROPERTIES OF STAR AND LINEAR POLY(L-LACTIDE)
Grzegorz Lapienis1 , Ewa Piorkowska2 , Joanna Bojda2 , Michal Cichorek2
1
Department of Polymer Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of
Sciences, Poland
2 Department of Polymer Structure, Centre of Molecular and Macromolecular Studies, Polish Academy of
Sciences, Poland
The aim of the study is comparison of crystallization, structure and properties of 6 arm star-shaped
poly(L-lactide) (PLLA) with its linear analog.
PLLAs with molar mass Mw of 140 kg/mol were polymerized in bulk at the temperature of 130 o C.
The polymerization was initiated with dipentaerythritol in the presence of tin octoate as a catalyst [1].
The resulting polymers contained a low content of unreacted L-lactide (≤ 0.5 mol %) and were further
purified by precipitation from methylene chloride solution into methanol, homogenized in the molten state,
and analyzed by different methods. Crystallization, supermolecular structure, thermal, mechanical and
rheological properties of both PLLAs were examined.
Acknowledgment
This research project has been supported by the National Science Centre, Poland, grant No UMO2013/09/B/ST5/03619.
References
1. M. Srisa-ard, Y. Baimark, J. Appl. Sci., 2010, 10, 1937-1943.
99
Talk Number: 19 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
CHEMICAL MODIFICATION OF PROTEIN-BASED ADHESIVES FOR CONSTRUCTION APPLICATIONS
Shane Frazier1 , Wil Srubar1
1
Civil, Environmental, and Architectural Engineering, University of Colorado Boulder, United States of
America
Wood and engineered wood are among the most common materials used in building and construction.
A large percentage of engineered wood products contain adhesives that emit volatile organic compounds
(VOCs). Research has shown that VOCs have the potential to cause short- and long-term health effects.
Beyond health effects, commercially available wood adhesives are manufactured from nonrenewable sources
and are not biodegradable. Recent research has focused on the synthesis and characterization of alternative
adhesives from renewable resources, including starch, lignin, and gelatin. While preliminary studies
have shown that gelatin exhibits promising mechanical and adhesive properties compared to commercial
adhesives, one significant disadvantage that remains - especially if it is to be used as a construction material
- is gelatin’s inherent hygroscopicity.
This presentation will highlight current research on evaluating the feasibility of gelatin-based materials to serve as low-VOC construction adhesives. In this presentation, the effect of gelatin-to-water
concentration and gelatin source (i.e., porcine vs. bovine) on mechanical properties, thermal properties,
water and water-vapor absorption will be discussed. Given the wide range of material properties reported in
the literature, significant effort is currently being placed on correlating material properties to gelatin source
and amino acid content. Specifically, food grade porcine and bovine, BioReagent grade Type A porcine skin,
BioReagent grade Type B bovine skin, and pharmaceutical grade fish gelatin will be used in the synthesis
and characterization of gelatin films with varying gelatin-to-water concentrations. To counter gelatin’s
hygroscopicity, the effect of chemical additives (e.g., tannic acid, silane) on mechanical and moisture barrier
properties will also be presented. Achievable mechanical properties, moisture resistances, and VOC contents
of the gelatin-based adhesives investigated herein will be discussed in comparison to commercially available
wood adhesives.
100
Talk Number: 20 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
MOLECULAR DYNAMICS IN ELECTROSPUN FIBERS OF PLASTICIZED POLYLACTIDE
Xavier Monnier1,4 , Nicolas Delpouve1 , Neil Basson4 , Alain Guinault2 , Sandra Domenek3 , Allisson Saiter1 ,
Peter E Mallon4 , Eric Dargent1
1
AMME-LECAP EA 4528 International Lab., Normandie University, Université and INSA Rouen, France
Laboratoire PIMM, UMR 8006, ENSAM-CNRS-CNAM, Paris, France
3 UMR1145 Ingénierie Procédés Aliments, AgroParisTech, France
4 Division of Polymer Science, Department of Chemistry and Polymer Science, University of Stellenbosch,
South Africa
2
Polylactide (PLA) micro and nanofibers produced by the electrospinning process are used in several
fields including in applications for tissue engineering, filtration and electronics. The microstructure and
molecular dynamics of these electrospun fibers are tied to the macroscopic properties of the materials. The
electrospinning process itself can lead to non-equilibrium microstructures due to the complex processes
involved including the alignment and stretching of the molecules and the rapid solvent evaporation amongst
others. It is, therefore, important to understand both the microstructure and molecular dynamics, as the
alpha relaxation processes, to gain an understanding of the properties of these materials. In this study,
a thermodynamic approach was used to calculate the cooperativity length using modulated temperature
differential scanning calorimetry (MT-DSC). This technique has been widely used to provide evidence for
the effects of confinement [1], orientation [2], and plasticization [3] in many polymers including PLA.
To our knowledge, no studies have been done on the effect of the electrospinning process on the cooperativity
in PLA. In this work we investigate the cooperativity length at the glass transition in the bulk polymer and
the electrospun PLA fibers using Donth’s approach [4]. The possible correlations between the cooperativity
length and the inter- and intra-chain distances in the amorphous phase as determined [5] by wide angle
X-ray scattering (WAXS) were also investigated.
1. Arabeche, K. et al. Fragility and molecular mobility in micro- and nano-layered PC/PMMA
films. Polymer 55, 1546-1551 (2014).
2. Delpouve, N., Delbreilh, L., Stoclet, G., Saiter, A. & Dargent, E. Structural Dependence of the Molecular
Mobility in the Amorphous Fractions of Polylactide. Macromolecules 47, 5186-5197 (2014).
3. Dobircau, L. et al. Molecular mobility and physical ageing of plasticized poly(lactide). Polym. Eng. Sci.
in press DOI: 10.1002/pen.23952 (2014).
4. Donth, E. The size of cooperatively rearranging regions at the glass transition. J. Non-Cryst. Solids 53,
325-330 (1982).
5. Stoclet, G., Seguela, R., Lefebvre, J. M., Elkoun, S. & Vanmansart, C. Strain-Induced Molecular Ordering
in Polylactide upon Uniaxial Stretching. Macromolecules 43, 1488-1498 (2010).
101
Talk Number: 21 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
TRIBOLOGICAL PROPERTIES OF ANTIBACTERIAL POLYMER COMPOSITES
Witold Brostow1 , Stevens Brumbley2 , Marina Gakhutishvili1,4 , Nathalie Hnatchuk4 , Justin Youngblood4 , Sundari Pokharel3
1
2
3
4
Department of Materials Science and Engineering, University of North Texas, U.S.A
Department of Biological Sciences, University of North Texas, U.S.A.
Department of Chemistry, University of North Texas, U.S.A.
Faculty of Exact and Natural Sciences, Ivane Javakhishvili University, Georgia
One does not need to argue the importance of providing antibacterial activity to materials. The way it
was done earlier was simply using materials which can destroy bacterias. There are immediate problems
since some such materials including arsenic are highly toxic; they do destroy bacterias but not only .... One
option which has been used before our project began was using low molecular weight antibacterial agents.
This represents progress as compared to ‘nude’ arsenic or arsenic oxide; however, toxicity is mitigated only
to some extent while the service life is insufficient.
Our approach is different. We put arsenic (III) oxide into poly(vinyl chloride) (PVC). Sufficient antibacterial activity is achieved. The antibacterial material so obtained is non-irritant and non-toxic. At
the same time, the PVC-based composite has high thermal stability as demonstrated by thermogravimetric
analysis (TGA, Perkin Elmer). Thermal transitions have been located by differential scanning calorimetry
(DSC, Perkin Elmer). Still further, we have determined scratch resistance in a Microscratch Tester from
CSM, Peseux, Switzerland. Higher scratch resistance than in neat PVC has been demonstrated, including
stronger viscoelastic scratch recovery (the bottom of the groove goes up inside of 2 minutes).
Pertinent references:
[1] Patel M. B., Patel S. A., Ray, A., Patel R. M. Synthesis, characterization, and antimicrobial activity of acrylic copolymers. J. Appl. Polymer Sci. 2003; 89, 895-900.
[2] Tashiro T. Antibacterial and bacterium adsorbing macromolecules.
2001; 286, 63-87.
Macromol Mater.
[3] MuÅĹoz-Bonilla A., Fernandez-Garcia M., Polymeric materials with antimicrobial activity.
Polymer Sci. 2012; 37, 281-339.
102
& Eng.
Progr.
Talk Number: 22 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
LENGTH SCALE AT THE GLASS TRANSITION IN SEMI-CRYSTALLINE COMPATIBILIZED POLYLACTIDE/CLAY NANOCOMPOSITES
Nicolas Delpouve1 , Francesca Cicogna2 , Werner Oberhauser3 , Lucia Conzatti4 , Elisa Passaglia2 , Allisson
Saiter1
1
2
3
4
AMME-LECAP EA 4528 International Lab., Normandie University, Université et INSA Rouen, France
ICCOM, CNR UOS Pisa, Italy
ICCOM, CNR Firenze, Italy
ISMAC, CNR Genova, Italy
During the last ten years, great attention has been paid to the effects of interfaces and geometrical
confinement on the molecular dynamics of polymers [1,2,3]. One of the characteristic parameters describing
the glass transition is the cooperativity length which provides the average dimension of the alpha relaxation
process. To investigate the cooperativity length from calorimetric measurements, the Donth’s approach [4]
is the most appropriated. Previous works have highlighted that interfacial interactions between amorphous
polymer and exfoliated clays lead to a cooperativity length increase while confinement of polymer chains in
the galleries of clays (intercalated nanocomposite) produces a strong reduction of cooperativity [5]. In this
work we propose to investigate the nature of the polymer/clay interactions thanks to the cooperativity length
determination in Polylactide-based nanocomposites with the presence of polybutyrate adipate terephthalate
(PBAT) compatibilizer. Polylactide (PLA) is a semi-crystalline polymer which thermal crystallization can
easily be tailored due to its slow kinetic, and can induce different crystalline forms (α and δ) depending on
the crystallization temperature [6,7], leading to strongly ordered or defective crystals. So this study aims at
picturing the dissociated or cumulated impact of compatibilization and crystallization on the cooperativity
in exfoliated and intercalated morphologies.
(1) Schick, C. Eur. Phys. J. Spec. Top. 2010, 189, 3-36.
(2) Napolitano, S.; Wübbenhorst, M. Polymer 2010, 51, 5309-5312.
(3) Erber, M.; Georgi, U.; Müller, J.; Eichhorn, K.-J.; Voit, B. Eur. Polym. J. 2010, 46, 2240-2246.
(4) Donth, E. J. Non-Cryst. Solids 1982, 53, 325-330.
(5) Saiter, A.; Prevosto, D.; Passaglia, E.; Couderc, H.; Delbreilh, L.; Saiter, J. M. Phys. Rev. E 2013, 88,
042605.
(6) Righetti, M. C.; Tombari, E. Thermochim. Acta 2011, 522, 118-127.
(7) Delpouve, N.; Saiter, A.; Dargent, E. Eur. Polym. J. 2011, 47, 2414-2423.
103
Talk Number: 23 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
HYDROGEN BONDING INDUCED NANOPHASE SEPARATION OF GIANT SURFACTANTS TOWARD SUB-10-NM HYBRID ORDER NANOSTRUCTURES
Zhiwei Lin1 , Stephen Z. D. Cheng1
1
Department of Polymer Science, The University of Akron, United States
Assemblies and fabrications of hybrid materials containing functionalized nanoparticles (NPs) have attracted
numerous research interests over the past several decades. Giant surfactants are regarded as a library of new
hybrid materials based on polymer-tethered molecular NPs. In this work, two series of giant surfactants,
composed of a hydrophilic fullerene (AC60) NP tethered with a polystyrene-block-poly(ethylene oxide) (PSb-PEO) at the PS chain end (AC60-PS-PEO) or the junction point between two blocks (PS-(AC60)-PEO),
were designed to investigate their assemblies in the bulk. It was revealed that the incorporation of AC60
NPs induces the nanophase separation of intrinsically disordered PS-b-PEO with low molecular masses. A
variety of ordered nanostructures were formed including lamellae, double gyroids and cylinders with domain
sizes smaller than 10 nm. Two pairs of topological isomers, AC60-PS50-PEO45 and PS50-(AC60)-PEO45,
AC60-PS78-PEO45 and PS78-(AC60)-PEO45, were specifically investigated to reveal the topological effects
on assembled giant surfactants. It was found that the similar ordered nanostructures with different domain
sizes are resulted from assemblies of these topological isomers.
104
Talk Number: 24 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
TWO-DIMENSIONAL NANO-CRYSTALS OF MOLECULAR JANUS PARTICLES
Hao Liu1 , Chih-Hao Hsu1 , Zhiwei Lin1 , Kan Yue1 , Wen-Bin Zhang2 , Stephen Z. D. Cheng1
1
2
Department of Polymer Science, The University of Akron, U.S.A
College of Chemistry and Molecular Engineering, Peking University, P. R. China
In this work, we report the molecular design, synthesis and self-assembly of a series of novel molecular
Janus particles based on three nano building blocks (or called molecular nanoparticles, MNP), i.e., polyhedral oligomeric silsesquioxane (POSS) and hexa-molybdate, a Lindqvist-type polyoxometalate (POM), and
[60]fullerene (C60) derivatives. These amphiphilic molecular Janus nanoparticles was produced by covalently
connecting hydrophobic crystalline BPOSS with a charged hydrophilic MNP. The rational strategy to obtain self-assembled two-dimensional (2D) nano-crystals with definite and uniform thickness was based on
the distinct interactions of the constitutional moieties. Symmetry breaking in both chemical composition
and geometric shape leads to the formation of bilayered molecular packing setting through crystallization in
solution. In a polar solvent, individual two-dimensional (2D) nanosheets are formed with a thickness corresponding to the stack of two molecular layers driven by the directional crystallization of the POSS cages.
Aggregations of the nanosheets along the normal dimension are prevented due to the favored solvating interactions with the external ionic layers. This “bottom-up” fabrication of 2D nanosheets provides an alternative
strategy toward self-assembled 2D nanostructures.
105
Talk Number: 25 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
EFFECTS OF UV EXPOSURE ON PHYSICAL PROPERTIES OF CARBON
FIBER/PPS THERMOPLASTIC COMPOSITES
Khairul B. Mahat1 , Ibrahim Alarifi1 , Abdulaziz R Alharbi1 , Dr. Ramazan Asmatulu1
1
ME, Wichita State University, United States
The recent attentions in the applications of the fiber reinforced thermoplastic composite have raised
some concerns because of the ability and performance of the fiber reinforced thermoplastic composite
after long-term exposures to environmental weathering (e.g., UV radiation, moisture, and oxygen). This
weathering can be very destructive to the thermoplastic polymers; hence, a systematic study of the UV
radiation effects on the properties of fiber reinforced thermoplastic composite is crucial for industrial
applications. The major objective of the project was to study the correlation between thermoplastic
fabrication parameters and the final properties of composites. In this study, carbon fiber (CF) reinforced
polyphenylene sulfide (PPS) thermoplastic composites were manufactured using high temperature press
after optimizing the parameters. Subsequently, the effects of long term UV exposures on the thermal and
mechanical properties of CF/PPS thermoplastic composites were investigated in detail. The test results
showed that the correlation between the processing parameters and the physical properties of the laminate
composites were in all good agreements. The test results also revealed a significant decrease in the glass
transition temperature, as well as storage modulus, and tensile strengths. Furthermore, short (200 hrs) and
long (300 hrs) term UV exposures changed various thermal and mechanical properties of the thermoplastic
PPS composites. This study can provide some preliminary knowledge to engineers and scientists in the field
and develop new set of structural composites.
Keywords: PPS Films, Carbon Fibers, Thermoplastic Composites, UV Light Exposure, Mechanical
Properties.
106
Talk Number: 26 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
NANOMANUFACTURING POLYACRYLONITRILE NANOFIBER YARNS
Jase Kaser1 , Dimitry Papkov1 , Yuris Dzenis1 , Yong Liu1
1
Mechanical & Materials Engineering, University of Nebraska-Lincoln, United States
Nanomanufacturing Polyacrylonitrile Nanofiber Yarns
Jase Kaser (Presenting), Dimitry Papkov, Yuris Dzenis, Yong Liu
Continuous nanofibers (NFs) are an emerging class of materials with unique property combinations
and the potential to produce the next generation of advanced fibers. Our previous research found extraordinary simultaneous increases in NF strength, modulus and toughness with the decrease of their diameters
into the ultrafine (<250nm) range. Handling and utilization of individual NFs with such small diameters
is impractical for any macroscopic applications, and requires assembly of these NFs into yarns or other
macroscopic assemblies. During the manufacture of such assemblies, precision control over their different
aspects (such as pitch angle, yarn diameter, and NF diameter distribution within the yarn) is needed. A
novel nanomanufacturing process, which allows precision NF yarn production in “one-shot” was developed,
and a parametric study of nanomanufacturing parameters and their impact on the yarn characteristics was
performed. The manufacturability of nanofiber yarns with varying fiber diameter, yarn diameter, and pitch
angle was demonstrated through control of the spinning distance, rotation speed of the disc collector and
other process and solution parameters. Preliminary mechanical testing showed a significantly increased
strain to failure compared to individual NFs, leaving large room for mechanical properties’ improvement and
process optimization. The experimentally obtained mechanical properties were also compared with results
from numerical simulations.
107
Talk Number: 27 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
INTEGRATING C60 NANOPARTICLES INTO TIO2 NANOFIBERS VIA ELECTROSPINNING PROCESS FOR ENHANCED ENERGY CONVERSTION EFFICIENCIES
Manish A. Shinde1 , Abdulaziz R Alharbi1 , Ibrahim M. Alarifi1 , Dr. Ramazan Asmatulu1
1
Mechanical Engineering, Wichita State University, United States
TiO2 nanofibers incorporated with C60 nanoparticles at 0, 2, 4, and 8wt.% were produced using electrospinning process. The chemical utilized for the electrospinning process included poly (vinyle acetate),
dimetylfomamide, titanium (IV) isopropoxide and acetic acid in the presence and absence of C60 nanoparticles. The resultant nanofibers were heat treated at 300 o C for 2 hrs in a standard oven to remove all
the organic parts of the nanofibers, and then further heated up to 500 o C in Ar for additional 12 hrs to
crystalline the TiO2 nanofibers. SEM, TEM and XRD studies showed that C60 and TiO2 nanofibers were
well integrated in the nanofiber structures. The TiO2 and C60 nanofibers were then mixed in a solution
to form a paste which is then applied on a conductive glass by using a doctor blading technique to make
various DSSCs. This technique enables to create solar cells with variable thicknesses of 7 µm to 45 µm.
The ffects of the manufacturing technique, thickness of the paste, different percentages of C60 nanoparticles
on overall efficiency of the solar cell were studied. This paper also includes the TiCl4 treatments, which
greatly increases the efficiency of DSSCs. This study may guide some of the scientists and engineers to tailor
the energy bang gap structures of some of the semiconductor materials for different industrial applications,
including DSSC, water splitting, catalyst, batteries, and fuel cell.
Keywords: Electrospinning, TiO2 Nanofibers, C60 Nanoparticles, Heath Treatment, DSCC, Efficiency.
108
Talk Number: 28 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
AGEING OF A THREE-LAYER PAPER USED IN THE INSULATION OF AN ELECTRIC MOTOR FOR THE AUTOMOTIVE TRACTION
Florian Loubeau1,2,3 , Pascal Rain1,2 , Anne Durieux3
1
2
3
G2Elab, Univ. Grenoble Alpes, FRANCE
G2Elab, CNRS, FRANCE
Electric Materials Department, RENAULT SA, FRANCE
Electrical Insulation System (EIS) of the studied electric motor is composed of enameled wires, insulation
papers and impregnating resins. This EIS is subjected to various stresses: thermal (chemical kinetics,
thermal expansion), environmental (water absorption, oxidation, various pollutions), mechanical (vibrations,
frictions) and electrical (surge voltage applied by the inverter). In low voltage motors, thermal stress is
considered as the most influent in the degradation of the EIS.
Thermal class of these materials is generally given by the suppliers and corresponds to a lifetime of
20,000 hours at this temperature. Criterion for this end of life is chosen by the supplier. It can be a ratio of
mass loss, a relative decrease of Partial Discharge Inception Voltage (PDIV), or of the dielectric loss factor...
To determine the thermal class of these materials according to a functional property of our application, the
behavior of materials during thermal aging was studied. Samples of papers, enameled wires, resin wafers
and of a simple model of the EIS composed of these three materials were subjected to thermal aging at
190o C, 205o C and 220o C.
Results coming from the mass losses of the NKN three-layer paper (Nomex extregistered polyaramide /
Kapton extregistered polyimide / Nomex extregistered polyaramide) show a mechanism in two steps: the
first part of the curve corresponds to a first order reaction and the second part to a zero order reaction.
The first order reaction could correspond to a fast oxidation of structural irregularities and the zero order
reaction to the degradation of the structural unit. Apparent rate constants and activation energies have
been calculated following the Arrhenius law.
Physicochemical characterizations of the ageing by IR spectroscopy and dielectric spectroscopy were also
performed. IR spectroscopy shows for the Nomex a decrease of the N-H amide group absorption band and
the apparition of cyano groups. Regarding the Kapton, the imide group is more impacted by the degradation
than the ether group. Dielectric spectroscopy showed a decrease of the polarization and of the losses around
10 000 Hz. This value is typically the frequency used by the inverters of electrical vehicles.
109
Talk Number: 29 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
A STUDY OF THE EFFECTS OF SPIN COATING ON PVDF FILMS
Mitchell Schmidt1
1
Physics, University of Nebraska at Lincoln, USA
My research revolves around studying the properties of organic ferroelectrics. I specifically work with
Polyvinylidene fluoride (PVDF). Ferroelectric properties have been studied for years as they hold great
potential in a variety of fields including ferroelectric RAM, ferroelectric tunnel junctions and various sensor
devices. To study the properties of PVDF, thin films of the material are created. Currently there are two
ways to create thin PVDF films, Langmuir-Blodgett (LB) deposition and spin coating. LB deposition has
been utilized in our lab for years and thus is a very refined and useful technique. Spin coating on the other
hand has been only used in the creation of thick films and thus is not understood as well. My project
examined the possible potential for creating uniform thin films with spin coating. Though spin coating has
been used in the creation of PVDF samples for years the creation of high quality samples below 50 nm has
been tricky. My role has been to attempt this by adjusting various parameters such as, spin speeds, solvents
concentration, quantity of solvent dispersed, time span of spinning and so on. Each parameter’s effect was
studied in the creation and optimization of thin films. To test the effect of spin coating I utilized various
known tests. The most basic test was to measure the capacitance as a function of voltage or temperature.
Such scans indicate the level of crystalline structure in the material. Further test included doing pyro-electric
scans which measured the induced polarization caused by laser beams. In addition AFM, PFM, XRD and
ellipsometry were all useful techniques to infer a sample’s thickness, roughness and quality.
