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Appendix 1 Functions of PFAS, the uses and substitutions of Specialist Equipment Japan Electric Measuring Instruments Manufacturers' Association (JEMIMA) Appendix 1 Functions of PFAS, the uses and substitutions of Specialist Equipment Appendix 1-1 The characteristics and functions of PFAS This document is the appendix 1 of the general comment to the Restriction report on Per- and polyfluoroalkyl substances (PFAS) from Japan Electric Measuring Instruments Manufacturers' Association (JEMIMA) submitted on 15 September 2023 1 / 12 Appendix 1 Functions of PFAS, the uses and substitutions of Specialist Equipment Japan Electric Measuring Instruments Manufacturers' Association (JEMIMA) Table of content The characteristics and functions of PFAS Summary Chemical resistance Ozone resistance Repellency from water and oil / non-adhesion Heat resistance Electric insulation Low friction, self lubrication Gas barrier properties/Gas permeation properties Low refractive index Weatherability Durability Resistance to creep / