ISPO - 26. Jan. 2016-1
State of play for DWRs Current and future (legal) challenges Stefan Posner stefan.posner@swerea.se 2
Short about Stefan Posner and Swerea IVF Stefan Posner Polymer and textile chemist with over 30 years experience in research on chemicals in textiles and polymeric materials in cooperation with international companies, authorities and academia in several international projects over the years. Stefan is since many years working with legal preparatory work on chemicals for UNEP Stockholm Convention, EU Commission and several National Authorities and is deeply involved in research to substitute hazardous chemicals with a recent certain focus on highly fluorinated substances and flame retardants but other groups of hazardous chemicals have been in focus in the past. Swerea IVF offers advanced R&D and consulting services to the manufacturing and engineering industry. Our goal is the rapid introduction of new technologies and methods to practical use in our customers' operations. Our customers include industrial companies as well as public institutions, that turn to us to develop their future resource efficient products and processes. http://swerea.se/en/start2/ Swerea IVF is part of the Swerea Group, a Swedish industrial research group that encompasses Sweden's industrial research institutes within the fields of materials, process, product and production technology. http://www.swerea.se/en/ 3
Presentation PFAS chemistry general orientation DWR chemistry - an orientation Hazards state of the art Regulatory issues - current and ongoing SUPFES Potential risks - the holistic approach Performance - whats really required Ongoing and results Conclusions Questions 4
What are highly fluorinated compounds/ polymers? Surfactants extremely low surface tension Fluorinated tail Spacer Hydrofilic group Side chain fluorinated polymers extremely low surface energy Fluoropolymers e.g PTFE - another chemistry Perfluorinated polymer chain (extremely long chains) 5
Terminology PFAS; chemicals that contain one or more perfluoroalkyl moieties, CnF 2n+1. In the past, PFASs were often referred to as PFCs (per- and polyfluorinated chemicals) The family of PFAS PFAA; Perfluoroalkyl acids PFCA; Perfluoroalkyl carboxylic acid PFSA; Perfluoroalkane sulfonic acids Compounds derived from perfluoroalkane sulfonyl fluoride (PASF) Fluorotelomer (FT)-based compounds Per- and polyfluoroalkyl ether (PFPE)-based compounds 6
Electrochemical fluorination - ECF H(CH 2 ) n SO 2 F (n = 4, 6, 8, 10) e - + HF ECF Input PFAS Perfluoroalkyl sulfonamide F(CF 2 ) n SO 2 NH 2 Output PFAS F(CF 2 ) n SO 2 F Perfluoroalkyl sulfonyl fluoride F(CF 2 ) n SO 2 NH 2 Perfluoroalkyl sulfonamide R = H, Me, Et, Bu F(CF 2 ) n SO 2 N(R)CH 2 CH 2 OH N-Alkyl Perfluoroalkyl sulfonamido alcohol (Meth)acrylate monomer R = H, CH 3 F(CF 2 ) n SO 2 N(R)CH 2 CH 2 OC(O)CR=CH 2 Perfluoroalkyl sulfonate F(CF 2 ) n SO 3 M Surfactants Amide Ethoxylate Oxazolidinone Phosphate Silane Sulfate Surfactants Adipate Fatty acid ester Phosphate Oligomeric Surfactants M = H, NH 4, K, Na, T ran s o r m a ti o n Final degradation products are perfluorinated sulfonic acids (PFSA) n = 4 formation to PFBS n = 6 formation to PFHxS n = 8 formation to PFOS n = 10 formation to PFDS F(CF 2 ) n SO 2 N(R)CH 2 CH 2 CH 2 N(CH 3 ) 2 Surfactants Betaine Sulfobetaine Cationic 7
Telomerization CF 3 CF 2 -I + CF 2 =CF 2 Input PFAS Output PFAS F(CF 2 ) n I (n = 4, 6, 8, 10, ) F(CF 2 ) n-1 CO 2 M Perfluoroalkyl iodide M = H, NH 4, K, Na, F(CF 2 ) n CH 2 CH 2 I Fluorotelomer iodide F(CF 2 ) n CH 2 CH 2 SO 2 Cl Fluorotelomer sulfonyl chloride F(CF 2 ) n CH 2 CH 2 SO 2 N(R)CH 2 CH 2 CH 2 N(CH 3 ) 2 F(CF 2 ) n CH=CH 2 Fluorotelomer olefin F(CF 2 ) n CH 2 CH 2 Si(OR) 3 Silane F(CF 2 ) n CH 2 CH 2 O H Fluorotelomer alcohol (Meth)acrylate monomer R = H, CH 3 F(CF 2 ) n CO 2 M F(CF 2 ) n CH 2 CH 2 OC(O)CR=CH 2 T ran s f o r m at i o n Final degradation products are perfluorinated carboxylic acids (PFCA) n = 4 formation to PFBA n = 6 formation to PFHxA n = 8 formation to PFOA n = 10 formation to PFDA Surfactants Betaine Sulfobetaine Cationic Oligomeric Surfactants Surfactants Ethoxylate Phosphate Sulfate 8
Versatile uses of PFAS Global market information on PFAS Identified applications based on market information, in descending order are: Synthesis Chemicals Electronics Products Printing Products Cosmetic Products Textile / leather impregnation Pharmaceuticals Plant protection Biocides Paints Adhesive raw materials Paper impregnation Foam-based fire extinguishing agents 9
Poor market information on PFAS Information on how the substance is used (about 3000 substances), had about half unknown use. The market information found for most PFAS was often short. Information on functionality such as "surfactant" could be linked to 20% of the PFAS substances. PFAS that were called surfactants had a wide range of applications often briefly described. For a third of all the substances that were identified (approximately 1000 PFAS), a bit more detailed market information was available. A report from the Swedish Chemicals Agency (2015) Occurrence and use of PFAS and alternatives 10
Categories and applications of PFAS Category Subcategory Some applications Salts K +, Li +, NH + 4 Amines Ammonium Salts Amphoterics Surfactant in fire-fighting foam, surfactant for alkaline cleaners, emulsifier in floor polish mist, suppressant for metal plating baths, surfactant for etching acids for circuit boards, inks. Photoresist Mist suppressant for metal plating baths Mist suppressant for metal plating baths Water/solvent repellence for leather/paper. Oil recovery 11
Categories and applications of PFAS Category Subcategory Some applications Carboxylates Antistatic agent in photographic paper. Optical elements Polymers Amides Oxazolidinones Alcohols, silanes, alkoxylates, fatty acid esters, adipates, urethanes, polyesters, acrylates Copolymers, phosphate esters Pesticide active ingredient Waterproofing casts Soil/water repellence for carpet, fabric/upholstery, apparel, leather, metal/glass Soil/water repellence for carpet, fabric/upholstery, apparel, leather, metal/glass. Oil/water repellence for plates, food containers, bags, wraps, folding cartons, containers, carbonless forms, masking papers 12
Emissions of PFAS Subcategory Emissions K +, Li +, NH 4 + Non textile and leather applications Direct emissions as ingredients/ processing aids Amines Ammonium Salts Amphoterics 13
Emissions of PFAS Subcategory Carboxylates Amides Oxazolidinones Alcohols, silanes, alkoxylates, fatty acid esters, adipates, urethanes, polyesters, acrylates Copolymers, phosphate esters Emissions Transformation/degradation products Textile and leather applications Transformation/degradation products Impurities/residual 14
DWR chemistry and physics Chemical DWR Fluorocarbon-based Silicon-based Hydrocarbon-based polymers Physical DWR Plasma technology Superhydrophobic HC-DWR Si-DWR FC-DWR
What are durable water repellents (DWR)? Multi-layered outdoor fabric with different functions External fabric Steam/sweat Wind/rain Polymer backbone Fiber binding groups Hydrophobic groups for textile repellency single fiber Monolitic PTFE membrane or microporous membranes Inner lining 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 yet be achieved by the fiber materials alone
Hazards of concern for DWR chemicals (actually a concern for all chemicals) Persistence (P): Substances that are persistent are highly stable and resist the natural processes of degradation. Bioaccumulation (B). Substances that bioaccumulate are readily absorbed in fatty tissue and can accumulate in the body fat of living organisms. These substances become more concentrated as they move up the food chain, especially into larger longer-living organisms. Long-Range Transport (LRT): Substances that are released in one part of the world and have the ability to can travel far from their original source via wind, water, and, to a lesser extent migratory species Toxicity (T): Substances that are toxic chemicals that laboratory, field, and health studies have linked to certain adverse (chronic and acute) health effects in people and wildlife. 17
Hazards - PFAS Persistent (P) o PFAS do not occur in nature no natural system that have the ability to degrade PFAS o F- C bond is very strong, meaning that all PFAS are extremely persistent. Bioaccumulation (B) o PFAS are hydrofobic and oleofobic meaning that these substances do not really bioaccumulate in the same way as other organic substances. o Some PFAS have a high biomagnification potential Toxicity (T) o Some have shown human and environmental toxicity 18
DWR - polysiloxanes Some manufactured intermediates Abbrevia;on Name CAS no. D4 D5 D6 MM (or HMDSO) Octamethyl cyclotetrasiloxane Decamethyl cyclopentasiloxane Dodecamethyl cyclohexasiloxane 556-67-2 541-02-6 540-97-6 Hexamethyl disiloxane 107-46-0 Polysiloxanes MDM Octamethyl trisiloxane 107-51-7 MD2M Decamethyl tetrasiloxane 141-62-8 MD3M Dodecamethyl pentasiloxane 141-63-9
POP assessment (Stockholm Convention (SC)) of siloxanes Substance Persistence Bio accumulati on LRT Adverse effects: ecotoxicity Adverse effects to human health Decamethyl cyclopentasiloxane (D5) vpvb Dodecamethyl cyclohexasiloxane (D6) Yes Yes Yes No No Yes No Yes No No Decamethyl tetrasiloxane (MD2M) Equivocal data No Yes No No Octamethyl cyclotetrasiloxane (D4) Yes Yes Yes Yes Yes vpvb and T, pot. POP Octamethyl trisiloxane (MDM) Equivocal data Yes Yes No No Source: UNEP/POPS/POPRC.10/INF/8/Rev.1
Water repellent cotton and cotton/pet blends A classic cationic textile surfactant is 1-(stearamidomethyl) pyridinium chloride SC assessment: No P, B, no T N + Cl - NH O The substance reacts with cellulose at elevated temperatures to form a durable water-repellent finish on cotton There are also other similar resins used to water repellent cotton Sometimes these treatments are adressed as paraffin wax treatments
Superhydrophobic repellents Hyperbranched hydrophobic polymers (dendritic, i.e., highly branched polymers) and specifically adjusted comb polymers as active components Superhydrophobic No public means hazard contact data angles larger than 150 that can be applied available in coatings, textile, leather etc. Dendrimers may be in the region of nano sized materials meaning features with an average diameter between 1 to 100 nm There are now cationic dendrimers applied to improve bonding to cotton. Cationic properties may be considered concerning cytotoxicity
Fluoro silicone structures for DWR treatment? SiO 2 (silicon dioxide) molecules which are perflourinated. formula contains SI-F, that means, that the fluorine is bonded to the silicon dioxide. Still very little information of this groups of alternative DWR treatments on textiles.