110
Talk Number: 30 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
INVESTIGATION OF ELECTRONIC PROPERTIES OF A GRAPHENE FIELD EFFECT TRANSISTOR
Simon Schönherr1 , Stefan Wagner2 , Himadri Pandey2 , Jasper Ruhkopf2 , Max Lemme2
1
2
Department Q2, Fürst-Johann-Moritz-Gymnasium, Germany
Graphene-based Nanotechnology, University of Siegen, Germany
Graphene is a material that has garnered enormous scientific and technological interest, since it was reported
for the first time in 2004[1]. This interest is mainly due to the unique properties of graphene, including
its attractive electronic and mechanical properties as well as the excellent thermal conductivity. These are
a consequence of its two-dimensional structure consisting of a single atomic layer of carbon. Graphene
is therefore a promising material for field effect transistors (FETs)[2,3]. In this experimental study we
investigated the electronic properties of graphene with a prototype of a graphene FET. In this prototype,
in which the graphene channel is contacted by gold source and drain contacts, the current between source
and drain is controlled by the gate voltage of a silicon back-gate. In a typical chip layout, 250 individual
FET devices were fabricated on one chip[4]. The graphene was deposited by chemical vapor deposition.
The transfer characteristics of the graphene-FET were characterized using a 3 point probe setup. The drain
current flowing through the graphene channel was recorded as a function of the gate voltage. The transfer
curves show a characteristic V shape. Drain currents were thus measured for positive as well as negative
gate voltages. This ambipolar behavior confirms that graphene conducts both electrons and holes. Secondly,
substantial drain currents were observed for all gate voltages between -5 V and +10 V: the minimum drain
current is at least 60% of the maximum drain current over the gate voltage range. This observation can be
explained with the energy band diagram of graphene, which does not contain any band gap (zero band gap
semiconductor). Consequently, graphene-FETs in the investigated configuration with a single layer graphene
channel can probably not be seen as an alternative for silicon-based FETs in logic circuits because of the
fact that the FET is always turned on. This behavior prevents the use of these FETs in a system, in which
the difference between 0 and 1 (on & off) is the general principle. Nevertheless an application of graphene
in high frequency circuits is still possible, especially because of the high carrier mobility of graphene[5].
[1]
[2]
[3]
[4]
[5]
K.S. Novoselov et al. Science 2004, 306, 666
A.K. Geim et al. Nat Mater 2007, 6, 183
M.C. Lemme et al. IEEE Electron Device Lett. 2007, 28, 282
A.D. Smith et al. Accept. Solid State Electron. 2015
M.C. Lemme et al. MRS Bull. 2014, 39, 711
111
Talk Number: 31 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
BROADBAND DIELECTRIC RELAXATION ANALYSIS ON THE REINFORCEMENT OF ANTHRACENE-FUNCTIONALIZED EPOXY COMPOSITES
Rui Ding1 , Sabrina Wells2 , Jamie Messman2 , Daniel Bowen2 , Nicola Bowler1
1
2
Materials Science and Engineering, Iowa State University, United States
Department of Energy’s National Security Campus, Honeywell FM&T, LLC, United States
Two polycyclic aromatic hydrocarbon (PAH) derivatives, namely anthracene (up to 5 wt.%,) and 2-aminoanthracene (up to 10 wt.%) were dispersed in a model epoxy matrix as novel composite dielectrics. The dielectric
relaxation properties of anthracene-functionalized epoxy composites were investigated via broadband dielectric spectroscopy over the frequency range from 0.02 to 1,000,000 Hz and temperature range from -100 to
130 o C. Within the measured domain, four phenomena, namely α-, β-, and γ-relaxation processes and ionic
conductivity are identified for all the samples. The Havriliak-Negami (HN) dielectric relaxation model was
applied to parametrically fit each relaxation and the characteristic relaxation times of the anthracene-functionalized epoxy composites were compared. A significant increase of glass transition temperature (Tg) is
observed in the system with coexistence of anthracene and 2-aminoanthracene, by both dielectric spectroscopy
and differential scanning calorimetry (DSC).
112
Talk Number: 32 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
SYNTHESIS AND PROPERTIES OF REACTIVE OLIGOMERS BASED ON A PEROXY DERIVATIVE OF AN EPOXY RESIN AND 1,4- BUTANEDIOL
Witold Brostow1 , Olena Astakhova2 , Ostap Ivashkiv2 , Olena Shyshchak2 , Haley Lobland1
1
2
Materials Science and Engineering, University of North Texas, USA
Polymer Chemistry and Technology, Lvivska Politechnika National University, Ukraine
Oligomers products with various functional groups are widely used as crosslinking and modified agents of
polymeric mixtures. We have synthesized an oligomer containing simultaneously peroxy and hydroxy groups.
The oligomer has the molecular mass M = 490 g/mol and active oxygen content 1.9 %. The presence of hydroxy groups is confirmed by absorption band at 3384 cm-1 in IR-spectrum. The presence of the
peroxy groups is confirmed by the band at 1380 and 1360 cm-1 and ether bond - at 1248 and 1040 cm-1
(formed by the interaction of peroxide oligomer with butanediol).
Our oligomer has been studied as active additive to epoxy-oligoesteric mixtures on the basis of an industrial
dianic epoxy resin with the epoxy number 20.0 % and an oligoesteracrylate on the basis of triethyleneglycol
and methacrylic acid with M = 280 g/mol. The synthesized oligomer constitutes 10/100 mass parts of the
mixture. The crosslinking was studied stepwise: first at room temperature and then at 383 and 423 K
for 15, 30, 45, 60 and 75 minutes. The polymeric films so obtained are characterized by good adhesion to
substrates, hardness between 0.7 and 0.8 in relative units and gel-fraction content 80-96 %.
113
Talk Number: 33 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
SYNTHESIS AND CHARACTERIZATION OF POLYMERS WITH ANTIBACTERIAL PROPERTIES BASE ON TRICLOSAN ACRYLATE
Wilson Isidro Cardona1 , Anny Catalina Ospina1 , Carlos Alberto Pelaez1 , Luis Fernando Giraldo1
1
Instituto de Química, Universidad de Antioquia, Colombia
In this research a monomer of triclosan acrylate was synthesized by reacting acryloyl chloride with triclosan in
the presence of a base. The monomer was polymerized by free radical bulk polymerization in order to obtain
the homopolymer of triclosan acrylate and the copolymers with styrene at different molar ratios. The final
polymers were characterized by infrared spectroscopy, differential scanning calorimetry, thermogravimetric
analysis and gel permeation chromatography. The antibacterial activity for the polymers was determinate
against Bacillus subtilis, Staphylococcus aureus and Escherichia coli. The results show that the monomer
of triclosan and its homopolymer had the higher antibacterial activity and an important reduction in the
bacterial population was also achieved with only 10 % of TCA in polystyrene. The glass transition temperatures for the copolymers were between the Tg for the homopolymer of TCA (58 o C) and polystyrene (75
o C), indicating a good compatibilization of both monomers. The higher number and weight average molecular weights for the copolymers were 12628 and 32941 g/mol, respectively. These polymers have potential
applications in paint and coating industry and medical devices.
114
Talk Number: 34 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
USING CURING KINETICS TO CONTROL THE MECHANICAL PROPERTIES
OF SIMULTANEOUS ACRYLATE/EPOXY IPNS DURING PHOTO CURING OF
GRADED MATERIALS
Marzieh Bakhtiary Noodeh1 , Wenlong Li1 , Steven Araujo2 , Nicolas Delpouve2 , Jean-Marc Saiter2 , Mehrdad
Negahban1
1
2
Mechanical & Materials Engineering, University of Nebraska-Lincoln, United States
LECAP, University of Rouen, France
Interpenetrating polymer networks (IPNs) are made from two or more polymer networks that are cured
simultaneously to achieve interpenetration, and can be usually made to express a range of characteristics
between those of the constructing networks [1]. One way to achieve grading with an IPN system is to vary
the amount of the components. This can be used to vary not only mechanical properties, but also optical,
electrical and other properties. The main issue is how to control the composition, yet obtain an IPN with
good properties. Normally the networks of IPNs with good characteristics are grown concurrently and, thus,
this type of IPN is called a Simultaneous IPNs [2, 3]. We studied how one can control the curing kinetics
for photo cured systems to get Simultaneous IPNs of acrylate and epoxy with different final mechanical
properties. Laser assisted UV-light curing on a Rapid Scan FTIR equipped with a temperature controlled
ATR was used to follow the construction of the networks and to design the controlling method. It is shown
that by this method one can get a wide range of properties starting from a single mixture. This UV-light
controlled process can be used in photolithography to vary properties in a 3D printing system.
115
Talk Number: 35 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
MOLECULAR STRUCTURE PARAMETERS INFLUENCE ON DEFORMATION
MECHANICS OF AN ORIENTED CRYSTALLINE POLYMER
Ulmas Gafurov1
1
Composite Materials, Institute of Nuclear Physics, Uzbekistan
Taking into account that real crystalline polymer molecular and supra-molecular structure and the
interconnecting macromolecules have different conformation links we have carried out modeling of an
oriented polymer deformation and creep molecular processes. We have considered two-phase model of
an oriented flexible-chain crystalline polymer type of linear polyethylene micro-fibrils of which consist
of interchanging crystalline and amorphous regions. In the deformation molecular mechanics modeling
the Frenkel-Kontorova’s crowdion was used for condition of balance and longitudinal mobility of an
interconnection macromolecular chain.
The dislocation formation is stimulated by thermo-fluctuation and stressed load and is accompanied
molecular chains exit of crystallites, elongation of amorphous section of interconnecting molecular chain
and correspondingly lead to local loads relaxation on their amorphous sections as well as by conformation
regroupings of these sections in some conditions especially for flexible chain polymer.
The load relaxation value and the dislocation evolution depends except of macromolecular chain parameters mainly from dimension sizes of an interconnecting amorphous section and of initial local load on
it, presence of cross-links, interpenetrating, loops in neighboring amorphous sections, defect structure of
polymer crystallites. .
For high-oriented flexible-chain crystalline polymers at the certain values of slippage chains number
there was the further discontinuous jump conformation structure (conformation straightening) of the
interconnecting amorphous section.
The dislocation forming thermo-activation energy values for various loads and the longitudinal sizes
of crystal and amorphous regions are designed.
The dislocation moving to amorphous region lead to the interconnecting chain pulled into crystallite
with local load value increasing on amorphous section and the thermo-fluctuation energy dissipation.
In a real polymer there is the wide distribution over the amorphous and crystalline regions sizes. As
a result of this in the polymer being under external load the values of the local loads on the amorphous
sections, correspondingly the activation energy for the dislocation formation and the velocity of the molecular
chains longitudinal mobility and molecular deformation process will be also different.
116
Talk Number: 36 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
NOVEL CHART FOR REPRESENTATION OF MATERIAL PERFORMANCE AND
RELIABILITY
Franz Lanyi1 , Peter Kunzelmann1 , Dirk W. Schubert1
1
Institute of Polymer Materials, Friedrich-Alexander-University Erlangen-Nuremberg, Germany
In modern industrial production lines various process and material parameters determine the properties of
the final product. Thus, a process optimization procedure has to take into account a large design space
containing several parameters. As a consequence the evaluation of the influence of single process parameters
on the final product properties can be quite complicated. Usually a certain property of a product, for
example the mechanical strength, has to satisfy a defined specification. In terms of quality control not only
the performance of the material but also the reliability of the specified values has to be considered.
The Weibull statistic gives an interesting approach to evaluate both, material’s performance and reliability.
Regarding the mechanical properties e.g. in terms of the stress at break the Weibull analysis leads to a
characteristic failure constant σ b,0 at which 63.2 % of the samples will break. Additionally, the Weibull
modulus m can be regarded as a measure for the width of the distribution of the measuring results. High
values of m represent a narrow distribution and thus a better reliability. Moreover, the Weibull modulus
m is independent of the absolute value of the measuring data. Therefore, it is possible to compare samples
produced under different conditions. The standard deviation and the interquartile range are often used to
quantify the scatter of empirical data. It is shown within this work that the Weibull modulus m can be a
more precise discriminator for the evaluation of the reliability because it is rather stable against outlaying
values.
As an example this study concentrates on the mechanical properties of melt spun fibres consisting of blends
from polypropylenes with different molar masses produced under various process conditions. This work
presents a novel chart which allows one to compare different samples on the basis of the Weibull statistics
whereat the Weibull modulus m is plotted over σ b,0 . Defining a reference material, the m-σ b,0 -map can
be split into quadrants, whereat each quadrant designates an improvement or worsening of material’s
performance and reliability with respect to the reference. An evaluation in terms of performance and
reliability of great sets of data is easily applicable. It will be shown that the Weibull statistic can also be
applied to the Young’s Modulus, the elongation at break and the tensile energy absorption.
117
Talk Number: 37 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
U-SHAPED PROBES FOR CHARACTERIZATION OF POLYMERS USING CONTACT RESONANCE ATOMIC FORCE MICROSCOPY
Ehsan Rezaei1 , Joseph Turner1
1
Mechanical and Materials Engineering, University of Nebraska-Lincoln, USA
Contact resonance atomic force microscope (CR-AFM) methods have been commercially used to quantify
the elastic and viscoelastic properties of a variety of materials such as polymers, ceramics and biological
materials. This approach involves measurement of the resonant frequencies of the AFM probe both for the
free case and the case for which the tip is in contact with a sample. Vibration models of the probe and
tip-sample contact models are then used to determine the sample properties from the frequency behavior
and to create images of the sample properties. U-shaped AFM probes have been developed to allow local
heating of samples and the resonances of these probes are much more complex. A simplified analytical model
of these U-shaped probes is described here. This three beam model (TBM) includes two beams clamped at
one end and connected with a perpendicular cross beam at the other end. The sensitivities of the modes
to the specimen properties are then examined using a tip-sample contact represented by three orthogonal
Kelvin-Voigt models for the vertical, lateral and axial stiffness of the contact. In this poster, we demonstrate
the mode frequency sensitivity to the contact stiffness changes. The frequencies and mode shapes that result
from this model agree well with solutions created using the finite element method (FEM). As expected, the
modes involving symmetric flexural motion of the legs are most sensitive to the vertical contact stiffness
while the modes associated with unsymmetric flexural motion of the legs are most sensitive to the lateral
contact stiffness. This work is anticipated to provide a simple analysis method allowing U-shaped probes
with CR-AFM to be used for polymers.
118
Talk Number: 38 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
STUDY OF AMORPHOUS
NANOCOMPOSITE FILMS
Session: W4: Poster (Ballroom)
AND
CRYSTALLINE
PHASES
IN
BIO-BASED
Sebastien Charlon1 , Nadege Follain1 , Laurent Delbreilh2 , Eric Dargent2 , Jeremy Soulestin3 , Michel
Sclavons4 , Stephane Marais1
1
2
3
4
PBS UMR6270, Université de Rouen, France
AMME-LECAP, Université de Rouen, France
Institute, Ecole de Mines de Bouai, France
IMCN Institute, Catholic University of Louvain la Neuve, Belgium
With the emerging environmental concerns, many research works are focused on the use of biodegradable
polymers with the aim of reducing plastic pollution [1].
Among them, PolyButylene Succinate (PBS) and polyButylene Succinate Adipate (PBSA) are expected
to be promising candidates to substitute common polyolefins due their good properties (biodegradability,
processability, chemical resistance, mechanical performances [2]. However, their softness and their poor
barrier properties [3] limit their use in industrial applications like packaging.
One of the relevant ways to significantly improve these characteristics is to incorporate nanofillers,
even at low content. In this work, an optimized 5 wt% [4] nanoclay content (unmodified montmorillonite
(MMT) and organo-modified montmorillonite (OMMT)) was introduced within PBS and PBSA matrices by
melt blending processing.
To date, a higher crystallinity degree for PBS-based films than for PBSA-based films was calculated
by X-ray diffraction and Differential Scanning Calorimetry (DSC) measurements. These experiments did
not reveal any microstructure variation with nanofiller loading. Polarized optical microscopy showed that
the introduction of MMT lead to decrease spherulite sizes while the opposite effect was observed with
the incorporation of OMMT. Finally, Broadband Dielectric Spectroscopy (BDS) experiments exposed one
α-relaxation and two β-relaxations for both PBS and PBSA-based films, respectively associated to the
motion of polymer chains and of small polar groups. Glass transition temperature determined from BDS
curves was founded lower for PBSA than PBS, as observed by DSC measurements. Moreover, relaxations
are not modified by the presence of nanofillers, revealing that only the crystalline phase of polymer is
affected by the clay introduction.
[1] P. Bordes, E. Pollet, L. Avérous, Progress in Polymer Science, 2009, 34, 125-155
[2] T. Fujimaki, Polymer Degradation and Stability, 1998, 59, 209-214
[3] K. Okamoto, S.S. Ray, M. Okamoto, Journal of Polymer Science: Part B: Polymer Physics, 2003, 41,
3160-3172
[4] B. Alexandre, D. Langevin, P. Médéric, T. Aubry, H. Couderc, G.T. Nguyen, A. Saiter, S. Marais,
Journal of Membrane Science, 2009, 328, 1316-1324
119
Talk Number: 39 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
MICROSTRUCTURE, AMORPHOUS PHASE DYNAMICS AND BARRIER PROPERTIES IN MULTILAYER COEXTRUDED POLYLACTIDE
Samira Fernandes Nassar1,2,3 , Nicolas Delpouve1 , Alain Guinault2 , Laurent Delbreilh1 , Cyrille Sollogoub2 ,
Sandra Domenek3 , Eric Dargent1
1
2
3
AMME-LECAP EA 4528 International Lab., Normandie University, Université and INSA Rouen, France
Laboratoire PIMM, UMR 8006, ENSAM-CNRS-CNAM, Paris, France
UMR1145 Ingénierie Procédés Aliments, AgroParisTech, France
The development of biopolymers for food-packaging applications implies combining ecofriendly character
and non-toxicity to specific industrial requirements as low-cost and good mechanical, thermal and barrier
properties. Polylactide (PLA) has exhibited promising applications in the past decades due to its performance in renewability, biodegradability, biocompatibility, and mechanical properties [1]. As one of the major
challenges to consider producing high performance PLA packaging at a large scale lies in the improvement
of its barrier properties, the tailoring of the PLA microstructure from thermal crystallization [2,3], drawing
[4], or shish-kebab crystallization [5] has been strongly investigated in the recent years. New strategies
are actually studied to obtained stronger effects. One of them consists in the geometrical confinement of
the polymer at the molecular scale using the layer-multiplying co-extrusion process combined eventually
with annealing processes to create nanometric thickness layers. This technology is environmentally friendly
and health secured and has already proved its efficiency to improve the gas barrier properties for other
polymers [6]. In this work we propose to design monolayer and multi-layer coextruded PLA and to analyze
the relationships existing between its microstructure and the resulting gas barrier properties. Eventually as
transport properties are mainly governed by the diffusion in the amorphous phase, a picture of the molecular
dynamics in the amorphous phase will be given.
(1)
(2)
(3)
(4)
(5)
15,
(6)
Auras, R.; Harte, B.; Selke, S. Macromol. Biosci. 2004, 4, 835-864.
Guinault, A.; Sollogoub, C.; Ducruet, V.; Domenek, S. Eur. Polym. J. 2012, 48, 779-788.
Cocca, M.; Lorenzo, M. L. D.; Malinconico, M.; Frezza, V. Eur. Polym. J. 2011, 47, 1073-1080.
Delpouve, N.; Stoclet, G.; Saiter, A.; Dargent, E.; Marais, S. J. Phys. Chem. B 2012, 116, 4615-4625.
Bai, H.; Huang, C.; Xiu, H.; Zhang, Q.; Deng, H.; Wang, K.; Chen, F.; Fu, Q. Biomacromolecules 2014,
1507-1514.
Carr, J. M.; Mackey, M.; Flandin, L.; Hiltner, A.; Baer, E. Polymer 2013, 54, 1679-1690.
120
Talk Number: 40 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
RELAXATION OF SHEAR-INDUCED PRECURSORS IN POLY(LACTIC ACID)
Manon Tesserau1 , Ezequiel Morin2 , Benjamin Schamme1 , Constantine Tarawneh2 , Antonella Esposito1 , Li
Tan3 , Eric Dargent1 , Lucia Fernandez-Ballester3
1
2
3
Advanced Materials and Mechanical Engineering, AMME-LECAP International Laboratory, France
Transportation Center for Railway Safety, University of Texas - Pan American, United States
Mechanical and Materials Engineering, University of Lincoln-Nebraska, United States
Semicrystalline polymers are usually processed from their molten state and subjected to intense shear
and/or elongation flows [1]. Within the past few years, a whole array of studies has shown that flow
has a large impact on crystallization kinetics and morphology of semicrystalline polymers and therefore,
on final properties [2]. Understanding flow induced crystallization (FIC) is thus of utmost importance
of the production of tailored-properties products, particularly with polymeric materials. Theoretical and
experimental work highlighted that final morphology is dictated by structures present in the melt at the
early stages of shear and crystallization [3]. These structures are called precursors and their nature is
currently under investigation [4-5].
However, FIC studies were mainly focused on industrial polymers as polypropylene, polyethylene or random
copolymers but fewer on biopolymers [6]. As one of the most promising biopolymers, Poly(lactic acid)
(PLA) exhibits a reliable panel of performances in terms of availability, biocompatibility and biodegradability.
Using a commercial PLA, a fiber pull-out technique coupled with polarized optical microscope and a
hot stage has been used, as in terms of sensitivity is the most powerful indicator of melt perturbations. The
distinct morphological zones that happen after shear and relaxation (cylindritic or highly nucleated morphology and classical spherulitic morphology) have been used as an indicator of whether full reequilibration
has been attained or not in the sheared melt. Quantitative data as lifetime of precursors, t*, has been investigated in a wide range of relaxation temperatures and compared to other industrial semicrystalline polymers.
[1] Bove, L.; Nobile, M. R. 2002. Macromolecules Symposium. 185, 135-147.
[2] Hsiao, B. S.; Yang, L.; Somani, R. H.; Avila-Orta, C. A.; Zhu, L. 2005. Phys. Rev. Lett. 94, 117802.
[3] Kornfield, J.; Kumaraswamy, G.; Issaian, A. 2002. Ind. Eng. Chem. Res. 41, 6383-6392.
[4] Balzano, L.; Kukalyekar, N.; Rastogi, S.; Peters, G. W. M.; Chadwick, J. C. Phys. Rev. Lett. 2008. 100,
048302-048304.
[5] Azzurri, F.; Alfonso, G. C. 2005. Macromolecules. 38, 1723-1728.
[6] Xu, H.; Xie, L.; Chen, Y. H.; Huang, H. D.; Xu, J. Z.; Zhong, G. J.; Hsiao, B. S.; Li, Z. M. 2013. ACS
Sustainable Chem. Eng. 1, 1619-1629.
