Nanotechnologies Potential in Forest and Paper Industry Nano-Hemicelluloses Nano Hemicelluloses For Barrier/Strength g Improvements p Improvements in Tensile Index with 4% Applie d Glucuroxylan Tensilee Index 60 50 40 30 20 SW ECF P l Pulp Bulk E i h Enrich Xylan Surface E i h d Enriched Xylan Very recent developments in nano-lignin suggest new barrier opportunities Nano-Enhanced Paper: Coatings C Current S Studies di n n NH3+ Cl- N Cl+ Nanosized TiO2 materials enhance titania’s unique i properties ti by b giving i i large l surface f areas Tube Hollow ball Hollow ball Belt Film Super hydrophobic Barrier Coating Super-hydrophobic Method M th d off enhancing h i hydrophibicity: h d hibi it Lowering L i surface f energy by coating of hydrophobic material. However the material with the lowest surface However, energy (6.7 mJ/m2 for a surface with regularly aligned closest-hexagonal-packed –CF3 groups) gives i a water t contact t t angle l off only l around d 120o. Super hydrophobic surface: Both receding Super-hydrophobic advanced water contact angles above 150o. and Water, W t i ice, grease, and d bio bi contaminants t i t will ill nott be b able to deposit on super-hydrophobic surfaces Lotus Effect (a) (b) (c) Figure 1. (a) SEM images of the lotus leaf surface. Schematic representation of the self-cleaning mechanism: moving of water droplet along contaminated smooth (b) and rough (c) surfaces. http://www.biologie.uni-hamburg.de Coatings with hydrophobic silica (colloidal silica + FAS-17) Figure 4. SEM images of films on glass and the shapes of water droplets on the films. (a) glass + heptadecafluorodecyltrimethoxysilan (FAS-17) coating; (b) film from methanol based colloidal silica and (c) film from methyl ethyl ketone (MEK) based silica. T. Watanabe, et al, “Processing of roughened silica film by coagulated colloidal silica for super-dydrophobic coatng” J Materials Sci Lett 2001, 20, 1975. Barrier Coating with Nanomaterials • PolymerPolymer P l -clay l nanohybrids h b id are important i new materials i l – Improve modules, scratch properties, strength, stiffness, heat resistance and preservation preservation, etc. etc – Increase barrier properties for gas, water and grease – Can C be b usedd for f textile, t til painting, i ti coating, ti andd many others th • Barrier properties are very important for some paper products, such as containers for milk, milk juice, juice ice cream, cream meet, meet fish, fish fruit, fruit microwave fast food, food plates and boxes, drink cups, photo papers, p p , etc • Problems of waxed food containers: unun-recyclable, cannot be used as containers for milk, juice, ice cream, fast food, food plates Nano-Optical p Effects New Value Added Features: Opticals Objective: Develop new fiber-based products that take advantage of the special optical and photonic properties of nanomaterials and that enable manufacturers to: o Increase opacity and light barrier properties of paper and paperboard o Utilize new methods for holographic imagery and graphics on paper surfaces o Employ novel optical effects on paper surfaces and in paper webs Abalone Shell Source: Belcher et al 1999 Target market opportunities: o Lightweight printing papers with high opacity o Paperboard with high light barrier for packaging light-sensitive contents without use of metal foil o Papers and folding cartons with new security and anti-counterfeiting features o White White-surfaced surfaced paper and paperboard with high content of recycled and/or unbleached fiber Enabling technologies – pre-competitive research: o Photonic effects of nanomaterials for light scattering, light absorption, light transmission wavelength shifting transmission, shifting, etc. etc o Imaging and holography with nanoparticles o Nanomaterials that react to ambient stimuli optically, electronically, or mechanically Processes for preparing commercial quantities of photonic nanomaterials and for applying ultra-thin coatings onto paper surfaces Nanostructured Filler Engineering: Mg(OH)2 Nanobelts synthesized by Y. Deng Low cost Low density (2.4) High brightness No retention aid is needed (good formation) L iimpactt on paper strengths Less t th Nano-Filler Nano Filler Properties Nanostructured Filler Engineering Nanosilicate Fibril Fillers Vijay Mathur, 2004 TAPPI Paper Summit, May 3-5, 2004, Atlanta, GA, USA Nanostructured Filler Engineering Clay Charge Charge Polymer Polymer Polymer Control Coated clay 36 34 - Layer-by-layer coating on clay fillers - Tailor fill surface properties - Enhances tensile and other physical properties - 32 Tensiile Index Charge 30 28 26 5% 10% 15% Percentage clay 20% 9 layer Nano-Enhanced Paper: Surface Fibrilation SEM of Fiber Nano-Enhanced Paper: p ZDT Strength Improvement 100 90 80 ZDT (PS SI) 70 60 50 40 30 20 10 0 Control Nano fibril 33% increase in ZDT Nano-Enhanced Paper: p Folding Strength Improvement 2 Folding In ndex (times**cm /g) 4 3.5 3 2.5 2 15 1.5 1 0.5 0 Control Nano fibril 3.5 time increases in the folding strength Polymer Polymery -Nanoclayy Composites p Th thickness The thi k off nanoclay in the composite is about 1nm. B i coating Barrier ti for f food containers and paper packages Water and vapor resistance, fatty and oil resistance,, board strength Key Issues Using PolymerNanoclay for Barrier Coating • Water Based – Emulsion/miniemulsion polymerization • Uniformed Distribution (no aggregates in the polymer matrix) – Correctly using surfactant • Strong affinity between polymer and nanoclay – Seeding and modification technology H2O H2O Functional PaperPaper-Packaging • Nano N particles i l embedded b dd d in i cellulosic ll l i fibers can pprovide: – Unique antianti-bacterial fungal properties – Timed Ti d release l – Environmentally y responsive p signals g Advanced Bio-Based Materials mm Research Opportunities 100 μm 1μ μm 10 nm 10 μm nm Nanocellulose 1 cm H+/Enzyme/ M h i l Mechanical AFM of Cellulose Nanowiskers OAc HO O O O OH AcO O HO O Birefringence of Cellulose Nanowiskers OH O-Xylan O Crosslinked Xylan Films W t Vapour Water V Transmission/h T i i /h 400 300 200 100 0 0% Green Package 5 % Sulfonated Whiskers 10 O2 & strength TEM of Cellulose Nanowiskers1 • Nano in Pulp and Paper – – – – – – – – – – – Nanofiller Engineering Superhydrophobic – Superhydrophilic Fibers Barrier coatings and Films Nanostructured Papermaking Additives Optical Properties Improved Printing Higher Bulk Porous Structures Foams Composites Intelligent lli Paper
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