Current legal PFAS status - International Conventions and EU Regulation (December 2015) Fluoro chemicals (PFAS) Abbr. CAS RN Norway REACH candidate List (SVHC) REACH annex XVII EU POP Regulation Stockholm convention Perfluorooctane sulfonic acid and related substances PFOS 1763-23-1 X Restriction annex B Pending Perfluorohexane sulfonic acid PFHxS 108427-53-8 Perfluorononaoic acid and its ammonium salt PFNA 375-95-1 4149-60-4 X Perfluorooctanoic acid and related substances PFOA 335-67-1 Restricted (PFOA and 7 related substances) X Restriction proposal POP candidate Pentacosafluorotridecanoic acid PFTrDA 72629-94-8 X Tricosafluorododecanoic acid PFDoA 307-55-1 X Henicosafluoroundecanoic acid PFUnA 2058-94-8 X Heptacosafluorotetradecanoic acid PFTA 376-06-7 X
SUPFES Acknowledged: Christina Jönsson, Stefan Posner, Sandra Roos, Anne-Charlotte Hanning, Philip Gillgard (Swerea IVF) Greg Peters, Hanna Holmquist (Chalmers) Steffen Schellenberger, Ian Cousins (SU Stockholm University) Ike van der Veen, Jana Weiss, Pim Leonards (VU University Amsterdam) Contact person Christina Jönsson Christina.jonsson@swerea.se 25
SUPFES - Substitution of prioritized poly- and perfluorinated substances to eliminate diffuse sources Swerea IVF is coordinator Project duration until 2017 Project budget: 1,85 M 29/01/ 2016 26
Swerea IVF Textile Research SUPFES VU University Amsterdam Stockholm University Chalmers University SUPFES objective: Characterize the physical performance and assess the risks of alternative Durable Water Repellent (DWR) chemistries for textiles Performance Testing LCA, LCC Chemical Screening & Leaching Studies Hazard Assessment: Measure & Model Risk & Life Cycle Assessment (LCA) A unique consortium of scientific and industrial partners with strong stakeholder involvement
SUPFES approach substitution in practice Task 3 Case studies: - Impact and Risk assessment - Technical performance Task 1 Characteriza;on of PFAS in use Task 2 Selec;on of alterna;ves Toxicity and exposure assessment 28
Potential risks - the holistic approach Production Use End of life Site emissions chemicals management Diffuse emissions ecodesign 29
Components in the holistic approach Chemical hazard assessment - inherent hazard properties Technical/functional assessment technical performance test schemes 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)
Performance - whats really required? 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)
Ongoing and results Case studies Vitally important Work wear Medical application Chemical production Performace level Comfort Bad weather and leisure clothing Repellency against blood, acids Water repellency Ambulance jacket (work wear) Outdoor Jacket ( extreme ) Children s overall Outdoor Jacket ( leisure ) Specifications Test methods 32
Content of DWR chemicals in treated materials Materials collected and studied: Commercial jackets, gloves, trousers (50 articles) from outdoor and textile industry with DWR Alternative compounds applied as DWR to PA and PES (PET) materials Textiles analysed for the presence of ionic and neutral PFASs using validated method Extraction of textile (9.8 cm2)
Ongoing and results Main PFASs detected in textile samples ØPFBA ØPFBS Ø8:2 FTOH 47% of samples 18% of samples 92% of samples 2 2 0.02-28 µg/m 0.02-42 µg/m 1.5-380 µg/m2 (median (median 0.17 µg/m2) (median 0.69 µg/m2) 17 µg/m2) ØPFHxA ØL-PFOS Ø10:2 FTOH 76% of samples 18% of samples 90% of samples 0.03-6.4 µg/m2 0.02-3.2 µg/m2 0.06-130 µg/m2 (median (median 0.21 µg/m2) (median 0.09 µg/m2) 4.1 µg/m2) ØPFOA 96% of samples 0.01-5.1 µg/m2 (median 0.25 µg/m2) Ø6:2 FTOH Ø8:2 FTAC 88% of samples 46% of samples 0.43-360 µg/m2 0.29-280 µg/m2 (median (median 24 µg/m2) 2.6 µg/m2) Ionic PFASs and neutral PFASs are detected in textiles of outdoor clothing at quantifiable concentrations. Neutral PFASs are present at higher concentrations then ionic PFASs.