121
Talk Number: 41 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
EFFECT OF COPOLYMER CONTENT ON FLOW-INDUCED CRYSTALLIZATION
Ramin Hosseinabad1 , Frederic Aubin1 , Hugo Boitoit1 , Eric Dargent2 , Lucia Fernandez-Ballester1
1
2
Mechanical and Materials Engineering, University of Nebraska-Lincoln, United States of America
Advanced Materials and Mechanical Engineering, AMME-LECAP International Laboratory, France
Semi-crystalline polymers melts are often subjected to strong flows while undergoing processes. It is well
known that flow can significantly alter the kinetics of crystallization and the resulting semi-crystalline
structure, which in turn deeply affects the material properties of the final product. Therefore, it is
important to understand the basic mechanism and the variables that control flow-induced crystallization. In
general, both the molecular structure and the processing conditions significantly impact the crystallization
process. Here, the role of co-monomer content and temperature on flow-induced crystallization are examined.
In this study, isotactic polypropylene and random ethylene co-monomers are subjected to short pulses of
high shear stresses at several crystallization temperatures. The critical shear stress for formation of a highly
oriented skin was studied for each of the polymer grades. It was found that for polypropylene homopolymer,
the critical shear stress for crystallization temperature of 140C was smaller than that for 150C. However, the
critical shear stress was indistinguishable between 150C and 160C. For polypropylene with 3% co-monomer,
the critical shear stress also increased when crystallization temperature was raised up from 140C to 150C.
However, further temperature increase to 160C resulted in disappearance of the highly oriented skin layers:
instead, a different morphology was obtained at the highest levels of shear stress, which was observed as
somewhat bright areas under the polarizing optical microscope. Finally, polypropylene with 7% ethylene
co-monomer exhibited the same trend and value for critical shear stress at crystallization temperature of
130C and 140C. In this case, however, rising the crystallization temperature to 150C resulted in almost
complete disappearance of the highly oriented skin. The behavior of the real-time birefringence during and
right after cessation of the shear pulse was examined. The observed trends and their relationship with
subsequent structure development for each of the three polymer grades will be discussed.
122
Talk Number: 42 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
THE POSS AND MWCNT MODIFIED GLASS TRANSITION TEMPERATURE TG
OF POLY(VINYL CHLORIDE)
Jolanta Tomaszewska1 , Tomasz Sterzynski2 , Katarzyna Skórczewska1 , Jacek Andrzejewski2
1
Faculty of Chemical Technology and Engineering, UTP UNIVERSITY OF SCIENCE AND TECHNOLOGY, Poland
2 Institute of Materials Technology, Poznan University of Technology, Poland
The aim of our studies was to modify specifically the poly(vinyl chloride) (PVC) by using of nanoadditives
like polyhedral oligomeric silsesquioxane (POSS) and multi-wall nanotubes (MWCNT). As a nanofiller
three types of polyhedral oligomeric silsesquioxanes and multiwall carbon nanotubes were used. The
nanocomposites of PVC with various contain of fillers (concentration of POSS was in the range between 0.5
and 10 wt.%, the MWCNT contain was between 0.01 wt.% and 0.05 wt.%) were prepared by melt mixing
processing. As matrix the PVC compound in a form of dry blend, containing stabilizer and paraffin wax
was applied. The POSS and MWCNT were introduced into the PVC matrix by different procedures of
compound preparation, followed by melt mixing.
Our interest was to determine the influence of the nanomodification on certain properties of PVC,
like glass transition temperature; a property which determines the possible applications of this polymeric
material, thus the temperature dependent macromolecular mobility.
The glass temperature was measured by means of dynamic mechanical analysis DMA, differential
scanning calorimetry DSC and dielectrical measurements. The effect of a fabrication way of the nano
modified PVC on the glass transition temperature has also been investigated.
By use of MWCNT always an increase of Tg of PVC with increasing concentration of the nanoadditive was noted, signifying an important effect of nanotubes on the PVC chain mobility. The saturation - like
effect was observed already by the MWCNT contain equal to 0.01-0.02 wt.%.
An opposite effect, i.e. a decrease of Tg was found in the case of PVC modification with polyhedral
oligomeric silsesquioxane, particularly with 3-chloropropyl POSS and those containing methacryl and octyl
groups. This observation may be an indication of a plastyfing effect, due to a possible introduction of POSS
molecules between the PVC macromolecules.
In every case, the higher was the frequency used in our experiment, the higher was the value of the
Tg .
123
Talk Number: 43 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
INFLUENCE OF STRUCTURAL FEATURES OF POROGEN MOLECULES
ON
THERMAL
PROPERTIES
AND
POROSITY
OF
NANOPOROUS
POLYCYANURATE-BASED FILM MATERIALS
Kristina Gusakova1 , Jean-Marc Saiter2 , Alexander Fainleib1 , Olga Grigoryeva1 , Daniel Grande3
1
Department of Heterochain Polymers and Interpenetrating Polymer Networks, Institute of Macromolecular
Chemistry of the National Academy of Sciences of Ukraine, Ukraine
2 AMME-LECAP International Lab. Institute for Material Research, Université de Rouen, France
3 Institut de Chimie et des Matériaux Paris-Est, UMR 7182 CNRS - Université Paris-Est Créteil Val-deMarne, France
The present communication is focused on the investigation of the influence of molecular and structural
features of porogens on thermal behaviour and porosity characteristics of nanoporous polycyanurate-based
film materials produced via the chemically-induced phase separation technique. For this purpose, several
high-boiling temperature (Tb ∼280-380o C) low-molecular phthalates were used as porogens. The molecular
radius of all the phthalates was varied in the range of 0.405-0.545 nm. Miscellaneous investigations of both
isothermal (at 50, 100, 150 and 250o C for 48 h) and dynamic (starting from 30 up to 700o C at 20o C/min)
heating of nanoporous films in either inert or air atmosphere were fulfilled. Isothermal annealing experiments
showed similar kinetic behaviours for all the nanoporous PCN-based materials studied. Therefore, the
identity of processes occurred while annealing at 50-150o C was concluded. Standard TGA measurements
demonstrated high thermal stability of all the samples before and after isothermal annealing (at T up
to 150o C), regardless of the porogen structure. A drastic darkening and a significant decrease in the
thermal stability of the nanoporous PCN-based samples annealed at 250o C confirmed the occurrence
of thermal-oxidative degradation at such an annealing temperature. The presence of nano-sized pores,
before and after isothermal annealing, disregarding the temperature of annealing was confirmed using
several techniques, including SEM, N2 sorption, and DSC-based thermoporometry. A strong influence of
the porogen structure was evaluated on the porosity characteristics, and consequently on the desorption
behaviour of nanoporous PCN-based films annealed at 50-150o C. It was also established that the formation
of the most thermodynamically stable porogen-containing PCN networks allowed for introducing larger
porogen amounts, thanks to the deferment of the phase separation process. As a result, the generation of
relatively more dense and homogeneous nanoporous structures could be achieved.
This investigation could be useful for a possible prediction of long-term properties of porous film materials
derived from thermosetting densely crosslinked polycyanurates and related (co)polymers.
Acknowledgements. The authors are thankful to the National Academy of Sciences of Ukraine and
the “Centre National de la Recherche Scientifique” for financial support through PICS project No 5700
(Ukraine-France cooperation 2011-2013).
124
Talk Number: 44 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
INVESTIGATION OF FRACTURE BEHAVIOR OF HETEROGENEOUS POLYMER MIXTURES SUBJECTED TO VISCOELASTIC DEFORMATION USING MICROSTRUCTURAL MODELING
Keyvan Zare Rami1 , Yong-Rak Kim1 , Taesun You1
1
Civil engineering, University of Nebraska Lincoln, USA
This paper presents a microstructural modeling of heterogeneous polymer mixtures where viscoelastic and
fracture are significant sources of energy dissipation and failure-associated phenomena. Complex geometric
characteristics of mixture microstructures are represented by an image technique, and individual mixture
constituents such as elastic particles and surrounding viscoelastic matrix are characterized for their material
properties. In addition, cohesive zones are embedded in the mixture microstructure to account for fracture
within the mixture microstructure. A series of laboratory tests are performed to obtain elastic, viscoelastic,
and fracture properties of the mixture components and overall damage-associated performance of the entire
mixture. The computational microstructure modeling is validated by comparing simulation results with the
experimental test results of the mixture. The results presented in this paper clearly indicate that the effect of
microstructure and individual component material properties on the overall macroscopic damage-associated
behavior of the heterogeneous media.
125
Talk Number: 45 (Poster)
Time: Wednesday, May 13, 2015 1:50 PM
Session: W4: Poster (Ballroom)
POLAR PHASE GENERATION IN PVDF, THROUGH AMPHIPHILIC IONIC LIQUID MODIFIED MULTIWALLED CARBON NANOTUBES: EFFECT OF ANION
Ali Bahader1 , Haoguan Gui1 , Huagao Fang1 , Yu Li1 , Shaojun Wu3 , Yunsheng Ding1,2
1
Polymer Science and Engineering, Hefei University of Technology, China
Provincial Key Laboratory of Advanced Functional Materials and Devices, Hefei University of Technology,
China
3 Institute of optoelectronics, Hefei University of Technology, China
2
This study describe the effect of multiwalled carbon nanotubes (MWCNT), ionic liquid (IL) and IL modified MWCNT on the crystallization and polar phase generation of melt crystallized PVDF. The surface of
MWCNT was modified with two types of ILs, 1-hexadecyl-3-methyl-imidazolium bromide [C16MIM][Br] and
1-hexadecyl-3-methyl-imidazolium hexafluorophosphate [C16MIM][PF6]. The nanocomposites were characterized using FE-SEM, FTIR-ATR, XRD, DSC and EDX. Surprisingly, the results demonstrate that the
presence of IL accelerated the process of PVDF crystallization, because IL are well-known to act as a plasticizer for polymers and retard the crystallization process. Both, IL and IL-modified MWCNT are able to
generate β/γ phase/s of PVDF. The role of the anion also proved very effective, in terms of fast crystallization
process and β/γ phase generation.
126
Thursday, May 14, 2015 Starting: 8:30 AM
TH1: Plenary (Henzlik 124)
Session Chair: Yuris Dzenis
Assistants: Kaspars Maleckis, Zesheng Zhang
Talk:
1. (8:30 AM, Plenary) Cheng: GIANT POLYHEDRA AND GIANT SURFACTANTS BASED ON
NANO-ATOMS: TUNING FROM CRYSTALS, TO QUASICRYSTALS, TO FRANK-KASPER
PHASES: AN INTERCONNECTION BETWEEN SOFT AND HARD MATTER
Dr. Stephen Z.D. Cheng, Frank C. Sullivan Distinguished Research Professor, Robert C. Musson Professor,
Trustees Professor, NAE, Department of Polymer Science, The University of Akron
127
Talk Number: 1 (Plenary)
Time: Thursday, May 14, 2015 8:30 AM
Session: TH1: Plenary (Henzlik 124)
GIANT POLYHEDRA AND GIANT SURFACTANTS BASED ON NANO-ATOMS:
TUNING FROM CRYSTALS, TO QUASICRYSTALS, TO FRANK-KASPER
PHASES: AN INTERCONNECTION BETWEEN SOFT AND HARD MATTER
Stephen Z. D. Cheng1
1
Department of Polymer Sceince, The University of Akron, USA
In order to create new functional materials for advanced technologies, both precise control over functionality
and their hierarchical structures and orders are vital for obtaining the desired properties. Among all the
giant molecules, giant polyhedra are a class of materials which are utilized by deliberately placing precisely
functionalized polyhedral oligomeric silsesquioxane (POSS) and fullerene (C60) molecular nano-particles
(MNPs) (so-called “nano-atoms”) at the vertices of a polyhedron. Giant surfactants are polymer tail-tethered
“nano-atoms” where the two components have drastic chemical differences to impart amphiphilicity. These
giant polyhedra and giant surfactants capture the essential structural features of their small-molecule
counterparts in many ways but possess much larger sizes, and therefore they are recognized as size-amplified
versions of those counterparts. One of the most illustrating examples is a series of novel giant tetrahedral and
giant surfactants which possess precisely defined amphiphilic MNPs with different geometric combinations.
When both geometrical and chemical symmetry are disrupted and these giant tetrahedra and surfactants
are functionalized they become building blocks for hierarchical ordered structures. A range of ordered
super-lattice structures of this class of materials: crystals, quasicrystals and Frank-Kasper phases have been
investigated in the condensed bulk state and thin films, revealing the interconnections between soft matter
and hard matter in sharing their common structures and fundamental behavior.
Speaker Background
Professor Cheng received his Ph.D. in Chemistry from Rensselaer Polytechnic Institute in 1985 with
Professor Bernhard Wunderlich. Following a postdoctoral fellowship at RPI he joined the faculty in the
Department of Polymer Science at the University of Akron in 1987. He served stints as Chairman of the
Department of Polymer Science and Dean of the College of Polymer Science and Polymer Engineering and
is currently the Frank C. Sullivan Distinguished Research Professor. Dr. Cheng is also a Member of the
National Academy of Engineering. His research interests center on the condensed states in polymers, liquid
crystals, surfactants and micelles, and focuses on the interactions, responses, dynamics, and structures
of materials on varying length and time scales in which the material itself embodies the technology. His
research activities include investigations of transition thermodynamics and kinetics in metastable states,
ordered structures and morphologies, surface and interface structures in electronic and optical materials and
advanced functional hybrid materials.
128
Thursday, May 14, 2015 Starting: 9:45 AM
TH2_1: FIC (Henzlik 124)
Session Chair: Yuris Dzenis
Assistant: Kaspars Maleckis
Talks:
1. (9:45 AM, Keynote) Galeski:
CRYSTALLIZATION AND MELTING PHENOMENA IN
NANOFIBER REINFORCED POLYMER NANOCOMPOSITES
2. (10:25 AM, Invited) Papkov: POLYMER CRYSTALLINITY AND TOUGHNESS: INCREASING
PLASTICITY OF CONTINUOUS POLYACRYLONITRILE NANOFIBERS THROUGH CRYSTALLIZATION SUPPRESSION
3. (10:45 AM, Oral) Sterzynski: ECOLOGICALLY FRIENDLY MULTILAYER WPC/SRC CONSTRUCTION MATERIALS; PRODUCTION, STRUCTURE AND PROPERTIES
4. (11:05 AM, Oral) Gonçalves: XANTHAM GUM AND CHITOSAN AS NATURAL ADHESIVES
FOR CORK
5. (11:25 AM, Oral) Bin: TRANSCRYSTALLIZATION IN CARBON FIBRE FILLED POLY (L-LACTIC ACID) COMPOSITES UNDER TEMPERATURE GRADIENT
6. (11:45 AM, Oral) Alharbi: SYNTHESIS AND ANALYSIS OF ELECTROSPUN SRTIO3
NANOFIBERS WITH NIOX NANOPARTICLES SHELLS AS PHOTOCATALYSTS FOR WATER
SPLITTING
129
Talk Number: 1 (Keynote)
Time: Thursday, May 14, 2015 9:45 AM
Session: TH2_1: FIC (Henzlik 124)
CRYSTALLIZATION AND MELTING PHENOMENA IN NANOFIBER REINFORCED POLYMER NANOCOMPOSITES
Andrzej Galeski1 , Stanislaw Galeski1,3 , Ewa Piorkowska1 , Kinga Jurczuk1 , Gilles Regnier2 , Artur Rozanski1
1
2
3
Polymer Physics, Centre of Molecular and Macromolecular Studies, Poland
PIMM, Arts et Metiers, ParisTech, 75013 Paris , France
present address: Department of Physics, ETH, Zurich, Switzerland
Recently we have developed a method of transformation of solid polymer particles into nanofibers in-situ
during compounding with other polymers in the molten state [1,2]. The prerequisite is a reduced number
of entanglements in the particles that allows to limit the strain hardening and facilitates the deformation
into nanofibers under shear forces during mixing. Polytetrafluoroethylene nanofibers obtained in this way
exhibit strong nucleation ability towards many polymer matrices, including isotactic polypropylene.
The crystallization kinetics in such systems can be analysed based on the probabilistic model and
equally well in terms of extended volume developed to describe the overall crystallization kinetics in
nanocomposites with embedded finite length nanofibers exhibiting nucleation ability. The validity of the
model was confirmed by a computer simulation and also by comparison with the crystallization kinetics
data of polyamide 12 nanocomposites with carbon nanonubes. The overall crystallization kinetics in
polymer nanocomposites with nucleating nanofibers for isothermal and nonisothermal crystallization,
length and orientation distribution of nanofibers, nucleation on nanofiber surfaces with different density
including transcrystallization, and curved nanofibers was described. Crystallization of nanocomposites of
PP with nucleating PTFE nanofibers and PA12 with MWCNTs was studied. Those nanofibers strongly
nucleate crystallization and the slope of ln[-ln(1-alpha)] vs.ln(t) is close to 2, indicating 2-dimensional growth.
On the other hand transformation of solid polymer particles into long and thin nanofibers affects
their melting behavior, reflected in a decrease of the melting temperature inversely proportional to nanofiber
thickness. The interfacial tension causes also that nanofibers start to melt from their ends. We have
observed a decrease of Tm of polymer nanofibers with decreasing thickness, following the Gibbs-Thomson
equation where interfacial tension plays also an important role. PE nanofibers cannot be very thin because
they can melt even below 120 o C.
This research project has been supported by the statutory funds of CMMS PAS and from funds of
the National Science Centre on the basis of the decisions number DEC-2012/04/A/ST5/00606.
1. K.Jurczuk, A.Galeski, E.Piorkowska, Polymer, 54, 4617-4628 (2013)
2. K.Jurczuk, A.Galeski, E.Piorkowska, J. Rheol.,58, 589-605, 2014
130
Talk Number: 2 (Invited)
Time: Thursday, May 14, 2015 10:25 AM
Session: TH2_1: FIC (Henzlik 124)
POLYMER CRYSTALLINITY AND TOUGHNESS: INCREASING PLASTICITY
OF CONTINUOUS POLYACRYLONITRILE NANOFIBERS THROUGH CRYSTALLIZATION SUPPRESSION
Dimitry Papkov1 , Yuris Dzenis1
1
Mechanical and Materials Engineering, University of Nebraska - Lincoln, USA
Strength of structural materials and fibers is usually increased at the expense of strain at failure and toughness. Polyacrylonitrile (PAN) is a popular precursor for production of carbon fibers. Electrospinning is
an emerging technique that allows production of continuous polymer precursor nanofibers. Recently our
group reported significant scale effects in mechanical properties of individual electrospun polyacrylonitrile
nanofibers. The nanofibers showed remarkable (two orders of magnitude) increases in strength and stiffness, as well as toughness (three orders of magnitude). The largest increases were recorded for the ultrafine
nanofibers smaller than 250 nanometers. Structural investigations and comparisons with mechanical behavior
of annealed nanofibers allowed us to attribute ultrahigh ductility and toughness to low nanofiber crystallinity
resulting from rapid solidification of ultrafine electrospun jets. Here we show that further reducing the crystallinity through changes in the system solvent from dimethylformamide to dimethyacetamide and addition
of small amounts of plasticizer (ethylene carbonate) result in improved nanofiber plasticity and, subsequently,
further improvements in nanofiber toughness. We further show that the observed size effects in mechanical
properties shift to the intermediate diameter range (250-500 nm), offering the possibility of easier nanofiber
processability and handling. For the first time we show experimental evidence of improved polymer chain
orientation in individual nanofilaments with the decrease in their diameter. The described modifications
show the ability to tailor the mechanical properties of the nanofibers in the strength/toughness property
space, which is highly desirable for safety critical applications in composites.
131
Talk Number: 3 (Oral)
Time: Thursday, May 14, 2015 10:45 AM
Session: TH2_1: FIC (Henzlik 124)
ECOLOGICALLY FRIENDLY MULTILAYER WPC/SRC CONSTRUCTION MATERIALS; PRODUCTION, STRUCTURE AND PROPERTIES
Artur Kosciuszko1 , Tomasz Sterzynski2 , Kazimierz Piszczek1
1
Polymer Division, Faculty of Chemcial Technology and Engineering, University of Technology and Life
Science, Bydgoszcz, Poland
2 Faculty of Mechanical Engineering and Management, Polymer Division, Poznan University of Technology,
Poland
The hybrid polymer composites composed of Wood Polymer Composite (WPC) and Self Reinforced
Composites (SRC) layer (-s) have been produced and characterized. The main idea was to produce a
material with sufficiently high mechanical properties, easy to recycle after the end-of-life time. Accordingly,
the material is composed of one polymer, in this case isotactic polypropylene (iPP), used in various forms,
and a filler in a form of wooden flakes. On this way the full material recycling may be performed, making
the reprocessing of this composite material possible.
The sheets of SRC and WPC are placed alternatively, allowing to achieve a material with well-defined
properties, where as well as isotropic or/and anisotropic properties, depending on the of iPP fibers position
(direction) in the SRC, may be realized.
The difficulties appearing by the production of such composite materials, like constitution of temperature
processing windows where the iPP matrix will remains in molten state and the fibers are non-melted, as well
as the resolving of the adhesion problem between the SRC and the WPC will be presented and discussed
from both, technological and structural point of view.
132
Talk Number: 4 (Oral)
Time: Thursday, May 14, 2015 11:05 AM
Session: TH2_1: FIC (Henzlik 124)
XANTHAM GUM AND CHITOSAN AS NATURAL ADHESIVES FOR CORK
Isabel Vale1 , Carolina Gonçalves1 , Diana Paiva1 , Margarida Bastos1 , Fernão Magalhães1
1
Chemistry - LEPABE, Faculty of Engineering of the University of Porto, Portugal
Composites based on cork (bark of Quercus suber L.) have been receiving increasing interest for different
applications. Cork combines a unique set of properties like elasticity, resilience, impermeability, low density,
and very low conductivity of heat, sound and vibration. Moreover, its use is supported by sustainable
forest practices. Cork composites provide added design flexibility and environmental advantages, like ease
of incorporation of pre and post-consumer wastes. But one increasing requirement has been the replacement
of synthetic adhesives, like reactive polyurethane (PUR) or formaldehyde-based resins, by natural binders
from renewable resources. This presents particular challenges, especially when mechanical performance and
water resistance are needed.
The viability of using two widely available polysaccharides, xanthan gum (XG) and chitosan (CS) as
cork binders was studied. The adhesives were used as water solutions with concentrations of 6 wt.%
or lower. For XG, chemical oxidation was investigated as a strategy to provide water resistance and
reactivity. Periodate oxidation allowed C-C cleavage between adjacent -CHOH groups, forming dialdehydes.
NH2OH-HCl titration of the oxidized gum (XGox) indicated aldehyde contents of about 60%. 1H-NMR
confirmed formation of aldehyde groups.
Bond strength (BS) tests were performed on cork samples after drying the glued joints for 2 h at
120 o C. Results showed that CS (6 wt.%) yielded similar BS as a reference PUR adhesive, being 50 %
higher than XG. BS decreased as CS or XG concentrations were lowered, due to depletion of binder in the
glued joint. When performing the tests after immersion of the glued samples in water for 24 h at 20 o C, XG
showed null BS, while CS displayed 40 % lower strength. This was expected considering that XG is soluble
in water while CS in insoluble, as long as nonacidic conditions are used.
