1. No category

Assessing the performance and
environmental safety of
alternative fluorinated and nonfluorinated DWR technologies
Steffen Schellenberger1, Hanna M. Andersson2, Philip
Gillgard3, Ian T. Cousins1
1ITM,
Stockholm Univ., Sweden
2Chalmers Univ. of Technology, Gothenburg, Sweden
3Sverea IVF, Gothenburg, Sweden
Substitution of prioritized poly- and perfluorinated
chemicals to eliminate diffuse sources (SUPFES)
SUPFES’ objective:
Characterize the physical
performance and assess the
risks of alternative DWR
chemistries for textiles
Presentation’s objective:
VU
University
Amsterdam
Stockholm
University
Chemical Screening
& Leaching Studies
Hazard Assesment:
Measure & Model
Chalmers
University
Risk & Life Cycle
Assesment (LCA)
Swerea IVF
Textile
Research
Performance Testing
SUPFES
Provide a preliminary
performance and hazard
assessment using existing data
A unique consortium
of scientific and
industrial partners with
strong stakeholder
involvement
Why do we need water and stain repellency?
Liquids with decreasing polarity
water
Sauce
Oil
Surveys show that
consumers are not
well aware of oil
repellency
Water repellency is a key
requirement in waterproof
apparel
Soil/oil/stain repellency also
desired property in waterproof
apparel and indispensable for
protective clothing (e.g.
ambulance jacket, military)
What are durable water repellents (DWR)?
Multi-layered outdoor fabric with
different functions
Hydrophobic groups for
textile repellency
Polymer backbone
Fiber binding groups
single fiber
PTFE membrane
 Durable Water Repellency (DWR) is the
hydrophobic coating added to the fabric fibers to
make them water and oil resistant
 Fabric’s ability to withstand the penetration of
water and oil cannot be achieved by the fiber
materials alone
DWR-chemistry
C8-Benckmarc Fluorocarbon (FC)
Phase out by 2015
DWR
Alternatives
Fluorocarbon (FC)
Polysiloxane (Si)
Hydrocarbon (HC)
Polydimethylsiloxanes
DWR based on fatty
acids
Hydrophobic
groups
n=3
e.g. C6
Fluorotelomer
Note: dendrimer and resin-based stearic acid melamine DWR technologies are also
on the market.
Performance testing
Textile requirement profile
durability
handle
water repellency
100,0
90,0
80,0
70,0
60,0
50,0
40,0
30,0
20,0
10,0
0,0
antistatic
oil repellency
dry soil repellency
soil release
resistance to
rubbing
Very different performance requirements in textiles
Battery of
different
material
performance
tests are
performed
Chemical alternatives assessment in
SUPFES
• Chemical hazard assessment – principles of green
chemistry: ensure inherently safer products
• Technical/functional assessment – technical
performance test battery, literature data here
• Risk assessment, hazard assessment in combination
with exposure assessment – diffuse emissions via e.g.
household waste water
• Life cycle assessment (LCA) on four garment types
• Economic assessment – Life cycle costing (LCC)
Chemical hazard assessment
Used the GreenScreen®
method
1.
Assess and classify
hazards for 18 hazard
endpoints
2.
Classification leads to an
overall benchmark score
http://www.greenscreenchemicals.org
Benchmark U = unspecified due to insufficient data
Hazard endpoints in GreeenScreen®
GreenScreen hazard endpoints
GreenScreen® methodology 1
a. Determine identity of chemical(s) to assess
1.
2.
3.
4.
C8 FTOH-based DWR as benchmark
C6 FTOH-based DWR
Paraffin wax-based DWR
Siloxane-based DWR
Further considerations:
– DWR based on formulations with multiple components
(“active ingredients” only, formulations highly variable)
– Parent (e.g. acrylate polymers), residual side chains
(FTOHs) and/or transformation products (PFOA, PFHxA)?
– Uncertain which are the relevant components for
siloxanes/silicones (also dendrimers, resin-based
melamines)
GreenScreen® methodology 2
b. Research & collect data (or estimate data) for 18 hazard
endpoints
c.
Classify hazard level for each endpoint (i.e., vH, H, M, L,
vL)
d. Determine level of confidence (High or Low) in each
hazard classification
e. Document findings & conclusions and fill in the Hazard
Summary Table
f.
Use Hazard Summary Table to obtain overall benchmark
score (1, 2, 3, 4 or U)
Data sources for GreenScreen®
General approach: data searches, modelling, readacross and existing assessments
 PFOA: Harmonized classification, annex VI CLP (later add 8:2
FTOH and acrylate polymers?)
 PFHxA: Peer-review papers and results from standardized
tests (later add 6:2 FTOH and acrylate polymers?)
 Waxes: ToxServices GreenScreen assessment 2013, (Paraffin
wax: CAS #8002-74-2)
!
Siloxanes/silicones: Complex polymeric mixtures based on
polydimethylsiloxanes (PDMS). Notified classifications under
CLP (i.e. the companies’ own classifications) for short-chain
siloxanes. Merged data from several substances!
(CLP = EU Regulation on Classification, Labelling and Packaging of
substances and mixtures)
GreenScreen® hazard classification
summary: preliminary results
Group I Human
C
M
R
Group II and II* Human
D
E
AT
ST
N
single
repeated*
single
repeated*
SnS*
SnR*
IrS
IrE
PFOA
M
L
M
H
DG
M
DG
H
DG
DG
DG
DG
DG
vH
PFHxA
L
L
M
M
DG
L
DG
DG
DG
DG
DG
DG
M
vH
Siloxanes
M
DG
DG
DG
DG
H
M
DG
DG
DG
DG
DG
H
M
Paraffin Wax
L
L
L
L
DG
L
M
DG
DG
DG
L
DG
L
M
Ecotox
AA
Fate
CA
P
Physical
B
Rx
Benchmark
F
PFOA
L
L
vH
H
DG
DG
1
PFHxA
L
L
vH
vL
DG
DG
1
Siloxanes
vH
vH
vH
H
vH
H
1
Paraffin Wax
L
L
L
vL
L
L
3
Paraffin Wax assessment:
TOXSERVICES 2013.
Paraffin Wax (Melting Point
45 to 48°C) (CAS #8002-742) GreenScreen™
Assessment.
DWR properties comparison
Water repellency
(ISO 4920)
90,0
80,0
70,0
60,0
50,0
40,0
30,0
Fluorocarbon (C8)
20,0
Hazard assessment
(GreenSceen)
10,0
0,0
Durability 2000 rubs
(abrasion test ISO
12945)
Fluorocarbon (C6)
Silicone
Hydrocarbon (Wax)
Performance Data from BSc thesis of Alice Davies,
under the Supervision of Dr. John Williams
(School of Fashion and Textiles,
De Montfort University, Leicester)
Oil repellency
(ISO 14419)
11/17/2014
“An Evaluation Of The Test Methods Used For
Assessing Durable Water Repellent Fabrics Within
The Outdoor Industry”
14
Conclusions and next steps
• Non-fluorinated DWRs are competitive regarding water
repellency, but only fluorinated DWRs can currently offer oil
repellency
• Only hydrocarbon waxes are classified as non-hazardous
according to the preliminary GreenScreen® hazard
assessment
• SETAC opening address – there are rarely any simple solutions
Next steps
• Refine hazard assessments
• Identify additional relevant substances for each group, e.g.
precursors and polymers in the fluorocarbon category
• Fill data gaps where possible and prioritize data generation
needs for the SUPFES project
• Conduct risk and life cycle assessments
Thank you for your attention!
www.supfes.eu