Patterns of PFASs in textile samples using a validated analytical method 0% 10% 20% C4 C8 40% other C8 Chemistry No. Supplier 1 22 24 26 28 C6 30% G F F E A 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% 60% 70% 80% 90% 100% C6 Chemistry No. Supplier 9 30 33 35 B 2 L A K I 0% 10% 20% 30% 40% 50%
Possible mechanisms for releases of chemicals from DWR-treated fabrics
Weathering Ø Preliminary data showed degradation of PFAS à No carry-over of ionic PFASs Ø 9 jacket samples before and after weathering Ø 2 SUPFES textiles (PA and PES (PET)) with each batch were free of ionic PFASs Sample 1: Before Sample 1: After Ø Humidity + UV Ø 300 hours à lifetime of a jacket Sample 25: Before Sample 25: After
Water and oil repellency performance testing Spray test (ISO 4920) Determination of water resistance to surface wetting 250 ml water Spray rating Determination of the remaining water after the spray test Oil repellency (ISO 14419) Fluid rating γ [mn/m] mineral oil 1 35 65/45 hexadecane/hexadecane 2 31,5 hexadecane 3 27,5 tetradecane 4 26,5 dodecane 5 25,5 decane 6 23,3 octane 7 21,6 heptane 8 20,2 Oils with decreasing surface tension (γ) Spray rating [0-5] Determination of fabrics`s repellency with different oils
Washing Best formulations results (out of 14 in total) DWR Chemistry Fluoro C8 (telomer) (FC) Water repellent PA after 10 washes Water repellent PET after 10 washes Oil repellent PA after 10 washes 5 5 3,5 3,5 Oil repellent PET after 10 washes Fluoro C6 (telomer) (FC) 4 4,5 4,5 2,5 Fluoro C4 5 4 0 0 (ECF) (FC) Silicone (Si) 3 3 0 0 Paraffin (HC) 5 5 0 0 Finish based on botanical extracts (HC) 4 4 0 0 39 Note: 5 is best, below 3 is too low repellency
Laundering and tumble drying Nanomaterial in the life cycle - potential risk? Production Use End of life Textile industry (wool clothes manufacturing) Wool production Dying and fabric making Washing and drying
Scanning electron microscope (SEM) Lint from tumble dryer Nano size with possible content of hazardous DWR chemicals?
Status SUPFES Hazard assessment of DWR chemicals/physics
Hazard assessment of alternatives in SUPFES ongoing and conclusions Our preliminary hazard ranking suggests that hydrocarbon-based polymers are the most environmentally benign, followed by silicone- and PFASbased polymers. The silicone industry is committed to reduce the levels of residual cyclic volatile methyl siloxanes (DX) present in the silicone-based DWR products and this will lower the actual risks. There is a lack of information on the hazards associated with DWR nanotechnologies and these data gaps must be filled. To assess the human and environmental risks of critical chemicals from DWRs the exposure have to be 43 considered
Intended use of fabric Performance requirements Customer demands Life span Holistic considerations Fastness on fabric during use (weathering, abrasion and wash) Stability (degradation) Exposure mode Particle/fiber to air and water Leakage to air and water Quantity Lower amounts of more efficient chemicals vs higher amounts of low efficient chemicals Quality Byproducts Address legal verification possibility 44
Screening LCA Emission data will be included 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% Tillverkning jacka Transporter Användning jacka Resthantering jacka 45 Manufacture of the jacket, and the use, in which the jacket is assumed to be washed and dried a total of 100 times, dominates the environmental impact, while transport and waste management are negligible.
Take away message from our SUPFES experience so far: Consider and apply in one context and not separately only Substitution in practice o Technical performance o Health and environmental performance o Precautionary principle Holistic approach o Life cycle perspective Cost efficiency o Direct cost - Company o Indirect cost Socio-economic effects To be continued. 46
Thank you for your attention! http://www.supfes.eu Questions? 47
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