Interestingly, XGox showed dry BS 76 % higher than XG and 15 % higher than CS. Wet BS was
similar for XGox and CS. Oxidation of XG reduces its water solubility, as confirmed by total soluble
matter assays, due to decrease in hydroxyl content and possible self-crosslinking promoted by aldehyde groups, which explains higher water resistance. On the other hand, aldehydes also allow for
reaction with groups present in the cork structure, providing a covalent mechanism for increasing bond
strength and water resistance. Mixtures of XGox and CS did not yield better performances than XGox alone.
133
Talk Number: 5 (Oral)
Time: Thursday, May 14, 2015 11:25 AM
Session: TH2_1: FIC (Henzlik 124)
TRANSCRYSTALLIZATION IN CARBON FIBRE FILLED POLY (L-LACTIC ACID)
COMPOSITES UNDER TEMPERATURE GRADIENT
Yuezhen Bin1,2 , Shengnan Zhang1
1
2
Department of Polymer Science and Engineering, Dalian University of Technology, China
State Key laboratory of Fine Chemicals, Dalian University of Technology, China
As a kind of biodegradable and biocompatible thermoplastic resin, Poly (lactic acid) is widely applied in
packaging and biomedical industries. Many researches dealt with the addition of filler in PLA to improve
its crystallization rate. As well-known, the interfacial interaction between polymer matrix and filler plays
a dominant role in the mechanical property of composites. Recently, it has been receiving more and more
attention that interfacial crystallization may contribute to interfacial bonding of the composite. In this
study, thin films of carbon fibre (CF)/PLA and nickel plating carbon fiber (NiCF)/PLA composites were
made via solution casting and the transcrystallization behavior of composites was investigated. Samples were
crystallized on the temperature gradient stage with temperature ranging from 363 K to 413 K. Polarizing
microscope observation indicated that typical transcrystalline (TC) structure was formed in both CF/PLA
and NiCF/PLA composite films. For each composite, nuclei density on single fiber decreased and radius of
TC increased as crystallization temperature (Tc) increased. In addition, nuclei density on single NiCF was
higher than that on CF. SEM observation showed that NiCF had stronger ability to initiate heterogeneous
nucleation due to the existence of nano-nickel particles. However, the radius of TC in short NiCF/PLA
composite was smaller than that in CF/PLA at the same Tc. Crystallization kinetics analysis demonstrated
that the onset time of nucleation and the radius growth rate of TC increased as Tc increased. Furthermore,
kinetics analysis revealed that final size of TC was influenced by competition between transcrystallization
on fiber surface and spherulitic crystallization around the fiber.
References
1 Nanying Ning, Sirui Fu, Wei Zhang, et’al. Progress in Polymer Science, 2012, 37(10): 1425∼1455
2 Duigong Xu, Yuezhen Bin, Ping Tang. Macromolecules, 2010, 43(12): 5323∼5329
134
Talk Number: 6 (Oral)
Time: Thursday, May 14, 2015 11:45 AM
Session: TH2_1: FIC (Henzlik 124)
SYNTHESIS AND ANALYSIS OF ELECTROSPUN SRTIO3 NANOFIBERS WITH
NIOX NANOPARTICLES SHELLS AS PHOTOCATALYSTS FOR WATER SPLITTING
Abdulaziz R Alharbi1 , Ibrahim M. Alarifi1 , Waseem S. Khan1 , Dr. Ramazan Asmatulu1
1
Mechanical Engineering, Wichita State University, United States
Coaxial electrospinning process was used to produce core/shell SrTiO3- NiOx nanofibers. Poly(vinyl alcohol)
(PVA) was dissolved in mixture with DI water and acetic acid at 10:90 weight ratios, and then titanium
(IV) isopropoxide [C12H28O4Ti] and strontium nitrate [Sr(NO3)2] were added into the solution to form the
inner (core) layer. Polyacrylonitrile (PAN) polymer was dissolved in dimethylformamide (DMF) with 10:90
weight ratios. Nickel oxide [Ni2O3] was mixed with the solution to form the outer (shell) layer. This coaxial
electrospinning method generated uniform sized, defect-free fibers. The electrospun nanofiber samples were
annealed at 600 o C for 2 hours in air in order to remove the organic part and crystalline the amorphous
SrTiO3- NiOx nanofibers. Water contact angles were determined to identify surface hydrophobicity of
the nanofiber films. The UV spectrophotometer, fourier transform-infrared radiation (FT-IR), differential
scanning calorimeter (DSC) techniques were used to characterize structural properties of the SrTiO3- NiOx
composite. The morphology and dimensions of the nanofibers were observed by scanning electron microscope
(SEM). The images showed the fluctuation in the fiber diameters because of the two different polymeric
solutions electrospun at the same time. The structures of the calcined nanofibers were determined by
Raman spectroscopy, and X-ray diffraction (XRD), which clearly indicated the formations of SrTiO3 and
NiOx nanofibers structures. The fabrication of such core/shell SrTiO3-NiOx nanofibers through coaxial
electrospinning suggests the further enhancement and development of photocatalytic behaviors of the new
nanomaterials. This study can provide useful information for scientists, engineers, and manufacturers
working in the renewable energy and related fields, such as water splitting, sensors, solar cells, and catalysts.
Keywords: Coaxial Electrospinning, Core/Shell SrTiO3 and NiOx Nanofibers, Calcination, Photocatalysts,
Water Splitting.
135
Thursday, May 14, 2015 Starting: 9:45 AM
TH2_2: PPSC (Henzlik 53)
Session Chairs: Eric Dargent, Lucia Fernandez-Ballester
Assistant: Zesheng Zhang
Talks:
1. (9:45 AM, Keynote) Lefebvre: IN-SITU SAXS/WAXS INVESTIGATIONS ON DEFORMATION
INDUCED STRUCTURAL EVOLUTIONS IN AMORPHOUS AND SEMI-CRYSTALLINE POLYMERS
2. (10:25 AM, Oral) Mokni: EFFECT OF THE SUBLIMATION TEMPERATURE ON THE MORPHOLOGY AND CRYSTALLINITY OF PARYLENE D DEPOSITED BY CVD
3. (10:45 AM, Oral) Piorkowska: NUCLEATION OF HIGH-PRESSURE-INDUCED GAMMA FORM
IN ISOTACTIC POLYPROPYLENE IN NONISOTHERMAL CONDITIONS
4. (11:05 AM, Oral) Fernandez-Ballester: EFFECT OF COPOLYMER CONTENT ON FLOW-INDUCED CRYSTALLIZATION
5. (11:25 AM, Oral) Lugito: NOVEL APPROACHES TO ADVANCE UNDERSTANDING OF POLYMER CRYSTALLIZATION
6. (11:45 AM, Oral) Ding: EFFECT OF TRI-ARM STAR-SHAPED IMIDAZOLIUM IONIC LIQUID
OLIGOMER WITH PEG SEGMENT ON THE CRYSTALLIZATION BEHAVIORS OF POLY(LLACTIC ACID)
136
Talk Number: 1 (Keynote)
Time: Thursday, May 14, 2015 9:45 AM
Session: TH2_2: PPSC (Henzlik 53)
IN-SITU SAXS/WAXS INVESTIGATIONS ON DEFORMATION INDUCED
STRUCTURAL EVOLUTIONS IN AMORPHOUS AND SEMI-CRYSTALLINE
POLYMERS
Jean-Marc Lefebvre1 , Valérie Miri1 , Gregory Stoclet1 , Pepin Julie1 , Roland Seguela2
1
2
UMET, CNRS/Univ Lille, France
MATEIS, CNRS/INSA Lyon, France
The problem of thermally and mechanically-induced crystal phase transitions in semi-crystalline polymers
bearing H bonds is of prime importance in materials where anisotropic intermolecular interactions (van der
Waals vs H-bonding) result in the existence of crystal phases with sheet-like H-bonded structures. Materials
under consideration are polyamides 11 and 6. The use of in-situ characterization of these polymorphic
materials by wide angle and small angle X Ray scattering from a synchrotron source provides clear insights
into the role of these transitions on the mechanical behavior under uniaxial and biaxial drawing. The
structural characterization confirms the existence of a phase transition, the Brill transition, towards a HT
phase with hexagonal symmetry for some specific crystal structures (α’ and δ’ in PA11, α defective in
PA6). The most stable forms (α’ in PA11 and α in PA6) rebuild upon cooling. Under uniaxial drawing,
polyamides exhibit ductility, whatever the original crystal form is; an order→disorder transition occurs for
T<TBrill , which favors mesophase development (δ’ in PA11 and β in PA6), while above TBrill the HT
phase is mechanically stable. In the case of biaxial stretching, phases with H-bonded sheet-like organization
are brittle, contrary to mesomorphic and HT phases. These findings underline the need to monitor the
structural evolution in order to achieve proper solid-state biaxial stretching in industrial processing.
With respect to the cold drawing behavior of PLA, a combination of in situ SAXS and AFM studies
allows identification of the elementary plastic deformation mechanisms involved. It shows that a brittle
to ductile transition occurs when the draw temperature is increased and/or at decreasing strain-rate.
Morphological studies reveal that the brittle behavior of PLA is correlated with the occurrence of crazing,
whereas the ductile response implies dual plastic deformation mechanisms interacting in a rather unusual
way. In particular, in situ SAXS reveals the formation of “shear band crazes” and a tentative explanation of
their development is proposed. In addition this study shows shear banding, activated at high temperature,
plays a dual role. While shear bands promote the formation of crazes, they also stabilize them during their
growth.
137
Talk Number: 2 (Oral)
Time: Thursday, May 14, 2015 10:25 AM
Session: TH2_2: PPSC (Henzlik 53)
EFFECT OF THE SUBLIMATION TEMPERATURE ON THE MORPHOLOGY AND
CRYSTALLINITY OF PARYLENE D DEPOSITED BY CVD
Marwa Mokni1,2 , Abdelkader Kahouli1,2 , Emmanuelle Giroud3 , Vincent Mareau4 , Fethi Jomni2 , Alain
Sylvestre1
1
2
3
4
Genie electrical, Univ. Grenoble Alpes, G2Elab, France
Physical, Univ. of Tunis El Manar (LMOP), Tunisia
Material, Univ. Grenoble Alpes, Polytech Grenoble, France
Material, Univ. Grenoble Alpes, INAC-SPRAM, France
In the family of parylenes, (Poly-dichloro-para-xylylene) (PPXD) was the object of few attentions until
today by the scientific community. However, its chemical structure seems to project some properties between
PPX N and PPX C and so could be interesting to replace these latters for specific applications. In this way,
thin and transparent PPXD has been prepared by Chemical Vapor Deposition (CVD) from vapor-phase
pyrolysis of the cyclic tetrachloro-di-p-xylylene dimer. The dependence of (i) the sublimation temperature
(120-160 o C), (ii) the deposition time (5-660 min) and (iii) the deposition rate on the physical properties
of PPX D was investigated. Increasing sublimation temperature affects the surface morphology and the
crystallinity of the material. From Atomic Force Microscopy, one observes that the sublimation temperature
leads to an increase in the surface roughness from 4 to 5.4 nm. Wide Angle X-ray Diffraction (WAXD)
experiments allow identifying a monoclinic crystalline-α-form with reflection (020) at 2θ=12o C. A significant
decrease in the crystalline phases of the polymer for higher sublimation temperatures is observed. Finally,
crystalline phases are in depth investigated by polarized light microscopy.
138
Talk Number: 3 (Oral)
Time: Thursday, May 14, 2015 10:45 AM
Session: TH2_2: PPSC (Henzlik 53)
NUCLEATION OF HIGH-PRESSURE-INDUCED GAMMA FORM IN ISOTACTIC
POLYPROPYLENE IN NONISOTHERMAL CONDITIONS
Przemyslaw Sowinski1 , Ewa Piorkowska1 , Severine A.E. Boyer2 , Jean-Marc Haudin3
1
Department of Polymer Structure, Centre of Molecular and Macromolecular Studies, Polish Academy of
Sciences, Poland
2 Department of Physics and Mechanics of Materials, P PRIME Institute, ISAE-ENSMA, UPR CNRS 3346,
France
3 Centre for Material Forming, MINES ParisTech, UMR CNRS 7635, France
Isotactic polypropylene (PP) under atmospheric pressure crystallizes usually in the monoclinic alpha or
trigonal beta phase, the latter requiring appropriate nucleating agents. Crystallization of the orthorhombic
gamma form is facilitated by high pressure (P), although it requires also high temperature. Owing to its
unique structure with nonparallel chain alignment, it exhibits different mechanical properties than the alpha
form [1]. Recently, we demonstrated [2] that alpha-nucleants can nucleate the gamma form under high P at
200 o C. During processing crystallization is non-isothermal, hence our present study focuses on nucleation
of the gamma form in PP under high P during cooling.
The study utilized PP 3250MR1, Arkema. Three alpha-nucleants, calcium salt of cis-1,2-cyclohexanedicarboxylic acid, Hyperform HPN-20E, 1,3:2,4-bis(3,4-dimethylbenzylidene sorbitol), Millad 3988i,
Milliken Chemicals, poly(tetrafluoroethylene) (PTFE) submicron particles [3], Dispersez 200W, Polysciences,
and a known beta-nucleant - calcium pimelate, synthesized by us, were used. Neat PP and PP with 0.2
wt% of the nucleants were crystallized in a cell described elsewhere [1,2], under P ranging from 100 to 300
MPa, during cooling at approx. 8 o C/min and next analysed by different methods to examine crystallinity,
contents of crystallographic forms and spherulitic structure.
Crystallization temperature (Tc) of all the materials increased with increasing P. HPN-20E and PTFE
exhibited the highest Tc ; under 300 MPa Tc of PP with HPN-20E exceeded that of neat PP by 14 o C
Both, HPN-20E and PTFE increased also the gamma content and reduced the grain size. Calcium pimelate
had no such effect; it increased only the beta content. The effect of Millad depended on P. Under 100 MPa
it elevated Tc, and the gamma content, and strongly reduced the grain size, but the effect vanished with
increasing P.
The results show the possibility to nucleate the gamma form of PP under high P during cooling,
hence to increase its content and Tc, and to reduce the grain size.
Acknowledgement
CMMS PAN statutory funds and PAN/CNRS Collaborative Project 179990 High pressure crystallization
and structure of polymers based nanocomposites.
References
1. Lezak E, Bartczak Z, Galeski A. Macromolecules 2006, 39, 4811
2. Sowinski P, Piorkowska E, Boyer SAE, Haudin JM, Zapala K. Colloid Polym Sci DOI: 10.1007/s00396014-3445-z
3. Masirek R, Piorkowska E. Eur Polym J 2010, 46, 1436
139
Talk Number: 4 (Oral)
Time: Thursday, May 14, 2015 11:05 AM
Session: TH2_2: PPSC (Henzlik 53)
EFFECT OF COPOLYMER CONTENT ON FLOW-INDUCED CRYSTALLIZATION
Frederic Aubin1 , Hugo Boitoit1 , Ramin Hosseinabad1 , Eric Dargent2 , Lucia Fernandez-Ballester1
1
2
Mechanical and Materials Engineering, University of Nebraska at Lincoln, USA
Advanced Materials and Mechanical Engineering, AMME-LECAP International Laboratory, France
The effect of copolymer content on structure development during and after a short shear pulse has been
examined for polypropylene-based materials containing between 0 and 7% mol ethylene content. All
materials have similar molecular weight Mw , polydispersity, and rheological behavior in the melt. Flow
induced crystallization experiments at fixed temperature and wall shear stresses up to σ skin = 0.134MPa
showed a similar critical shear stress for formation of a highly oriented skin (σskin) for 0 and 3% copolymer
content. In contrast, further increase in copolymer content up to 7% required a slightly higher σ skin . In all
cases, σ skin was observed to plateau with increasing shearing time ts .
The relative amount of shish length/volume was estimated by applying a depth sectioning method to
the real-time optical measurements. Results indicate that as expected, for shear stress up to 0.123 MPa,
shish length/volume is larger for higher σ for first increases and then levels off with sufficient ts for all
materials. In contrast, at 0.134MPa, the relative shish length/volume for 0 and 3% copolymer content
is smaller than at 0.123. This unexpected behavior is shown to correlate with deviations in rheological
behavior and in the residual birefringence after flow.
140
Talk Number: 5 (Oral)
Time: Thursday, May 14, 2015 11:25 AM
Session: TH2_2: PPSC (Henzlik 53)
NOVEL APPROACHES TO ADVANCE UNDERSTANDING OF POLYMER CRYSTALLIZATION
Graecia Lugito1 , Eamor M. Woo1
1
Chemical Engineering, National Cheng Kung University, Taiwan
Recently, more and more research on polymer morphology have been conducted in order to study the properties - morphology correlation, which may bring us to the enhancement technique of polymer modification and
manipulation properties. Poly(trimethylene terephthalate) (PTT), a highly birefringent aromatic polyester,
has been investigated to explore the correlation between crystal morphology, optical birefringence properties,
and crystallization mechanism. PTT exhibits large and well-defined ring-banded spherulites which make
it a good candidate for the study of polymer crystallization and self-assembly. Optical interference colors
that ornament the morphological image of PTT crystal under POM are found to be strongly related not
only to the sample thickness, but also to the lamellar structure and arrangement within the spherulites.
Besides, banding patterns of the spherulites are also found to be varied with the curvature of the initial
nucleus. Chemical etching using methylamine vapor has been carried out on bulk samples of PTT with
different angles of dissection to see the intricate lamellar structures in the spherulites. A novel crystallization
mechanism of PTT has been built from comprehensive analyses of morphology, optical colors, and chemical
etching approaches.
141
Talk Number: 6 (Oral)
Time: Thursday, May 14, 2015 11:45 AM
Session: TH2_2: PPSC (Henzlik 53)
EFFECT OF TRI-ARM STAR-SHAPED IMIDAZOLIUM IONIC LIQUID
OLIGOMER WITH PEG SEGMENT ON THE CRYSTALLIZATION BEHAVIORS
OF POLY(L-LACTIC ACID)
Yu Li1 , Huagao Fang1 , Di Zhang1 , Pei Xu1 , Haibing Wei1 , Yunsheng Ding1,2
1
School of Chemistry and Chemical Engineering, Hefei University of Technology, China
Provincial Key Laboratory of Advanced Functional Materials and Devices, Hefei University of Technology,
China
2
Crystallization kinetics of the poly(L-lactic acid) (PLLA) due to the incorporation of a kind of tri-arm
star-shaped imidazolium ionic liquid oligomer with PEG segment (TSIL) has been studied. Crystallization
kinetic parameters, such as relative crystallinity, crystallization half time, crystallization rate constant and
Avrami exponents, had been determined by both isothermal and non-isothermal techniques using differential
scanning calorimetry (DSC). The experimental results based on isothermal and non-isothermal methods
show that the melt crystallization increases significantly with the incorporation of TSIL in the blends.
During the isothermal crystallization process at the crystallization temperature of 90o C, 95o C, 100o C and
105o C, respectively, addition of the 9wt% TSIL accelerates the crystallization of the PLLA greatly. During
the non-isothermal crystallization process, the crystallization behavior of the PLLA is found to be greatly
dependent upon both the cooling rates and the concentration of TSIL. The growth of crystallized spherulites
had also been monitored by polarizing optical microscope (POM), which confirms that the growth rate of
spherulites increases on the addition of TSIL in the blends, but the nuclear number decrease.
In this article, we have also investigated the morphology of the spherulites for PLLA and TSIL/PLLA
blends using POM. In the investigation, there are two kinds of spherulites observed under the POM at the
crystallization temperature of 108o C, 110o C and 115o C, respectively. When the weight content of TSIL is
below 9wt%, the well-defined highly birefringent spherulites can be observed, and when the weight content
of TSIL is up to 9wt%, the spherulites tends to coarse which can be seen. It is amazing to find that the
Maltese cross that we can find in the well-defined highly birefringent spherulites is not appeared in the coarse
spherulites. The growth rate of the coarse spherulites is much faster than that of the highly birefringent
spherulites. It is thought that the coarse spherulites nucleate and grow as the diffusion of the molecules of
the TSIL at the interfaces between the TSIL and PLA, and the well-defined highly birefringent spherulites
just nucleate and grow in the PLA matrix without the TSIL.
142
Thursday, May 14, 2015 Starting: 1:00 PM
TH3: Flory Medal Talk (Henzlik 124)
Session Chair: Jean-Jacques Pireaux
Assistants: John Jasa, Taylor Stockdale
Talk:
1. (1:00 PM, Prize Talk) Tashiro: CLARIFICATION OF MICROSCOPICALLY-VIEWED STRUCTURE-PROPERTY RELATIONSHIP OF POLYMER MATERIALS
Dr. Kohji Tashiro, Principal Professor, Department of Future Industry-oriented Basic Science and
Materials, Graduate School of Engineering, Toyota Technological Institute
143
Talk Number: 1 (Prize Talk)
Time: Thursday, May 14, 2015 1:00 PM
Session: TH3: Flory Medal Talk (Henzlik 124)
CLARIFICATION OF MICROSCOPICALLY-VIEWED STRUCTURE-PROPERTY
RELATIONSHIP OF POLYMER MATERIALS
Kohji Tashiro1
1
Future Industry-oriented Basic Science and Materials, Toyota Technological Institute, Japan
In these several decades, we have applied the various characterization techniques including synchrotron and
neutron diffractions, FTIR/Raman vibrational spectroscopy, computer simulation and so on for the clarification of structure-property relationship of polymers from the microscopic point of view.
[Structural Analysis using Quantum Beam and Vibrational Spectroscopy] We have been challenged to utilize
a high-energy synchrotron X-ray beam of short wavelength and a highly-brilliant neutron beam for the detailed crystal structure analysis of polymers including even the determination of hydrogen atomic positions.
Additionally, the combination of X-ray and neutron structure analyses or X-N method has allowed us to
estimate the bonded electron density distribution along the polymer skeletal chain, giving us a chance to
discuss the physical property from the experimentally-clarified electron level.
[Development of Simultaneous Measurement System to Trace the Structural Changes in the Phase Transitions] In order to trace the dynamic and hierarchical structural changes during the phase transitions, we
have developed the experimental system for the simultaneous time-resolved measurements of wide-angle
X-ray diffraction, small-angle X-ray scattering, Raman scattering or FTIR spectra during heating/cooling,
stretching/compression, and so on. As examples, the hierarchical structural changes occurring in the isothermal crystallization from the melt or glass or in the tensile deformation process have been clarified for the
various kinds of crystalline polymers.
[Molecular Theoretical Study of Structure-Property Relationship of Polymer Crystals] The molecular theory
including lattice dynamics has been developed for the prediction of the 3D elastic constants tensor and stressinduced molecular deformation mechanism of polymer crystals, for example. This theoretical prediction of
microscopic deformation of polymer chain has been probed successfully by the performance of actual X-ray
structure analysis of polymer crystal (polydiacetylene) under tension. The clarification of heterogeneous
stress distribution in the mechanically-deformed polymer substance has been also succeeded by analyzing
the shifts of X-ray diffraction peaks, Raman peaks and IR peaks detected under the external stress, from
which the existence of taut tie chains was proposed, which is quite important for the solution of industrial
problems about the mechanical toughness of polymers.
144
Thursday, May 14, 2015 Starting: 2:00 PM
TH4_1: CSPM (Henzlik 124)
Session Chairs: Joseph Alan Turner, Philip Yuya
Assistant: John Jasa
Talks:
1. (2:00 PM, Keynote) Yablon: ADVANCES IN ATOMIC FORCE MICROSCOPY (AFM) BASED
METHODS TO CHARACTERIZE POLYMER MATERIALS ON THE NANOSCALE
2. (2:40 PM, Invited) Yuya: EFFECT OF GOLD NANOPARTICLE ENHANCEMENT ON NANOMECHANICAL PROPERTIES OF CHITOSAN FILMS
3. (3:00 PM, Oral) Desyatova: CHARACTERIZATION OF THERMOMECHANICAL PROPERTIES
OF RECOMBINANT RESILIN USING ATOMIC FORCE MICROSCOPY
4. (3:20 PM, Oral) Turner: SIMULTANEOUS QUANTIFICATION OF THE IN-PLANE AND OUTOF-PLANE LOSS TANGENT OF POLYMERS USING CONTACT RESONANCE ATOMIC FORCE
MICROSCOPY
145
Talk Number: 1 (Keynote)
Time: Thursday, May 14, 2015 2:00 PM
Session: TH4_1: CSPM (Henzlik 124)
ADVANCES IN ATOMIC FORCE MICROSCOPY (AFM) BASED METHODS TO
CHARACTERIZE POLYMER MATERIALS ON THE NANOSCALE
Dalia Yablon1
1
SurfaceChar, SurfaceChar, USA
AFM based characterization methods are uniquely suited to identify and discriminate polymer materials
since this microscopy is inherently based on a mechanical interaction between tip and sample. An ongoing
challenge for these kinds of characterization methods is quantitative measurement of nanoscale viscoelastic
properties.
Recent progress has been achieved with advanced AFM methods to quantitatively measure the storage
modulus, loss modulus, and loss tangent of polyolefin containing blends. Both dynamic contact and
amplitude modulation based AFM methods are applied to measure the properties of PP-PE-PS and
PP-elastomer blends. The dynamic contact method show excellent sensitivity and accuracy where magnetic
actuation of the cantilever shows significant improvement in sensitivity to storage and loss modulus. The
loss tangent is also measured as a function of temperature, revealing important polymer transitions. Finally,
the use of multifrequency AFM methods, where the AFM cantilever is excited at multiple eigenmodes, is
shown to successfully discriminate materials in multi-component blends and materials.
146
Talk Number: 2 (Invited)
Time: Thursday, May 14, 2015 2:40 PM
Session: TH4_1: CSPM (Henzlik 124)
EFFECT OF GOLD NANOPARTICLE ENHANCEMENT ON NANOMECHANICAL
PROPERTIES OF CHITOSAN FILMS
Philip Yuya1
1
Mechanical & Aeronautical Engineering, Clarkson University, USA
Chitosan is a naturally derived polymer. It represents one of the most technologically important classes of
active materials with applications in a variety of industrial and biomedical fields. However, they are used
in limited applications because of disadvantages such as poor electromechanical properties, high brittleness
with a low strain at break, and sensitivity to water. In certain critical applications, the need arises to modify
the physical, mechanical and electrical properties of the polymer. When blends of polymer films with other
materials are used for medical devices, as is commonly the case, device performance directly depends on
the nanoscale morphology and phase separation of the blend components. Here, chitosan reinforced bionanocomposite films with varying concentrations of gold nanoparticles were prepared through a solution
casting method. Gold nanoparticles (∼ 32 nm diameter) were synthesized via a citrate reduction method
from chloroauric acid and incorporated in the prepared Chitosan solution. Uniform distribution of gold
nanoparticles was achieved throughout the chitosan matrix and was confirmed by SEM images. Synthesis
outcomes and prepared nanocomposites were characterized using TEM, SAED, SEM, EDX, XRD, UV-vis,
particle size analysis, zeta potential and FT-IR for their physical, morphological and structural properties.
Nanoscale mechanical properties of the nanocomposite films were characterized at room temperature, human
body temperatures and higher temperatures using instrumented nanoindentation techniques. The obtained
films were confirmed to be biocompatible by their ability to support the growth and proliferation of human
cells in vitro. Statistical analysis on mechanical properties and biocompatibility results, were conducted.
Results revealed significant enhancement on both the mechanical properties and cell adherence and proliferation. The results will enhance our understanding of the effect of nanostructures reinforcement on these
important functional polymeric thin films for potential biomedical applications.
147
Talk Number: 3 (Oral)
Time: Thursday, May 14, 2015 3:00 PM
Session: TH4_1: CSPM (Henzlik 124)
CHARACTERIZATION OF THERMOMECHANICAL PROPERTIES OF RECOMBINANT RESILIN USING ATOMIC FORCE MICROSCOPY
Anastasia Desyatova1 , Deepak Rudrappa2 , Paul Blum2 , Joseph Turner1
1
2
Mechanical and Materials Engineering, University of Nebraska-Lincoln, USA
School of Biological Sciences, University of Nebraska-Lincoln, USA
Resilin is one of the most efficient biological elastomeric proteins known today with resilience of over 90%,
long fatigue life and high elongation at failure. Recently produced recombinant resilins have demonstrated
promising mechanical properties for a wide range of engineering applications. However, their thermomenchanical properties at the nanoscale have not yet been characterized. Here, recombinant pro-resilin was
manufactured based on the first exon of the Drosophila CG15920 gene and crosslinked into a hydrogel using
ruthenium-mediated rapid photochemical crosslinking. Thermomecanical properties of dehydrated resilin
gel specimens were characterized using nano Thermal Analysis (nano-TA) and glass transition temperatures
(Tg) were obtained at scales less than 100 nm. The results show that Tg at the nanoscale is significantly
lower than that measured using differential scanning calorimetry at the macroscale (115 o C versus 170-180
o C). A thermal pre-treatment effect was also observed at the nanoscale with Tg gradually increasing up to
its macroscopic value. The increase in Tg can be related to the additional thermal crosslinking not reported
previously. These results improve our understanding of thermomechanical properties of the crosslinked resilin. The fact that resilin hydrogels can be thermally pre-treated allows manufacturing of resilin polymers
with heterogeneous tunable properties through nanoscale level pre-treatment [Support from the Nebraska
Center for Energy Sciences Research is gratefully acknowledged].
148
Talk Number: 4 (Oral)
Time: Thursday, May 14, 2015 3:20 PM
Session: TH4_1: CSPM (Henzlik 124)
SIMULTANEOUS QUANTIFICATION OF THE IN-PLANE AND OUT-OF-PLANE
LOSS TANGENT OF POLYMERS USING CONTACT RESONANCE ATOMIC
FORCE MICROSCOPY
Joseph Alan Turner1 , Ehsan Rezaei1
1
Mechanical and Materials Engineering, University of Nebraska-Lincoln, USA
Contact resonance atomic force microscope (CR-AFM) methods are relatively new measurement techniques
used to quantify the elastic and viscoelastic properties of numerous materials such as polymers, elastomers,
and biological materials. This approach involves measurement of the resonant frequencies of the AFM probe
both for the free case and the case for which the tip is in contact with a sample. Vibration models of the probe
and tip-sample contact models are then used to determine the sample properties from the frequency behavior
and to create images of the sample properties. More recently, U-shaped AFM probes were developed to allow
local heating of samples and the resonances of these probes are much more complex. These probes have
one distinct advantage over rectangular AFM probes in that specific modes allow in-plane and out-of-plane
tip-sample motion to be excited independently at the same location. In this presentation, we demonstrate
the use of this approach for measurement of the material loss tangent at local positions on several polymers.
The excitation area is on the order of a few tens of nanometers offering the potential for a wide range of
heterogeneous polymers and polymer composites.
149
Thursday, May 14, 2015 Starting: 2:00 PM
TH4_2: NANO (Henzlik 53)
Session Chair: Michael J. Serpe
Assistant: Taylor Stockdale
Talks:
1. (2:00 PM, Invited) Okamoto: EFFECT OF PARTICLE DISTORTION ON SAXS FROM OBDD
STUDIED USING PARACRYSTALLINE THEORY AND SELF-CONSISTENT FIELD THEORY
2. (2:20 PM, Invited) Matsuo: MECHANICAL AND DIELECTRIC PROPERTY OF POLYMERFILLER COMPOSITES IN TERMS OF THERMAL FLUCTUATION-INDUCED TUNNELING EFFECT
3. (2:40 PM, Oral) Song: REVERSAL NANOIMPRINTING AND FERROELECTRIC PROPERTIES
OF P(VDF-TRFE) COPOLYMER NANOSTRUCTURES ON FLEXIBLE PET SUBSTRATE
4. (3:00 PM, Oral) Hnatchuk: POLYCARBONATE AND POLYURETHANE NANO AND MICROHYBRID FOAMS
5. (3:20 PM, Oral) Park: CHARACTERIZATION OF CRYSTALLINE THERMOSETTING UREAFORMALDEHYDE RESINS
150
Talk Number: 1 (Invited)
Time: Thursday, May 14, 2015 2:00 PM
Session: TH4_2: NANO (Henzlik 53)
EFFECT OF PARTICLE DISTORTION ON SAXS FROM OBDD STUDIED USING
PARACRYSTALLINE THEORY AND SELF-CONSISTENT FIELD THEORY
Shigeru Okamoto1
1
Materials Science and Engineering, Nagoya Institute of Technology, Japan
An ordered-bicontinuous double diamond (OBDD) structure in diblock copolymers was first discovered in
1980s [1,2]. In mid 1990s, however, previously reported OBDD was reclassified to an ordered-bicontinuous
double gyroid (OBDG) [3,4], which brought about many controversies. Recently theoretical study [5]
suggested an OBDD structure in diblock copolymer/homopolymer blends. Our previous SAXS work
reported experimental results of structural transition between OBDD and OBDG with temperature, which
we analyzed by fitting with theoretical scattering profile calculated on the basis of a paracrystalline model.
However, the theoretical SAXS intensity was not successfully matched while the peak positions were
perfectly matched. We consider that it is necessary to match the theoretical intensity with the experimental
one in order to clearly prove the existence of OBDD.
A polystyrene-b-polyisoprene diblock copolymer (SI0426; Mn = 45000, fPS = 0.70), and a polyisoprene
homopolymer (PI0313; Mn = 18000) were used. DOP was added to the blend, SI0426/PI0313 (=75/25
wt./wt.), by 40 wt.%. The total volume fraction of polyisoprene was 48.9 %. The structure was measured
by SAXS at BL40-B2 in SPring8.
Theoretical profiles were obtained by Fourier transformation of a model prepared by translation of a unit
model. Our previous work suggested the dry-brush PI homopolymers added were accumulated inside nodes
of diamond networks to reduce the entropy loss of the block chains forming the nodes. However, this model
did not have a good agreement with the experimental data as mentioned above. Then we introduced a new
type of distortion to a unit model to obtain ‘larger nodes and thinner rods’ or ‘smaller nodes and thicker rods’.
Theoretical profiles for various volume fractions without the distortion showed that higher-order maxima is
more strongly affected by the fraction, while the second maximum is much less affected. Thus we introduced
the distortion to nodes and rods as described above. The second peak intensity is most affected among the
higher-oreder maxima, and the profile for the ‘smaller nodes and thicker rods‘ model had better agreement
with the experimental profile.
REFERENCES
[1] E. L. Thomas et al., Macromolecules, 1986, 19, 2197
[2] H. Hasegawa et al., Macromolecules, 1987, 20, 1651
[3] D. A. Hajduk et al., Macromolecules, 1994, 27, 4063
[4] D. A. Hajduk et al., Macromolecules, 1995, 28, 2570
[5] F. J. Marinez-Veracochea et al., Macromolecules, 2009, 42, 9058
151
Talk Number: 2 (Invited)
Time: Thursday, May 14, 2015 2:20 PM
Session: TH4_2: NANO (Henzlik 53)
MECHANICAL AND DIELECTRIC PROPERTY OF POLYMER-FILLER COMPOSITES IN TERMS OF THERMAL FLUCTUATION-INDUCED TUNNELING EFFECT
Masaru Matsuo1 , Panpan Zhang1 , Yuezhen Bin1 , Rong Zhang1
1
Department of Polymer Science and Materials, Dalian University of Technology, China
Mechanical and dielectric property of polymer-filler composites in terms of thermal fluctuation-induced
tunneling effect and dielectric stabilities of polyimide (PI)-vapor grown carbon fiber (VGCF) composites were
investigated to investigate the thermal stability of the composites. VGCF/PI composites were fabricated by
in situ polymerization to realize excellent dispersion of VGCFs in PI matrix. Adoption of VGCFs similar to
rigid carbon fibers is the strategy to investigate the conductive mechanism theoretically in terms of thermal
fluctuation-induced tunneling conduction.[1-2] Dynamic tensile modulus and X-ray intensity under applied
electric field were measured to investigate frequency-temperature dependence of the modulus by Joule heat
as well as air heat in relation to the electron transfer mechanisms. Such simultaneous measurements for
the mechanical and structural properties under electric field provided important information about the
characteristic of polymer-filler composites. As the results, good heat resistance of PI-VGCF composites
was clarified to be attributed to very few thermal fluctuation of PI chain arrangement in spite of collision
between electrons flowed out from the VGCF gaps and atoms of PI chains.
Based on the above thermal stability of the PI-VGCF composites, combination between DC component
of AC conductivity and DC conductivity by direct DC measurement was analyzed in terms of thermal
fluctuation-induced tunneling through thin barriers in order to evaluate the average gap distance D between
adjacent vapor grown carbon fibers (VGCFs) in polyimide (PI) matrix. The phase lags of resistances for
complex impedance were evaluated by a two-circuit model with a 3.11 vol% and by a three-circuit model for
a 6.28 vol% containing the Contact Phase Element. The distance D was calculated by computer simulation
on the basis of the DC component of the AC conductivity. The values were 1.2 and 1.0 nm for the composites
with 3.11 and 6.28 vol%, respectively, independent of the applied voltage range 0.1-0.5 V. These reasonable
values accorded with those obtained by the direct DC measurement.
References
1) R. Zhang et al. Polymer J. 45, .1129 (2013),
2) R. Zhang et al. J. Phys. Chem. B. 118, 2226 (2014)
152
Talk Number: 3 (Oral)
Time: Thursday, May 14, 2015 2:40 PM
Session: TH4_2: NANO (Henzlik 53)
REVERSAL NANOIMPRINTING AND FERROELECTRIC PROPERTIES OF
P(VDF-TRFE) COPOLYMER NANOSTRUCTURES ON FLEXIBLE PET SUBSTRATE
Jingfeng Song1 , Haidong Lu1 , Shumin Li2 , Li Tan2 , Alexei Gruverman1 , Stephen Ducharme1
1
2
Physics & Astronomy, University of Nebraska-Lincoln, USA
Mechanical & Materials Engineering, University of Nebraska-Lincoln, USA
ABSTRACT
PVDF and its copolymers have found increasing application in a wide range of flexible electronic technologies,
such as nonvolatile memories, organic electronics, energy storage, and solid-state energy harvesting and
conversion. Up to now, many studies of ferroelectric polymer nanostructures have applied the traditional
direct nanoimprinting technique in which a hard mold is pressed against (PVDF)-based polymer film coated
on silicon wafer at raised temperature. The direct imprinting process often leaves a residual polymer layer
between the imprinted structures, and more importantly, the required high pressure of 20∼128 bars or
more during the imprinting makes it unsuitable for flexible substrates since their mechanical strength are
not sufficient for high pressure processing at raised temperature. Based on these considerations, we have
developed a low pressure reversal nanoimprinting method and fabricated large area, residual-layer-free
P(VDF-TrFE) 2D nanograting and 3D nanopillar structures on flexible PET substrate. The reversal
imprinting method is using low-cost polycarbonate and PDMS mold with no pretreatment necessary, and
the imprinted nanostructures showed very good piezoresponse. The low pressure reversal nanoimprinting
method with a soft mold is a promising approach to fabricate functional polymer nanostructures on flexible
substrate for flexible electronics applications.
ACKNOWLEDGMENT
We thank Prof. Barry Cheung for fruitful discussions, Prof. You Zhou for assistance with SEM and Dr.
Shah Valloppilly and Yunlong Geng for assistance with the x-ray data analysis. This work was supported
by the U.S. Department of Energy, Office of Basic Energy Sciences, under Award No. DESC0004530.
153
Talk Number: 4 (Oral)
Time: Thursday, May 14, 2015 3:00 PM
Session: TH4_2: NANO (Henzlik 53)
POLYCARBONATE AND POLYURETHANE NANO AND MICROHYBRID FOAMS
Witold Brostow1 , Chong Bo1 , Thomas Cloarec1 , Nathalie Hnatchuk1 , Yingji Wu1
1
Materials Science and Engineering, University of North Texas, USA
Metallic and polymeric foams have automatically light weight while their mechanical properties are
comparable to the respective solid materials. However, metallic foams corrode and recover poorly after large
stresses. Polymeric foams have a large area of applications; varying a polymer matrix, we can obtain flexible
or rigid materials while adding different fillers can improve properties and lower an overall cost. We use as
matrices two commercial polymers, a polycarbonate (PC) and a polyurethane (PU).
We use both physical and chemical procedures to produce foams. The physical methods of creating
foams require injecting carbon dioxide gas under pressure or else using a supercritical CO2. Along the
chemical route, polymers undergo a chemical reaction with a foaming agent specific for each polymer.
Depending on the chosen procedure and varying processing conditions such as time, temperature and
pressure, we can control the sizes of pores in the foams. We use a variety of nano- and micro-fillers, such
as carbon black, nanoclay, silica and fly ash. The filler nature, its concentration, particles shape and size
make a dramatic difference in the foam’s performance. Some of our fillers are quite inexpensive, including
even industrial waste. Filler concentration in the foams is varied from 0 to 30 wt. % with step of 2.5 %.
We observe a deterioration of mechanical properties of PC and PU foams when exceeding 30 % of the filler.
Creating foams with fillers allows us to enhance thermophysical, mechanical and tribological properties of
materials while lowering the product cost at the same time. Since some of our fillers are actually wastes,
recycling contributes to the environmental protection of our planet.
154
Talk Number: 5 (Oral)
Time: Thursday, May 14, 2015 3:20 PM
CHARACTERIZATION
OF
FORMALDEHYDE RESINS
Session: TH4_2: NANO (Henzlik 53)
CRYSTALLINE
THERMOSETTING
UREA-
Byung-Dae Park1 , Arif Nuryawan1 , Valerio Causin2
1
2
Department of Wood and Paper Sciences, Kyungpook National University, Republic of Korea
Department of Chemical Sciences, University of Padova, Italy
It is generally known that thermoset polymers such as epoxy resin and formaldehyde-based resins are essentially amorphous. In particular, urea-formaldehyde (UF) resin, a polymeric condensation product of
formaldehyde with urea, is one of the most important thermosetting formaldehyde-based resins, and being
widely used as wood adhesives. However, we here report that thermosetting UF resin of low formaldehyde/urea (F/U) mole ratio contains crystalline structures either in liquid or cured state. We employed
several characterization techniques, such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), wide angle X-ray diffraction (WAXD), small angle X-ray scattering (SAXS) to study the
crystalline structures of UF resins. These characterization results have revealed that UF resins with low F/U
mole ratio contain crystalline structures, even in the contact with wood. The presence of crystalline structures in UF resin indicates that a thermosetting polymer is a crystalline polymer. In addition, these results
also suggest that the crystallite formation in cured UF resin does not make contribution to its cross-linking
in the curing process, leading to a lower cross-linking density and consequent poor adhesion strength.
155
Thursday, May 14, 2015 Starting: 4:00 PM
TH5_1: BIOT (Henzlik 124)
Session Chair: Holger Schönherr
Assistant: John Jasa
Talks:
1. (4:00 PM, Keynote) Castano: ADVANCED NATURAL MATERIALS: FROM RICE HUSK TO
AEROSPACE SYSTEMS
2. (4:40 PM, Invited) Thomas: ROLE OF NANOPARTICLES IN COMPATIBILIZING IMMISCIBLE
POLYMER BLENDS
3. (5:00 PM, Oral) Gnuse: MECHANICALLY ACCURATE NANOFIBROUS VASCULAR GRAFT
MATERIALS
4. (5:20 PM, Oral) Laskar: EVALUATION OF POTENTIAL APPLICATION OF UNUSUAL POLYMERSOMES PREPARED FROM PH-RESPONSIVE DUAL HYDROPHILIC BIOCOMPATIBLE
RANDOM COPOLYMERS
156
Talk Number: 1 (Keynote)
Time: Thursday, May 14, 2015 4:00 PM
Session: TH5_1: BIOT (Henzlik 124)
ADVANCED NATURAL MATERIALS: FROM RICE HUSK TO AEROSPACE SYSTEMS
Victor M. Castano1
1
Centro de Física Aplicada and Tecnología Avanzada, Universidad Nacional Autónoma de México, Mexico
A review of the fundamental properties shared by many natural materials, from the standpoint of structure/properties relationships will be presented as a general theoretical framework. Then, a number of specific
examples will be elaborated, with emphasis on the advance applications that have, are or can be attained,
including fireproof building materials from rice husk, the bioproduction of nanoparticles from soil fauna,
the removal of metal ions from water from chicken feathers, to the production of light, radiation-resistant
materials for aerospace use from natural plants, and others in the biomedical arena. Finally, the future of
Materials Science and Engineering, from a perspective of Nature-made raw materials, will be discussed.
157
Talk Number: 2 (Invited)
Time: Thursday, May 14, 2015 4:40 PM
Session: TH5_1: BIOT (Henzlik 124)
ROLE OF NANOPARTICLES IN COMPATIBILIZING IMMISCIBLE POLYMER
BLENDS
Sabu Thomas1,2
1
Director,International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi
University,kottayam,Kerala, India
2 School of Chemical Sciences, Mahatma Gandhi University,Kottayam,Kerala, India
The use of nanofillers in polymer system has brought about wide appreciation due to the excellent
improvement in property it imparts in a polymeric material .This in turn have benefitted hugely the
industrial sector. While blending of polymers is always done to enhance the properties of polymer products,
the expected property is not always achieved due to the immiscibility faced by majority of the polymers.
As reported by many research groups, the addition of nanoparticles is a useful and interesting method
for compatibilization[3]. The use of nanofillers as a compatibilizer can impart significant changes to the
immiscible polymer blend system by various thermodynamic and kinetic phenomena.[1],[2]. Compatibilizer
in polymer blend can act different roles to do the compatibilization. By the reduction in interfacial energy
between the two phases or by permitting a finer dispersion during mixing, or by providing a hindrance
against gross segregation, or it can act by enhancing the interfacial adhesion. This paper will be presenting
a brief account of the recent work done in immiscible polymer blends where various nanofillers like carbon
nanotubes, nanoclay etc. were used as compatiblizers.[4-6]
1. M. Yoo., S. Kim & J. Bang, (2013). Journal of Polymer Science Part B: Polymer Physics, 51(7),
494-507.
2. Z. M. Zou, Z. Y. Sun, &, L. J. An (2014). Rheologica Acta, 53(1), 43-53.
3. I. Labaume, J. Huitric, P. Médéric & T. Aubry (2013). Polymer, 54(14), 3671-3679.
4. A. K. Zachariah, P. K. Mohammed and V. G. Geethamma, A. K. Chandra, P. K. Mohammedc and S.
Thomas (2014). RSC Adv., 4, 580458058,DOI: 10.1039/C4RA11307A,
5. A. K. Zachariah, S. Thomas, P. K. Mohammed and A. K. Chandra, patent le no.135/CHE/2012, 2012.
6. H. J. Maria, N. Lyczko, A. Nzihou, K. Joseph, C. Mathew and S. Thomas, Appl. Clay Sci., 2014, 87, 120
158
Talk Number: 3 (Oral)
Time: Thursday, May 14, 2015 5:00 PM
Session: TH5_1: BIOT (Henzlik 124)
MECHANICALLY ACCURATE NANOFIBROUS VASCULAR GRAFT MATERIALS
Trevor Gnuse1 , Kaspars Maleckis1 , Jason Mactaggart2 , Alexey Kamenskiy2 , Yuris Dzenis1
1
2
Mechanical and Materials Engineering, University of Nebraska, United States
Surgery, UNMC, USA
Cardiovascular disease is the leading cause of death and disability in the United States. Patients with
advanced stages of the disease frequently require surgical interventions involving replacement or bypass of
diseased arterial segments with an arterial substitute, such as a patch or a graft. Despite the long history of
this surgical procedure, in many cases patients experience complications, leading to unsatisfactory clinical
results or even failure of the graft. Our findings suggest that major cause of these complications may be the
drastically different mechanical properties of the soft arterial tissue and available rigid graft materials.
Here we present development and characterization of novel polymer nanofiber-based vascular graft materials.
These materials were designed to mimic fiber networks of collagen and elastin in the native arteries and
manufactured using controlled electrospinning. Flexible process parameters allowed us to mimic important
morphological features of arterial walls, such as orientation and buckling of filaments. This structural
mimicry in turn allowed us to closely match the key mechanical properties of the artery, such as non-linearity,
compliance and anisotropy. In order to perform the complex multidimensional optimization of these grafts
we used a set of different characterization methods, including structural studies with electron microscopy,
polarized Raman spectroscopy, thermal analysis, and biaxial mechanical characterization of the nanofibrous
constructs. Furthermore we also characterized mechanical properties of individual nanofibers.
Our results demonstrate that the developed nanofiber-based materials enable mimicking both structural
features and key mechanical properties of different types of tissues. The methods developed can be used to
design and fabricate novel graft materials targeting individual patients, thus significantly reducing the risks
of complications in the vascular graft bypass surgeries.
159
Talk Number: 4 (Oral)
Time: Thursday, May 14, 2015 5:20 PM
Session: TH5_1: BIOT (Henzlik 124)
EVALUATION OF POTENTIAL APPLICATION OF UNUSUAL POLYMERSOMES
PREPARED FROM PH-RESPONSIVE DUAL HYDROPHILIC BIOCOMPATIBLE
RANDOM COPOLYMERS
Partha Laskar1 , Sudip Kumar Ghosh2 , Joykrishna Dey1
1
2
Chemistry, Indian Institute of Technology, Kharagpur, India
Biotechnology, Indian Institute of Technology kharagpur, India
Polymeric nanocarriers are one of the important colloidal systems applied in the advancement of medication research. Polymeric vesicles or polymersomes among several polymeric nanocarriers have such a
paramount importance to play an integral role in drug delivery application to gene transfection. Since inception, polyethylene glycol (PEG) has been used as a hydrophilic modification of the various polymeric
systems for personal care products to drug delivery systems. In contrast, we report here, for the first
time, unusual polymersome formation by a series of pH-responsive dual hydrophilic random copolymers,
cysteine-conjugated-poly[glycidyl methacrylate-co-mPEG] in different ratio, where methoxy poly(ethylene
glycol) methacrylate (mPEG) behaves as hydrophobe. All the three polymers were observed to decrease the
surface tension of water even without having any typical hydrophobe in their backbone and were found to
form vesicular aggregates above a relatively low critical aggregation concentration (CAC). Their self-assembly
formation and microstructural properties were evaluated by steady-state fluorescence technique using various probes such as N-phenyl naphthylamine (NPN), pyrene and 1, 6-diphenyl-1, 3, 5-hexatriene (DPH). The
presence of vesicular assembly by these polymers was confirmed by electron micrographs and light scattering
technique. The polymersomes are nearly monodisperse and quite stable at biological pH and temperature.
Even the polymersome formation in water is devoid of any help of external stimuli (pH, temperature, light or
ionic strength) or usage of any hazardous organic solvent. All of them can be used as a depot for hydrophilic
as well as hydrophobic cargo. All the polymersomes have shown high blood compatibility and literally no
cytotoxicity up to very high concentration range. Their cell permeability efficiency was clearly observed by
fluorescein isothiocyanate (FITC) tagged polymers. Interaction study with Human Serum Albumin (HSA) at
biological pH proves their adequate binding nature with the carrier protein without disturbing the secondary
structure of HSA. The polymers not only can encapsulate the guests in their vesicular assembly but also
can release them with the change of pH especially at acidic pH. Thus these polymersomes may find a great
potential in drug delivery application like intravenous delivery systems.
160
Thursday, May 14, 2015 Starting: 4:00 PM
TH5_2: PMMS (Henzlik 53)
Session Chair: Zheng Li
Assistant: Taylor Stockdale
Talks:
1. (4:00 PM, Keynote) Saiter:
GLASSY POLYMERS
PHYSICAL AGEING AND COOPERATIVE RELAXATION IN
2. (4:40 PM, Oral) Hagg Lobland: BRITTLENESS OF POLYMERS AND THE RELATION TO
TOUGHNESS
3. (5:00 PM, Oral) Li: CHARACTERIZATION OF STRAIN-INDUCED ELASTIC ANISOTROPY,
EQUILIBRIUM STRESS, AND MODELING OF THE THERMAL-MECHANICAL RESPONSE OF
PEEK
4. (5:20 PM, Oral) Xu: VISUALIZED POLYMER PROCESSING: FAST COLLOIDAL PARTICLE
REDISTRIBUTION AT NON-PLANAR SOLIDIFICATION INTERFACE
161
Talk Number: 1 (Keynote)
Time: Thursday, May 14, 2015 4:00 PM
Session: TH5_2: PMMS (Henzlik 53)
PHYSICAL AGEING AND COOPERATIVE RELAXATION IN GLASSY POLYMERS
Jean-Marc Saiter1 , Mehrdad Negahban2
1
2
Institut des Matériaux de Rouen, Universite de Rouen, France
Mechanical and Materials Engineering, University of Nebraska-Lincoln, U.S.A.
For many years researches have been engaged in describing the time dependent properties of glassy materials,
with polymers accounting for a large portion of this effort. The particular difficulty is in the glass transition
range where the characteristic relaxation times go from seconds when above the glass transition temperature
to years when below the glass transition temperature. Even though the glass transition phenomenon is
still today one of the unsolved problems of condensed matter theories, the fact is that all the glasses and
all the liquids exhibit common behavior. These characteristics are: (a) Around the glass transition, the
molecular movements are cooperative; (b) Blow the glass transition, the relaxations show physical ageing,
are nonlinear, are non-exponential, show a characteristic time distribution, and display auto slow down.
We present a large series of data obtained from a wide number of different glasses, (organic and inorganic polymers) focused on the characterization of physical ageing and on the values of the cooperative
domains at their glass transitions. When measurements are performed on very old glasses, it clearly appears
that the concept of the existence of one homogeneous glassy structure which relaxes during time cannot
describe the behavior observed even if the material studied is a monoatomic glass (as for Selenium based
glasses). From this, we construct an understanding of how the concept of heterogeneities frozen in at Tg is
important to describe the behavior of the glass during ageing.
162
Talk Number: 2 (Oral)
Time: Thursday, May 14, 2015 4:40 PM
Session: TH5_2: PMMS (Henzlik 53)
BRITTLENESS OF POLYMERS AND THE RELATION TO TOUGHNESS
Witold Brostow1 , Haley E. Hagg Lobland1 , Sahil Khoja1 , Sameer Khoja1,2
1
2
Dept. of Materials Science & Engineering and Dept. of Physics, University of North Texas, USA
Texas Academy of Mathematics and Science, University of North Texas, USA
Brittleness is an important feature of materials but one often described by only qualitative characterizations.
A quantitative scale of brittleness for polymers was defined in 2006 [1]. Thus brittleness B is defined by
a mathematical relationship between the elongation at break (by quasi-static mechanical testing) and the
storage modulus (by dynamic mechanical analysis). The scale of B applies to both neat and composite
polymers [2, 3], while researchers at the University of Sichuan demonstrated that the dimensional stability
of laminates was inversely proportional to brittleness [4]. Furthermore, the usefulness of B is seen through
its connection to viscoelasticity of polymers [1, 2] and impact strength [3]. The frequent question of the
relationship between brittleness and toughness, however, is not fully answered [5]. There exist multiple
definitions of toughness. Based on a comparison to impact strength, we have observed there is not a simple
inverse proportionality with B. The area under a stress-strain curve is another commonly used measure
of toughness. We are examining the connection between brittleness and toughness so-defined. Through
our investigations we are arriving at better descriptions of these mechanical properties and improving our
capacity for the prediction of polymer performance and service life.
[1] W. Brostow, H.E. Hagg Lobland & M. Narkis. Sliding wear, viscoelasticity and brittleness of
polymers, J. Mater. Res. (2006) 21, 2422.
[2] W. Brostow and H.E. Hagg Lobland, Predicting wear from mechanical properties of thermoplastic
polymers, Polym. Eng. & Sci. (2008) 48, 1982.
[3] W. Brostow & H.E. Hagg Lobland. Brittleness of materials: Implications for composites and relation to
impact strength, J. Mater. Sci. (2010) 45, 242.
[4] Chen J, Wang M, Li J, Guo S, Xu S, Zhang Y, Li T, Wen M (2009) Eur Polym J 45:3269-3281.
[5] W. Brostow, H.E. Hagg Lobland and M. Narkis. The concept of brittleness and its applications. Polymer
Bull. (2011) 59, 1697.
163
Talk Number: 3 (Oral)
Time: Thursday, May 14, 2015 5:00 PM
Session: TH5_2: PMMS (Henzlik 53)
CHARACTERIZATION OF STRAIN-INDUCED ELASTIC ANISOTROPY, EQUILIBRIUM STRESS, AND MODELING OF THE THERMAL-MECHANICAL RESPONSE OF PEEK
Wenlong Li1 , Eric N. Brown2 , Philip J. Rae2 , George A. Gazonas3 , Mehrdad Negahban1
1
2
3
Department of Mechanical and Materials Engineering, University of Nebraska-Lincoln, United States
Los Alamos National Laboratory (LANL), Structure Property Relations, United States
U.S. Army Research Laboratory, Aberdeen Proving Ground, United States
Poly-ether-ether-ketone (PEEK) is a high performance semi-crystalline polymer that appeared in the 1980s
[1] and is extensively used in the chemical and mechanical applications due to its excellent chemical-resistance
properties, toughness, and good high-temperature properties. Like many polymers and some metals, it can
show a substantial development of anisotropy in its response after plastic flow. We added experimental
results on the development of anisotropy using ultrasonic, and equilibrium stress measurements through
cyclic loading [2] to the measurements of response under dynamic loading by Rae and Brown [3] to model
the response of PEEK.
Ignoring the possible recrystallization of PEEK during loading, we develop a preliminary thermo-mechanical model for PEEK that is capable to reproduce the experimentally evaluated equilibrium stress, the
development of elastic anisotropy, and thermal-mechanical response at the loading rate from 0.0001 to 3000
1/s over a temperature range from -85o C to 140o C and for loading up to 40% compression. The model
is a multidimensional single-element nonlinear thermodynamically-consistent model. This model matches
the measured thermo-mechanical response below the glass transition and correctly predicts the measured
tangent modulus at equilibrium.
1. Attwood, T.E., Dawson, P.C., Freeman, J.L., Hoy, L.R.J., Rose, J.B., Staniland, P.A.: Synthesis
and properties of polyaryletherketones. Polymer 22, 1096-1103 (1981)
2. Negahban, M., Goel, A., Delabarre, P., Feng, R.: Experimentally evaluating the equilibrium stress in
shear of glassy polycarbonate. J. Eng. Mater. Technol. 128(4), 537-542 (2006)
3. Rae, P.J., Brown, E.N., Orler, E.B.: The mechanical properties of poly (ether-ether-ketone) (PEEK)
with emphasis on the large compressive strain response. Polymer 48, 598-615 (2007)
164
Talk Number: 4 (Oral)
Time: Thursday, May 14, 2015 5:20 PM
Session: TH5_2: PMMS (Henzlik 53)
VISUALIZED POLYMER PROCESSING: FAST COLLOIDAL PARTICLE REDISTRIBUTION AT NON-PLANAR SOLIDIFICATION INTERFACE
Zhanping Xu1 , Hongfeng Yu2 , Li Tan1
1
2
Mechanical and Materials Engineering, University of Nebraska-Lincoln, United States
Computer Science and Engineering, University of Nebraska-Lincoln, United States
Freeze-drying has been widely used for polymer processing due to its accessibility, environment-friendly
nature, and wide varieties of porous structures. However, freezing is also a complex process that requires
a major investigation of the process conditions and the formulations. Particularly, the mutual interaction
between the growing solid-liquid interface and the solute content in the suspension plays a critical role in
the formation of different porous structures. We built a two-dimensional numerical model to simulation a
directional freezing in a colloidal suspension, with the focus of non-planar solidification interface and colloidal
particle redistribution. We will demonstrate an interactive platform by coupling simulation module with a
visualization module through high performance GPU devices.
165
Friday, May 15, 2015 Starting: 8:30 AM
F1: Plenary (Auditorium)
Session Chair: Lucia Fernandez-Ballester
Assistants: Marzieh Bakhtiary Noodeh, Mohammad Nahid Andalib
Talk:
1. (8:30 AM, Plenary) Segalman: USING BIOINSPIRED POLYMERS TO EXPLORE THE ROLE OF
SEQUENCE ON CONTROLLING POLYMER PROPERTIES
Dr. Rachel A. Segalman, Professor of Chemical Engineering and Materials, University of California, Santa
Barbara; Director of AFOSR-MURI on Thermal and Electrical Transport in Organic and Hybrid Materials
166
Talk Number: 1 (Plenary)
Time: Friday, May 15, 2015 8:30 AM
Session: F1: Plenary (Auditorium)
USING BIOINSPIRED POLYMERS TO EXPLORE THE ROLE OF SEQUENCE ON
CONTROLLING POLYMER PROPERTIES
Rachel Segalman1
1
Chemical Engineering and Materials, University of California Santa Barbara, U.S.A.
Chain shape and monomer sequence are two handles that affect polymer properties and self-assembly; however, it is difficult to control these handles in conventional synthetic polymers without also changing other
factors, such as chemistry. Polypeptoids, a class of sequence-specific bioinspired polymers, have a chain shape
that can be tuned by the introduction of monomers with bulky chiral aromatic side chains, allowing one to
induce a helical conformation while preserving the chemical nature of the side chains. Here, we examine
the rigidity of polypeptoid helices using small angle neutron scattering to measure the persistence length of
both a helical and a non-helical peptoid chain. Incorporation of these polypeptoids into block copolymers
enables a systematic study of the effect of chain shape on self-assembly while maintaining similar enthalpic
interactions. Because both the helical and non-helical peptoid blocks have similar flexibilities, it is shown
that the strength of segregation depends much more on monomer composition. These studies are a promising
basis for further examining the effect of monomer sequence control on block copolymer self-assembly. In this
talk, I will also discuss the use of this model system to understand the role of sequence on chain collapse and
globule formation in solution, polymer crystallization, and potential application as surface active agents for
anti-fouling.
167
Friday, May 15, 2015 Starting: 9:40 AM
F2_1: PS (Auditorium)
Session Chairs: Jean-Marc Saiter, Nicolas Delpouve
Assistant: Mohammad Nahid Andalib
Talks:
1. (9:40 AM, Keynote) Grande: DESIGN, SYNTHESIS, AND CHARACTERIZATION OF FUNCTIONAL DOUBLY POROUS CROSSLINKED POLYMERS
2. (10:20 AM, Keynote) López: A NEW METHOD TO MODIFY POLY(ARYLENE ETHERS) WITH
A MILD SULFONATION AGENT
3. (11:00 AM, Invited) Fors: DETERMINISTIC CONTROL OF POLYMER MOLECULAR WEIGHT
DISTRIBUTION
4. (11:20 AM, Oral) Neupane: CONVERSION OF PAPER WASTE INTO BIOPLASTICS (POLYLACTIC ACID)
5. (11:40 AM, Oral) Bhajiwala: MORPHOLOGICAL STUDY OF SPHERICAL MAGNESIUM
DICHLORIDE SUPPORTED TI BASED ZIEGLER NATTA CATALYST SYSTEM
168
Talk Number: 1 (Keynote)
Time: Friday, May 15, 2015 9:40 AM
Session: F2_1: PS (Auditorium)
DESIGN, SYNTHESIS, AND CHARACTERIZATION OF FUNCTIONAL DOUBLY
POROUS CROSSLINKED POLYMERS
Daniel Grande1
1
Complex Polymer Systems Laboratory, Institut de Chimie et des Matériaux Paris-Est, France
Over the last decade, the preparation of doubly porous materials has particularly attracted the focus of
researchers for the design of biocompatible scaffolds meant for biomedical applications. A hierarchical
double porosity may constitute a real benefit in the area of tissue engineering as the first porosity with pore
sizes higher than 100 µm may enable the seeding and development of suitable cell lines within the material,
while the second porosity with pore diameters lower than 1 µm should permit to improve the nutrient and
waste flow though the material when the macropores are clogged at the last stage of the cell culture. In this
context, different methodologies have hitherto been developed for the design and synthesis of such materials
displaying a double porosity. Temperature-induced phase separation in combination with particle leaching
has recently been reported for the design of poly(L-lactic acid) (PLLA), gelatin or PLGA scaffolds. Gas
foaming combined with particle leaching also seems to be appropriate for the preparation of doubly porous
PLLA- and PLGA-based frameworks when using dioxane/water as a porogenic solvent mixture and sodium
bicarbonate particles. In addition, High Internal Phase Emulsion (HIPE) templating has allowed for the
generation of hydrophilic polymeric materials presenting a hierarchically-structured porosity.
In order to develop more robust and versatile approaches to biocompatible doubly porous crosslinked
polymer materials, we propose novel porogen templating strategies through the use of two distinct types
of porogens, namely a macroporogen in combination with a nanoporogen. To generate the macroporosity,
either CaCO3 or NaCl particles or sieved PMMA beads are used, while the second porosity is obtained by
using either hydroxyapatite nanoparticles or a porogenic solvent. Such straightforward methodologies based
upon porogen removal allow for the preparation of relatively well-defined doubly porous poly(2-hydroxyethyl
methacrylate)-based materials. The porosity of the as-obtained biporous frameworks is characterized by
means of nitrogen sorption measurements, mercury intrusion porosimetry, and scanning electron microscopy.
Finally, the possibility to further functionalize such materials is investigated through an activation of
hydroxyl groups, and subsequent clickÂİ chemistry coupling with various amines.
169
Talk Number: 2 (Keynote)
Time: Friday, May 15, 2015 10:20 AM
Session: F2_1: PS (Auditorium)
A NEW METHOD TO MODIFY POLY(ARYLENE ETHERS) WITH A MILD SULFONATION AGENT
Natalia Andrea Agudelo1 , Juliana Palacio1 , Betty Lucy López1
1
Instituto de Química, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia, Colombia
A series of sulfonated polymers from PEEK and PEES were obtained using acetyl sulfate as mild sulfonating
reagent. First the thermoplastics polymers poly(ether ether ketone) (PEEK) and poly(ether ether sulfone)
(PEES) were synthesized by polycondensation reactions and characterized by gel permeation chromatography
(GPC) and thermal analysis. The sulfonation reaction was performed in the temperature range of 40-60o C
varying the reaction time from 3h to 12h. The modification of these materials was confirmed by spectroscopy
techniques such as Fourier transform infrared (FTIR). The degree of sulfonation (DS) was determined by 1H
NMR spectroscopy, thermogravimetric analysis (TGA) and by titration method, finding interesting relation
between the three used methods. The sulfonation degrees achieved values up to 38% at 40o C, 50% at
50o C, and 65% at 60o C for PEES samples and for the sample of PEEK the sulfonation degree did not
show changes at the conditions evaluated. Additionally, there was not polymer degradation, which was
corroborated by FTIR and 1H NMR. Differential scanning calorimetry (DSC) and TGA studies were carried
out to investigate the thermal properties and stability of the sulfonated polymers. Finally was evaluated
the modification of ABA triblock copolymers based on PEEK and PEES as middle block (B block) and
poly(methyl metacrylate) (PMMA) as end blocks (A block), under soft reaction conditions. The copolymers
will be evaluated as polymeric exchange membranes for fuel cells in future works.
170
Talk Number: 3 (Invited)
Time: Friday, May 15, 2015 11:00 AM
Session: F2_1: PS (Auditorium)
DETERMINISTIC CONTROL OF POLYMER MOLECULAR WEIGHT DISTRIBUTION
Brett Fors1
1
Department of Chemistry and Chemical Biology, Cornell University, USA
A polymer’s dispersity (Ð) is a commonly reported parameter that reflects the ratio of its weight average
and number average molecular weights (Mw and Mn, respectively). Many polymer properties have been
correlated with Ð, and values approaching unity are associated with controlled chain-growth polymerizations.
However, Ð does not rigorously describe the distribution of polymer chain sizes in a given sample, and it has
been postulated that variations in the shape and composition of this distribution will influence properties.
This presentation will detail a new modular approach for controlling the composition and shape of polymer
molecular weight distributions. Through a temporally controlled initiation strategy using controlled radical
polymerizations the length and molar quantity of polymer chains in a sample can be systematically controlled.
This method provides simple access to new materials and allows for the relationship between molecular weight
distribution and polymer properties to be fully explored.
171
Talk Number: 4 (Oral)
Time: Friday, May 15, 2015 11:20 AM
Session: F2_1: PS (Auditorium)
CONVERSION OF PAPER WASTE INTO BIOPLASTICS (POLY-LACTIC ACID)
Bishnu Prasad Neupane1
1
School of Health and Allied Sciences, Pokhara University, Nepal
The broadly apposite bioplastic, poly lactic acid was synthesized by using deinked paper waste as substrate
to Saccharomyces cerevisiae under controlled laboratory conditions. The substrate was initially subjected to
acid hydrolysis followed by alkali neutralization to attain a ideal neutral pH for the growth of Saccharomyces
cerevisiae. At regular intervals the amount of reducing sugar present in the samples were tested using DNS
method and the amount of sugar that was metabolized to alcohol and lactate were estimated using ferric
ammonium nitrate and ρ-hydroxy biphenyl method respectively. The lactic acid extract was concentrated
using a rotary vacuum evaporator and the amount was determined spectrophotometrically. The concentrated
extract was used for polymerization in the presence of stannous chloride. This resulted in the production of
white amorphous wafers. Polymerization trial with stannous chloride was done with 1ml of purified extract
with 0.1g of stannous chloride.
172
Talk Number: 5 (Oral)
Time: Friday, May 15, 2015 11:40 AM
Session: F2_1: PS (Auditorium)
MORPHOLOGICAL STUDY OF SPHERICAL MAGNESIUM DICHLORIDE SUPPORTED TI BASED ZIEGLER NATTA CATALYST SYSTEM
Hiren Manojkumar Bhajiwala1
1
Reliance Research & Development center, Reliance Industries Ltd, Hazira, India
The precursor of Ziegler-Natta catalyst plays an important role in maintaining the properties like porosity,
morphology, particle size and circularity. Which are very much important to get desired resin properties
[1-2]. These characteristic are monitored by various tools such as Scanning electron microscope (SEM) /
Transmission Electron Microscopy (TEM) /video microscopy, Surface area etc. The particle growth and its
morphology have been reported in many articles [3]. The catalyst morphology is a function of precursor
morphology and the final resin morphology is dependent on catalyst fragmentation pattern. The detail
understanding of the correlation between catalyst morphology and fragmentation pattern may be useful to
design a catalyst with desired performance. The several articles have explained fragmentation of catalyst
[4].
The surface morphology, topology, shape and physical structure of polypropylene resin particle synthesized using Z-N catalyst is an exact replication of base material used for catalyst. The surface
morphology of each stage precursor, catalyst and polymer resin has been studied using scanning electron
microscope. The SEM images of spherical primary particle of precursor indicated, it was generated from
numbers of tiny rod like secondary particle. The bunch of rod like tiny particle having lots of gape between
the each bunches, which forms porous structure of precursor. The supported Ti catalyst synthesized from
precursor showed exact replication of parent particle with slightly increase particle size. The catalyst showed
change in surface morphology of secondary particle with very high surface area compare to precursor. The
distribution of Ti on the support was found even on entire surface, which confirmed through energy dispersive
X-ray analysis (EDX). The morphology of polymer resin synthesized through slurry polymerization shows
exact replication of catalyst to polymer particle with 10-15 time particle growth.
References
1. R. Jamjah, G. H. Zohuri, J. Vaezi, S. Ahmadjo, M. Nekomanesh, M. Pouryari, J. App. Poly. Sci., Vol.
101, 3829-3834 (2006).
2. Zohuri, G. H., Ph.D. Thesis, University of Manchester Institute of Science and Technology (UMIST),
Manchester, 1993.
3. M. Abboud, P. Denifl, K.H. Reichert, J. App. Poly. Sci., Vol. 98, 2191-2200 (2005)
4. F. J. Karol, B. E. Wagner, I. J. Levine, G. L. Goeke, A. Noshay, R.B. Seymour, Cheng, T. Plenum: New
York, 1987.
173
Friday, May 15, 2015 Starting: 9:40 AM
F2_2: RSP/MPP (Heritage Room)
Session Chairs: Joseph Turner, Lucia Fernandez-Ballester
Assistant: Ehsan Rezaei
Talks:
1. (9:40 AM, Invited) Schubert: BINARY AND TERNARY BLENDS OF POLYPROPYLENE TYPESINFLUENCE ON THE HOMOGENEITY OF BIAXIAL ORIENTED FILMS
2. (10:00 AM, Oral) Chaganti: PLASTICIZED POLY (3-HYDROXYBUTYRATE): BIOBASED OLEGOMERIC DIISOCYANATE AS A TOUGHENER
3. (10:20 AM, Oral) Li: THE DYNAMIC FRACTURE BEHAVIOR OF PMMA
4. (10:40 AM, Oral) Wojtczak: ALL-POLYMER FIBRILLAR NANOCOMPOSITES
5. (11:00 AM, Oral) Akram: SOL-GEL DERIVED ORGANIC/INORGANIC HYBRID NANOCOMPOSITES FROM VEGETABLE OILS AS SURFACE COATING MATERIALS
6. (11:20 AM, Oral) Lin: CONTRIBUTION OF COLLAGEN FIBER UNDULATION TO MECHANICAL PROPERTIES OF TYPE I COLLAGEN GEL
174
Talk Number: 1 (Invited)
Time: Friday, May 15, 2015 9:40 AM
Session: F2_2: RSP/MPP (Heritage Room)
BINARY AND TERNARY BLENDS OF POLYPROPYLENE TYPES-INFLUENCE
ON THE HOMOGENEITY OF BIAXIAL ORIENTED FILMS
Dirk W. Schubert1 , Jochen Kaschta1 , Stephan Seidl1 , Peter Kunzelmann1
1
Material Science, Institute for Polymer Materials, Germany
Biaxial oriented polypropylene is one of the most used materials for industrial films and food packaging. In
terms of environmental and economic issues, the reduction of the film thickness, increasing the homogeneity,
enhancing the process efficiency and stability are in the focus of this work. To meet these demands, a
systematic investigation on the biaxial stretching process was made in this study. Therefore, two commercial
linear polypropylenes with different molar mass and a commercial long-chain-branched polypropylene were
used to obtain binary and ternary blends to adjust the elongation behavior on the molecular level. The
blending was carried out using a cast film process on a twin-screw-extruder. The cast films obtained, were
investigated via biaxial stretching varying the preheat time, the temperature and the stretching speed. The
thickness distribution of the films, were used as the measure for film homogeneity, before and after the film
stretching process. The obtained results reveal efficient and stable film stretching process conditions and a
desired polymer blend recipe.
175
Talk Number: 2 (Oral)
Time: Friday, May 15, 2015 10:00 AM
Session: F2_2: RSP/MPP (Heritage Room)
PLASTICIZED POLY (3-HYDROXYBUTYRATE): BIOBASED OLEGOMERIC DIISOCYANATE AS A TOUGHENER
Srinivasareddy Chaganti1,2 , Rameshbabu Padamati1,2 , Kevin O’connor3
1
The Centre for Research on Adaptive Nanostructures and Nanodevices, Trinity College Dublin, Dublin 2,
Ireland
2 School of Physics, Trinity College Dublin, Dublin 2, Ireland
3 NovaUCD, Belfield Innovation Park, University College Dublin, Belfield, Dublin 4, Ireland
Poly (3-hydroxybutyrate)’s (PHB) food packaging applications are limited due to its poor mechanical
properties, such as brittleness and low deformability. Although the mechanical properties of PHB have been
improved by addition of plasticizers [1-4], there is a demand to further improve the deformability and tensile
toughness for food packaging applications.
In the present work, the mechanical properties of PHB were tuned and enhanced by melt blending the
polymer with a biobased oligomeric diisocyanate synthesised from hexamethelene diisocyante. Oligomeric
diisocyanate was found to positively influence mechanical properties of PHB. PHB’s strain at break and
tensile toughness were improved with increasing weight fraction of oligomeric diisocyanate. The relative
elongation at break of PHB/oligomeric diisocyanate blends was increased by 275% and the tensile toughness
was increased by 293%. PHB’s glass transition temperature width (∆Tg) was influenced by oligomeric
diisocyanate. Glass transition onset temperature of PHB was shifted towards lower temperature with
increased weight fraction of oligomeric diisocyanate. The relative elastic modulus and storage modulus of
PHB/oligomeric diisocyanate blends at room temperature were decreased by 70% and 57% respectively.
The degree of crystallinity of PHB was effected by oligomeric diisocyanate where PHB/oligomeric diisocyanate blends exhibited lower crystallinity compared to PHB. The changes in mechanical properties of
PHB/oligomeric diisocyanate blends were mainly due to efficient weakening of intermolecular interactions in
the amorphous regions of PHB, and also a slight decrease in crystalline order of PHB.
* [email protected], [email protected]
References:
1. Bibers I, Tupureina V, Dzene A, and Kalnins M. Mechanics of Composite Materials 1999;35(4):357-364.
2. Choi JS and Park WT. Macromolecular Symposia 2003;197:65-76.
3. Wang LA, Zhu WF, Wang XJ, Chen XA, Chen GQ, and Xu KT. Journal of Applied Polymer Science
2008;107(1):166-173.
4. Abdelwahab MA, Flynn A, Chiou BS, Imam S, Orts W, and Chiellini E. Polymer Degradation and
Stability 2012;97(9):1822-1828.
176
Talk Number: 3 (Oral)
Time: Friday, May 15, 2015 10:20 AM
Session: F2_2: RSP/MPP (Heritage Room)
THE DYNAMIC FRACTURE BEHAVIOR OF PMMA
Zheng Li1 , Guiyun Gao1 , Jie Zhou1
1
Department of mechanics & Engineering Science, Peking University, China
Polymethyl methacrylate (PMMA) as a good transparent and typical tough engineering material is designed
to exhibit brittle fracture behavior of material in this paper. Semi-Circular Bending (SCB) specimens are
widely used in experimental analysis of complicated fracture processes due to their simple geometry and easy
loading control. Here SCB specimens of PMMA with different pre-crack angles and positions were employed.
An optical method of caustics was applied to obtain the dynamic fracture properties of PMMA, such as the
crack initiation, crack propagation, stress intensity factor and fracture toughness, etc. During the dynamic
crack propagation, the dynamic fracture parameters could be determined by measuring the caustic patterns
observed by a high speed camera. Moreover, we also compared the fracture mode of different pre-crack angles
and positions. Finally, the interaction between cracks or crack and damage in dynamic fracture process was
also investigated clearly by using this optical method. Results indicate that the fracture mode of SCB
specimen can be adjusted by pre-crack position and angle. The competition between cracks or influence of
damage could also be observed. The optical method of caustics is a proficient method to analyze the dynamic
fracture process and crack interaction.
177
Talk Number: 4 (Oral)
Time: Friday, May 15, 2015 10:40 AM
Session: F2_2: RSP/MPP (Heritage Room)
ALL-POLYMER FIBRILLAR NANOCOMPOSITES
Kinga Jurczuk1 , Malgorzata Wojtczak1 , Andrzej Galeski1
1
Department of Polymer Physics, Centre of Molecular and Macromolecular Studies Polish Academy of
Sciences, Poland
Polymers filled with ready-made polymer fibers may be substituted with success by nanocomposites with
nanofibrillar inclusions formed during compounding. It was already reported that polytetrafluoroethylene
(PTFE) nanofibers can be generated in situ by plastic deformation of chain-extended PTFE crystals
through shearing during compounding with different thermoplastic polymers [1, 2]. Now, we present how
the obtained method may be applied to other than PTFE crystalline polymers. Thus, HDPE powders were
synthesized via polymerization with controlled conditions like temperature and pressure. HDPE synthesis
was performed in toluene in the presence of methyl aluminoxane (MAO) and post-metallocene catalyst,
so-called FI catalyst, fluorinated bis(phenoxy imine) titanium complex at 10o C and 1 bar under atmosphere
of inert gas. The obtained polyethylene powder contained highly disentangled macromolecules, hence they
were capable of very large and easy deformation. The nascent powder consisted chain-extended crystals with
melting temperature around 140o C and degree of crystallinity of about 73%. The structure, thermal and
rheological properties of HDPE powders were characterized by different experimental techniques (e.g. SEM,
DSC, etc.). The all-polymer nanocomposites were produced by compounding of synthesized HDPE powders
at various concentration with various olefin copolymers at various processing conditions. The compounding
temperature was maintained below the melting temperature of HDPE crystals.
The studies revealed that HDPE crystals deformation efficiency can be affected by such factors: batch
of HDPE powder, type and viscosity of polymer matrix and shear rate or time of compounding. Those
factors influence significantly the composites morphology. For large single HDPE crystals with disentangled
macromolecules the deformation is easy and deformation ratios are large. The deformation of the HDPE
crystals leads to thin and strong nanofibers dispersed in the form of entangled network in the polymer
matrix. The obtained fibrillar nanocomposites are characterized by drastic changes of rheological and
mechanical properties in comparison to the polymer matrix..
The authors are indebted for financial support of the studies from the project of the National Science
Centre, Poland (DEC-2012/04/A/ST5/00606) 1.Jurczuk, K.; Galeski, A.; Piorkowska, E. Polymer 2013, 54,
4617-4628 2.Jurczuk, K.; Galeski, A.; Piorkowska, J.Rheol. 2014, 58, 589-605
178
Talk Number: 5 (Oral)
Time: Friday, May 15, 2015 11:00 AM
Session: F2_2: RSP/MPP (Heritage Room)
SOL-GEL DERIVED ORGANIC/INORGANIC HYBRID NANOCOMPOSITES
FROM VEGETABLE OILS AS SURFACE COATING MATERIALS
Deewan Akram1,2 , Eram Sharmin1,3 , Sharif Ahmad1
1
Materials Research Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi-110025, India
Department of Chemistry, Faculty of Science, Jazan University, P.O.Box 2097, Jazan, Kingdom of Saudi
Arabia
3 Department of Pharmaceutical Chemistry, College of Pharmacy, Umm Al-Qura University, Makkah AlMukarramah, PO Box 715, Postal Code: 21955, Kingdom of Saudi Arabia
2
Vegetable oils (VO) constitute the single, largest, easily available, low cost, non-toxic, non-depletable,
biodegradable family yielding materials that are capable of competing with fossil fuel derived petro-based
products. They bear multi functional groups and find applications in the development of low molecular
weight polymers such as alkyds, polyesters, polyesteramides, polyepoxies, polyols, and polyurethanes. VO
based polymers generally lack high mechanical strength due to their long aliphatic (flexible) fatty acid
chains. This can be overcome by the development of VO based organic/inorganic hybrids [O/IH], which
exhibit excellent combination of synergistic properties of both the organic and inorganic components.
In the present work, synthesis, characterization and coating properties of VO based O/IH materials are
described. Polyols from Ricinus Communis [RO], Linseed oil [LO] and tetraethoxyorthosilane [TEOS]
serve as organic and inorganic constituents, respectively. O/IH were prepared by “hydrolysis-condensation”
reactions. The hydroxyl groups of polyols condensed with TEOS, by “one-pot, two-step” reactions, forming
silica anchored polyol based O/IH which on addition reaction with isocyanate formed polyurethane hybrids.
In FTIR spectra, absorption bands at 800cm-1 (Si-O-Si sym str) and 1090.0cm-1 (Si-O-Si assym str)
confirmed the formation of silica particles in O/IH. TEM micrographs of O/IH revealed the presence of
unagglomerated and spherical silica particles. Thermogravimetric analysis showed multiple degradation
stages with the onset of degradation at 220o C-225o C. O/IH showed moderate to good antibacterial behavior
against E.coli and S.aureus. The physico-mechanical and barrier resistance performance of RO and LO
O/IH were conducted to evaluate their coating properties. LO based O/IH polyurethane coatings have
shown better corrosion protection efficiency compared to RO based O/IH polyurethane coatings.
Keywords: Ricinus communis, Linseed oil, TEOS, Organic/Inorganic hybrid, Nanocomposites, TEM,
Antibacterials, Coatings
179
Talk Number: 6 (Oral)
Time: Friday, May 15, 2015 11:20 AM
Session: F2_2: RSP/MPP (Heritage Room)
CONTRIBUTION OF COLLAGEN FIBER UNDULATION TO MECHANICAL
PROPERTIES OF TYPE I COLLAGEN GEL
Shengmao Lin1 , Linxia Gu1,2
1
2
Department of Mechanical and Materials Engineering, University of Nebraska-Lincoln, USA
Nebraska Center for Materials and Nanoscience, University of Nebraska-Lincoln, USA
Type I collagen, a major component of the extracellular matrix (ECM) of soft tissues, is widely used in
hydrogels for scaffold. The mechanical properties of collagen gel provide the basis of cell-scaffold interactions
and are essential in many scaffold design. Previous study has showed that the individual fiber structure
(including fiber length, diameter and strength) affect the mechanical properties of collagen gel. Thermal
undulation is another important characteristic and could be controlled by the temperature during the polymerization. However, its contribution to mechanical properties has seldom been studied. In current study,
the contribution of collagen fiber undulation was investigated through computational modeling. The collagen gel is modeled as three-dimensional random network of cross-linked fibers. Three different levels of
undulation along with straight collagen fiber network are compared together to unravel its effect on mechanical properties of the collagen gel. The results show that the stiffness of the collagen gel is reduced by the
undulation of the collagen fiber. This work would enhance our understanding of collagen gel mechanics and
better controlling its mechanical property under different polymerization condition.
180
Friday, May 15, 2015 Starting: 1:00 PM
F3: Awards and Closing Session
Session Chairs: Michael Hess, Jean-Marc Saiter, Jean-Jacques Pireaux, Mehrdad Negahban
Assistants: Wenlong Li, Ramin Hosseinabad, Marzieh Bakhtiary Noodeh
Index
Adams, Alina, 40
Ade, Harald, 95
Ade, Harald (Speaker), 24
Adhikari, Rameshwar (Poster), 84
Adhikari, Rameshwar (Speaker), 30
Agudelo, Andrea Natalia, 170
Ahmad, Sharif, 179
Akram, Deewan (Speaker), 179
Alarifi, Ibrahim (Poster), 106
Alarifi, Ibrahim (Speaker), 67
Alarifi, M. Ibrahim, 108, 135
Alharbi, Abdulaziz, 67
Alharbi, R Abdulaziz, 106
Alharbi, R Abdulaziz (Poster), 108
Alharbi, R Abdulaziz (Speaker), 135
Ameri, Tayebeh, 95
Anada, Yuichi (Speaker), 59
Andalib, Nahid Mohammad, 87
Andalib, Nahid Mohammad (Speaker), 74
Andrzejewski, Jacek, 123
Araujo, Steven, 29, 83, 85, 115
Asmatulu, Dr. Ramazan, 67, 106, 108, 135
Astakhova, Olena, 90, 91, 113
Aubin, Frederic, 122, 140
Bahader, Ali, 126
Bahrami, Mozghan, 62
Bakhtiary Noodeh, Marzieh (Poster), 115
Bashta, Bogdana, 90
Basson, Neil, 101
Bastos, Margarida, 133
Batteux, Florian, 29, 83, 85
Bellon-Fontaine, Marie-Noëlle, 72
Benetti, Maria Edmondo, 70
Bhajiwala, Manojkumar Hiren (Speaker), 173
Bin, Yuezhen, 152
Bin, Yuezhen (Speaker), 134
Blümich, Bernhard (Speaker), 18, 40
Blümich, Bernhard (Chair), 25
Blum, Paul, 148
Bo, Chong, 154
Boccaccini, Aldo, 73
Boitoit, Hugo, 122, 140
Bojda, Joanna, 99
Bowen, Daniel, 112
Bowler, Nicola, 97, 112
Boyer, A.E. Severine, 139
Brêda, José Carlos, 58
Brandel, Clement, 52, 93
Bratychak, Michael, 90, 91
Brodowsky, Hanna, 84
Brostow, Witold, 21, 60, 90, 91, 102, 113, 154, 163
Brown, N. Eric, 164
Browning, Jim, 33
Brumbley, Stevens, 102
Cai, Ronggang, 56
Cardona, Isidro Wilson, 114
Cartigny, Yohann, 52, 93
Castano, M. Victor (Speaker), 157
Causin, Valerio, 155
Causin, Valerio (Speaker), 70
Chaganti, Srinivasareddy (Speaker), 176
Chan, Chin Han, 42
Chan, Chinhan (Poster), 92
Chan, Chinhan (Speaker), 46
Chan, Chinhan (Chair), 55
Charlon, Sebastien, 119
Chen, Jihua, 33
Chen, Wei, 33
Chen, Zhong (Poster), 96
Cheng, Stephen, 87
Cheng, Z. D. Stephen, 104, 105
Cheng, Z. D. Stephen (Speaker), 128
Choi, Sung-Hyun, 76
Cichorek, Michal, 99
Cicogna, Francesca, 103
Cloarec, Thomas, 154
Conzatti, Lucia, 103
Coquerel, Gérard, 51
Coquerel, Gerard, 52, 93
Cornelius, Christopher (Chair), 39, 77
Cosby, Tyler James (Poster), 94
Daily, Connor (Poster), 97
Danieli, Ernesto, 40
Dargent, Eric, 51, 52, 93, 120, 121, 122, 140
Dargent, Eric (Poster), 101, 119
Dargent, Eric (Speaker), 27
182
Dargent, Eric (Chair), 136
Das, Amit, 30
Dazzi, Alexandre, 72
Delbreilh, Laurent, 27, 51, 119, 120
Delpouve, Nicolas, 83, 85, 101, 115
Delpouve, Nicolas (Poster), 103, 120
Delpouve, Nicolas (Speaker), 29
Delpouve, Nicolas (Chair), 168
Denchev, Zlatev Zlatan, 58
Denchev, Zlatev Zlatan (Speaker), 53
Dencheva, Vassileva Nadya, 53
Dencheva, Vassileva Nadya (Speaker), 58
Desai, Kiritbhai Bhavesh (Speaker), 50
Desyatova, Anastasia, 87
Desyatova, Anastasia (Speaker), 148
Dey, Joykrishna, 160
Ding, Rui (Poster), 112
Ding, Yaping (Speaker), 73
Ding, Yunsheng (Poster), 126
Ding, Yunsheng (Speaker), 142
Domenek, Sandra, 101, 120
Du, Xiaoyan, 95
Ducharme, Stephen, 45, 153
Ducharme, Stephen (Chair), 43
Dupray, Valérie, 51
Durieux, Anne, 109
Dzenis, Yuris, 74, 75, 87, 88, 107, 131, 159
Dzenis, Yuris (Speaker), 64
Dzenis, A Yuris, 68
Dzenis, Yuris (Chair), 127, 129
Gao, Guiyun, 177
Gautam, Kumar Surendra, 30, 84
Gazonas, George, 89
Gazonas, A. George, 164
Geohegan, David, 33
Ghosh, Kumar Sudip, 160
Giraldo, Fernando Luis, 114
Giroud, Emmanuelle, 138
Gnuse, Trevor (Speaker), 159
Gonçalves, Carolina (Speaker), 133
Goponenko, Alexander, 88
Goponenko, Alexander (Speaker), 68
Grande, Daniel, 124
Grande, Daniel (Speaker), 169
Granowski, Gregory, 60, 90
Grellmann, Wolfgang, 30, 84
Grigoryeva, Olga, 124
Gruverman, Alexei, 153
Grykien, Remigiusz, 34
Gu, Linxia, 180
Gu, Linxia (Chair), 69
Guenet, Jean-Michel (Speaker), 19, 26
Gui, Haoguan, 126
Guinault, Alain, 101, 120
Gusakova, Kristina, 124
Ha, Ligyeom, 74
Haas, Simon, 71
Hagg Lobland, E. Haley (Speaker), 60, 163
Harun, Mk, 92
Haudin, Jean-Marc, 139
Esposito, Antonella, 121
Hausberger, Andreas, 49
Heinrich, Gert, 30, 84
Fainleib, Alexander, 124
Heinz,
Hendrik, 98
Fang, Huagao, 126, 142
Henning, Sven, 30
Fatyeyeva, Kateryna, 27
Henning, Sven (Speaker), 15
Fernandez-Ballester, Lucia, 121, 122
Henning, Sven (Chair), 16
Fernandez-Ballester, Lucia (Speaker), 140
Fernandez-Ballester, Lucia (Chair), 37, 136, 166, 174 Heres, Maximilian, 94
Herry, Jean-Marie, 72
Fink, Rainer, 95
Hess, Michael (Chair), 11, 79, 181
Follain, Nadege, 119
Hidzir,
Mh, 92
Fors, Brett (Speaker), 20, 171
Hilfiker, James, 48
Fors, Brett (Chair), 11
Hnatchuk, Nathalie, 60, 102
Frazier, Shane (Poster), 100
Hnatchuk, Nathalie (Poster), 90, 91
Furgal, Joseph (Poster), 86
Hnatchuk, Nathalie (Speaker), 21, 154
Furgal, C Joesph, 62
Holzner, Armin, 49
Hong, Kunlun, 33
Gafurov, Ulmas (Poster), 116
Hosseinabad, Ramin, 140
Gakhutishvili, Marina (Poster), 102
Hosseinabad, Ramin (Poster), 122
Galeski, Andrzej, 178
Hsu, Chih-Hao, 105
Galeski, Andrzej (Speaker), 130
Hu, Gerald, 60
Galeski, Stanislaw, 130
Gan, Seng Neon, 42
Huang, Jinsong, 35
183
Huang, Jinsong (Chair), 23, 31
Im, Soohyok, 54
Ivashkiv, Ostap, 113
Jérusalem, Antoine, 89
Jahan, I Kazi, 68
Jakowski, Jacek, 33
Jamil, Tariq (Poster), 98
Janasz, Lukasz, 34
Jasa, John (Poster), 89
Jayasinghe, Gaya Hasani (Poster), 82
Jiao, Xuechen (Poster), 95
Jo, Won Ho (Speaker), 36
Jomni, Fethi, 138
Jonas, M. Alain (Speaker), 56
Jubeli, Emile, 72
Julie, Pepin, 137
Jurczuk, Kinga, 130, 178
Kahouli, Abdelkader, 138
Kamenskiy, Alexey, 159
Kammer, Hans-Werner, 46
Kaschta, Jochen, 175
Kaser, Jase (Poster), 107
Kern, Wolfgang, 49
Keum, Jong, 33
Khan, S. Waseem, 67, 135
Khoja, Sahil, 163
Khoja, Sameer, 163
Kim, Kyung Tae, 36
Kim, Yong-Rak, 54, 125
Kim, Yong-Rak (Chair), 47
Kosciuszko, Artur, 132
Kunzelmann, Peter, 117, 175
López, Lucy Betty (Speaker), 170
Lach, Ralf, 30, 84
Laine, Richard, 86
Laine, M. Richard (Speaker), 62
Lanceros-Méndez, Senentxu, 58
Lanyi, Franz (Poster), 117
Lapienis, Grzegorz, 99
Laskar, Partha (Speaker), 160
Le, Hai Hong, 30
Lee, Jiayin, 92
Lee, Jin Woo, 36
Lee, Min-A, 76
Lee, Soon Jeong, 74
Lefebvre, Jean-Marc (Speaker), 137
Lemme, Max, 111
Li, Shumin, 153
Li, Wei, 73
Li, Wenlong, 29, 83, 115
Li, Wenlong (Poster), 85
Li, Wenlong (Speaker), 164
Li, Xue (Speaker), 66
Li, Yu, 126, 142
Li, Zheng (Speaker), 177
Li, Zheng (Chair), 161
Liebscher, Marco, 30, 84
Lim, Yul Jung, 74
Lin, Shengmao (Speaker), 180
Lin, Zhiwei, 105
Lin, Zhiwei (Poster), 104
Liu, Hao (Poster), 105
Liu, Yong, 107
Lobland, Haley (Poster), 113
Loubeau, Florian (Poster), 109
Lu, Haidong, 153
Lugito, Graecia (Speaker), 141
Luszczynska, Beata, 34
Lyu, Min-Young (Speaker), 76
Mühlbacher, Inge, 49
Mactaggart, Jason, 159
Magalhães, Fernão, 133
Mahat, B. Khairul, 106
Makowski, Tomasz, 34
Maleckis, Kaspars, 159
Maleckis, Kaspars (Speaker), 75
Mallon, E Peter, 101
Manhart, Jakob (Speaker), 49
Marais, Stephane, 119
Mareau, Vincent, 138
Marlière, Christian, 72
Masruchin, Nanang, 70
Matsuo, Masaru (Speaker), 152
Meldrum, Tylor, 40
Menard, P. Kevin (Chair), 16
Menard, P. Kevin (Speaker), 12
Messman, Jamie, 112
Minutolo, Joseph, 94
Miri, Valérie, 137
Mokni, Marwa (Speaker), 138
Monnier, Xavier, 101
Morin, Ezequiel, 121
Nassar, Fernandes Samira, 120
Negahban, Mehrdad, 29, 83, 85, 89, 96, 115, 162, 164
Negahban, Mehrdad (Chair), 22, 181
Neupane, Prasad Bishnu (Speaker), 172
Nittler, Laurent, 28
Nougaret, Laurianne, 56
Nouman, Micheal, 72
184
Nuryawan, Arif, 155
O’connor, Kevin, 176
Oberhauser, Werner, 103
Odykirk, Timothy, 86
Okamoto, Shigeru (Speaker), 151
Oligschlaeger, Dirk, 40
Oliveira, Matos Filipa, 58
Ong, Chonghup, 92
Ospina, Catalina Anny (Poster), 114
Ouyang, Jianyong (Speaker), 32
Padamati, Rameshbabu, 176
Paiva, Diana, 133
Palacio, Juliana, 170
Pan, David, 62
Pandey, Himadri, 111
Papkov, Dimitry, 88, 107
Papkov, Dimitry (Speaker), 131
Papkov, Dimitry (Chair), 69
Park, Byung-Dae (Speaker), 155
Park, Byungdae, 70
Park, Seong-Yeol, 76
Passaglia, Elisa, 103
Patois, Tilia, 56
Pelaez, Alberto Carlos, 114
Petit, Samuel, 52, 93
Piorkowska, Ewa, 130
Piorkowska, Ewa (Poster), 99
Piorkowska, Ewa (Speaker), 139
Pireaux, Jean-Jacques (Speaker), 28
Pireaux, Jean-Jacques (Chair), 79, 143, 181
Piszczek, Kazimierz, 132
Poddar, Shashi (Speaker), 45
Pokharel, Sundari , 102
Pribil, Greg, 48
Rae, J. Philip, 164
Rain, Pascal, 109
Regnier, Gilles, 130
Renault, Margareth, 72
Rezaei, Ehsan, 149
Rezaei, Ehsan (Poster), 118
Rijal, Bidur, 27
Roether, Judith, 73
Roth, V. Stephan, 53
Rozanski, Artur, 130
Rudrappa, Deepak, 148
Ruhkopf, Jasper, 111
Saaid, Fi, 92
Sachdeva, Sanchit, 60
Sadat Ebrahimi, Mir Mortzea, 71
Saharin, Munirah Siti, 41
Saiter, Allison, 27
Saiter, Allisson, 101, 103
Saiter, Jean-Marc, 29, 42, 83, 85, 115
Saiter, Jean-Marc (Poster), 124
Saiter, Jean-Marc (Speaker), 17, 162
Saiter, Jean-Marc (Chair), 168, 181
Salim, Sugama Yoga (Speaker), 42
Sangoro, Joshua, 94
Sangoro, Joshua (Speaker), 57
Saunier, Johanna (Speaker), 72
Sayana, Susmitha, 60
Schönherr, Holger (Speaker), 14, 71
Schönherr, Simon (Poster), 111
Schönherr, Holger (Chair), 156
Schaller, Raimund, 49
Schamme, Benjamin (Poster), 121
Schamme, Benjamin (Speaker), 51
Schlögl, Sandra, 49
Schmidt, Mitchell (Poster), 110
Schubert, Dirk, 73
Schubert, W. Dirk, 117
Schubert, W. Dirk (Speaker), 13, 175
Schwahn, Evan (Poster), 83
Sclavons, Michel, 119
Segalman, Rachel (Speaker), 167
Seguela, Roland, 137
Seidl, Stephan, 175
Serpe, Michael J, 66
Serpe, J. Michael (Chair), 150
Serpe, J. Michael (Speaker), 65
Shao, Ming, 33
Sharmin, Eram, 179
Shinde, A. Manish, 108
Shyshchak, Olena, 113
Sim, Laihar, 46
Singh, Kawarpal, 40
Skórczewska, Katarzyna, 123
Sollogoub, Cyrille, 120
Song, Jingfeng (Speaker), 153
Soto-Puente, A. Jorge, 27
Soulestin, Jeremy, 119
Sowinski, Przemyslaw, 139
Srubar, Wil, 100
Stein, Gila (Speaker), 38
Sterzynski, Tomasz (Poster), 123
Sterzynski, Tomasz (Speaker), 132
Stockdale, Taylor (Poster), 87
Stoclet, Gregory, 137
Sudesh, Kumar, 42
Sumpter, Bobby, 33
Sun, Jianing (Speaker), 48
185
Sun, Kuan, 32
Sylvestre, Alain, 138
Tücking, Katrin-Stephanie, 71
Tan, Li, 29, 121, 153, 165
Tan, Li (Chair), 61, 63
Tarawneh, Constantine, 121
Tashiro, Kohji (Speaker), 41, 144
Tesserau, Manon, 121
Thomas, Sabu (Speaker), 158
Tomaszewska, Jolanta, 123
Tszydel, Izabela, 34
Turner, Joseph, 118, 148
Turner, Alan Joseph (Chair), 145
Turner, Alan Joseph (Speaker), 149
Turner, Joseph (Chair), 174
Yuya, Philip (Chair), 145
Zare Rami, Keyvan (Poster), 125
Zhang, Di, 142
Zhang, Lili, 89
Zhang, Panpan, 152
Zhang, Rong, 152
Zhang, Shengnan, 134
Zhang, Wen-Bin, 105
Zhang, Zesheng, 89
Zhou, Jie, 177
Zia, Wasif, 40
Zou, Yan (Poster), 88
Zubyk, Halyna, 91
Ulanski, Jacek (Speaker), 34
Vale, Isabel, 133
Vasquez, Yolanda, 82
Viel, Quentin (Poster), 93
Viel, Quentin (Speaker), 52
Wagner, Stefan, 111
Wei, Haibing, 142
Wells, Sabrina, 112
White, B. John, 60
Whittington, R. Abby (Speaker), 78
Winie, Tan, 46, 92
Wojtczak, Malgorzata (Speaker), 178
Woo, M. Eamor, 141
Woollam, John, 48
Wu, Shaojun, 126
Wu, Yingji, 154
Xia, Yijie, 32
Xiao, Kai (Speaker), 33
Xiao, Zhengguo (Speaker), 35
Xu, Chunye (Speaker), 44
Xu, Pei, 142
Xu, Zhanping (Speaker), 165
Yablon, Dalia (Speaker), 146
Yagoubi, Najet, 72
Yamane, Honami, 86
Yao, Qingqing, 73
Yi, Eongyu, 86
You, Taesun, 125
You, Taesun (Speaker), 54
Youngblood, Justin, 102
Yu, Hongfeng, 165
Yue, Kan, 105
Yuya, Philip (Speaker), 147
186
92
1
25
26
24
28
3
2
77
44
32
25
34
10
90
9
71
72
69
27
A2
B2
A1
A2
A1
B1
A2
8
45
62
20
60
38
18
61
79
80
33
24
39
A1
A2
A1
A1
A1
B2
A1
A2
B1
B1
B1
B2
B1
A1
B1
41
4
55
37
66
58
82
31
92
36
89
70
69
59
86
16
96
36
10
15
91
54
6
29
64
19
37
3
84
2
89
50
96
93
EY
73
79
PA
WA
Y
45
14
11
38
72
ONLY
71
80
90
70
A1
B2
B2
B2
A2
B2
A1
A1
B1
A2
A2
B2
A1
A1
B1
A1
95
28
37
38
37
63
56
67
88
53
37
17
16
74
57
51
95
B
97
13
91
A1
B1
A1
A2
A2
B1
B1
B1
A1
B1
B1
A2
A2
A2
A1
A1
85
94
5
7
65
46
51
56
82
21
35
30
48
73
82
68
44
VINE STREET
Sandoz Hall (SZRH)
Schramm Hall (SCRH)
Scott Engineering Center (SEC)
Seaton Hall (SEH)
Schorr Center (SHOR)
Selleck Quadrangle (SELK)
Sheldon Museum of Art (SHEL)
Smith Hall (SMRH)
Stadium Drive Parking Garage (SDPG)
State Museum of Natural
History (MORR)
Syford House (SYF)
Teachers College Hall (TEAC)
Technology Development
Temple Building (TEMP)
Theodore Jorgensen Hall (JH)
Track Office Building (TOB)
12
17th & Vine Recreation Fields
68
Y STREET
HOLDREGE STREET
Morrill Hall (MORR)
Nebraska Champions Club (NECH)
Nebraska Hall (NH)
Nebraska State Historical Society
Nebraska Union (NU)
Neihardt Residence Center
Oldfather Hall (OLDH)
Osborne Athletic Complex (MSTD)
Othmer Hall (OTHM)
Parking & Transit Services (SDPG)
Pershing Military & Naval
Science Building (M&N)
Piper Hall (PIPH)
Pound Hall (PRH)
Raymond Hall (RAYH)
Richards Hall (RH)
Robert E. Knoll Residential Center
Q STREET
R STREET
37
46
67
74
RK
83
84
39
93
89
40
41
42
Transportation Services (TRAN)
U Street Apartments (UST)
University Health Center (UHC)
University Housing Office (UHOF)
UNL Children's Center
UNL Credit Union (UNLCU)
Utility Plant (CCUP)
Van Brunt Visitors Center (RVB)
The Village (VILL)
Vine Street Apartments (2222, 2244)
Watson Building (WAT)
Westbrook Music Building (WMB)
Whittier Research Center (WHIT)
Wick Alumni Center (WICK)
Woods Art Building (WAB)
A1
B1
B1
B1
B1
B2
A1
A2
B1
B1
B1
A2
B1
B2
A2
®
43
Q STREET
R STREET
69
EAST CAMPUS
22
15
43
1
83
42
78
6
76
11
43
81
49
40
87
2
1
August 2010
The University of Nebraska-Lincoln is an equal opportunity educator and employer with a comprehensive plan for diversity. ©2008, The Board of Regents of the University of Nebraska. All rights reserved.
A2
A1
B1
A1
B1
A2
B1
A2
B2
A2
A1
A2
A2
B1
S STREET
Selleck
Recreation
Area
47
LL
U STREET
Inventory - Surplus Property
Jackie Gaughan Multicultural
Center (GAUN)
Kauffman Academic
Residential Center (KAUF)
Key Services (FMS)
Kimball Recital Hall (KRH)
Landscape Services (LAND)
Lied Center for Performing Arts (LIED)
Love Hall (LOVH)
Love Library (LLN) (LLS)
Mabel Lee Hall (MABL)
Manter Hall (MANT)
Mary Riepma Ross Media
Arts Center (RVB)
Memorial Stadium
Midwest Roadside Safety Facility (FMC)
Union
52
Devaney Sports Center (DEV)
Ed Weir Track & Soccer Stadium
Extended Education and Outreach (900)
Facilities Management and
Planning (FMP)
Facilities Management Shops (FMS)
Fairfield Hall (FAIR)
Haymarket Park Stadium
Complex (HAYB)
Hamilton Hall (HAH)
Harper Hall (HRH)
Hawks Championship Center (HCC)
Henzlik Hall (HENZ)
Heppner Hall (HEPP)
Hewit Academic Center (HEWA)
Hewit Place (HEWP)
Husker Hall (HUSK)
9
17
Broyhill Fountain
35
48
49
VA
16th STREET
47
26
8
18
Donaldson
Garden
50
66
PE
94
LO
85
REET
14
A2
B1
A1
B2
A2
A2
B1
B1
A1
7
51
34
VINE STREET
65
Mabel Lee Fields
TE
81
AN
T
17th S
97
A
6
Love
Garden
19
Mueller
Tower
63
64
W STREET
78
H
EET
Behlen Laboratory (BEL)
Benton Hall (BENH)
Bessey Hall (BESY)
Bioscience Greenhouses (BIOG)
Brace Laboratory (BL)
Burnett Hall (BURN)
Business Services Complex (BSC)
Campus Recreation Boat House (BOAT)
Campus Recreation Center (CREC)
Canfield Administration
Building (ADMN) (ADMS)
Cather Hall (CRH)
Coliseum (COL)
College of Business Administration (CBA)
Cook Pavilion (COOK)
The Courtyards (CORT)
Culture Center (333)
Madden
Garden
5
20
33
Cather
Garden
53
52
60
76
14th & Avery
Recreation Area
RT
STR
13
21
31
32
59
61
62
AVERY AVE.
77
82
NO
86
EET
12
4
Sheldon Sculpture
Garden
22
29
30
54
58
CREE
SALT
AY
ADW
K RO
87
B
18th
STR
14th & Avery Parking Garage (14PG) A1
17th & R Parking Garage (17PG) B2
1820 R (1820)
B2
19th and Vine Parking Garage
B1
420 University Terrace (420)
B2
501 Building (501)
A2
900 N. 22nd (900)
B1
940 N. 17th (940)
B1
Abel Hall (ARH)
B1
Alexander Building (ALEX)
A2
American Mathematics Competitions
Building (1740)
B1
Andersen Hall (ANDN)
B2
Andrews Hall (ANDR)
A2
Architecture Hall (ARCH) (ARCW) A2
Avery Hall (AVH)
A1
Beadle Center (BEAD)
B1
27
56
55
57
88
POINT OF INTEREST
VISITOR PARKING
GREEK HOUSING
POLICE
EMERGENCY PHONE
Sheldon
2
1
0
18
T
EE
TR
10
th
S
I-
IVE
DR
IU
M
SREET DIRECTION
ET
®
TRE
ST
AD
City Campus
T
14th S
TREET
University of Nebraska–Lincoln
14th STREE
A
h
19t
12t
hS
T
Henzlik
TREE
2
13th
S
RE
ET
14th
R EET
STREET
T
17th S
ST
15th STREET
D
2N
Transportation
Svcs.
City Campus
Nebraska
Innovation
Campus
STREET DIRECTION
Military Road
Devaney
Sports Center
Bessie St.
Ante
Holdrege St.
Holdrege St.
22nd St.
21st St.
20th St.
12th St.
k
19th St.
e
Cre
14th St.
9
pe
way
10th St.
D
OA
ILR
RA
FE
lo
Ante
Park
9th St.
Track
Office
Bldg.
y
Valle
Claremont St.
New Hampshire St.
OR
NN
TO
ING
RL
BU
COURT STREET
lope
Court St.
A
NT
SA
N/
ER
TH
Sheldon St.
Dudley St.
1
Cather/Pound
Recreation Fields
U St.
Apts.
Husker
Hall
Cather
Hall
'U' St.
'T' St.
Hewit
Place
Eastside
Suites
'R' St.
'R' St.
17th & R
Parking
Garage
5
University
Police
Andersen
Hall
Credit
Union
3
18th & R
Garage
50/50
Apartments
'Q' St.
23rd St.
Alexander
Building
University
Suites
22nd St.
1
'S' St.
Residential
Center
21st St.
1
420
Univ
Terrace
20th St.
Ross Media
Arts Center
Van Brunt
Visitors
Center
Wick
Alumni
Center
1
19th St.
Temple
Bldg. Mary Riepma
Pound
Hall
Knoll
'S' St.
Gaughan
Multicultural
Center
Guest & Visitor Parking
General Visitor Parking
1. Metered Parking
2. - Cashiered Facility (SDPG)
- Pay on Exit (Credit/Debit)
(14th & Avery Garage)
3. Morrill Hall Visitor
Current as of June 9, 2014
Vine St.
Beadle
Center
Selleck
Quad
Nebraska
Union
Love Garden
12th St.
11th St.
10th St.
9th St.
1
1
18th St.
College of
Business
Administration
Lied Center
for Performing
Arts
Q Place
Garage
Whittier Fields
22nd St.
Coliseum
Love Administration
Library
Bldg.
1
The
Courtyards
17th St.
Kimball
Recital
Hall
19th & Vine
Garage
Neihardt
Sheldon
Museum
of Art
'Q' St.
'P' St.
Campus Rec.
Facility
Hamilton
Hall
Woods
Art Bldg.
Westbrook
Music
Bldg.
'R' St.
Andrews
Hall
Burnett
Hall
University
Health Ctr.
'U' St.
Canfield
Architecture
Hall
University
Press
1
10
Vine St. Apts.
Seaton
Benton
Hall
Hall
Fairfield
Hall
Kauffman
Academic
Residential
Center
Greenspace
Behlen
Lab
Brace
Lab
Whittier
Building
Sandoz
Hall
'W' St
Children’s
Center
900 N. 22nd Street
1
Othmer
Hall
16th St.
'S' St.
11
Morrill
Hall
14th St.
501
Bldg.
Richards
Hall
Mueller
Tower
Oldfather Hall
Avery
Hall
Manter
Hall
Jorgensen
Hall
15th St.
1
'T' St.
Mabel Lee Fields
Teachers
College Hall
Abel
Hall
Scott
Engineering
Center
Henzlik Hall
3
Bessey Hall
Schorr
Center
Pershing
Military
& Naval
Science
Facilities
Management
Shops
Vine St.
13th St.
STADIUM DRIVE
th
Nor South
I-80 I-80
2
Stadium
Drive
Parking
Garage
6
Osborne
Athletic
Complex
1
1
Facilities
Management
& Planning
Nebraska
Hall
'W' St
Mabel Lee Hall
Ed Weir Track
Hewit
Academic
Center
X STREET
1
Utility
Plant
Cook
Pavilion
'U' St.
Boat House
Outdoor
Adventures
'Y' St.
Y STREET
8
21st St.
10th St.
1
Hawks
Championship
Center
Nebraska
Champions
Club
1
The
Village
Avery Avenue
'W' St
1
14th St.
14th &
Avery
Parking
Garage
k
y
Orchard St.
Business
Services
Complex
7
e
Cre
t
Sal
wa
oad
kR
e
Cre
Harper
Hall
Schramm University
Housing
Hall
Office
Smith
Hall
pe
'Y' St.
lo
Ante
Charleston St.
17TH STREET
Landscape
Services
Guest Parking
5. Admissions Office
6. CB3 & Athletics Performance
Lab
Campus Affilated Visitor Parking
7. Business Services Complex
8. Facilities Management & Planning
9. Continuing Education Visitors
10. Children’s Center
11. University Health Center Patient
'P' St.
HAYMARKET (vicinity of 7th & P Streets) - restaurants,
unique shopping and fun nightspots in restored turn-of-thecentury warehouses: antique shops, art galleries, Pinnacle
Bank Arena and more
DOWNTOWN LINCOLN, NE - MUSEUMS / ATTRACTIONS
The University of Nebraska–Lincoln is an equal opportunity educator and employer.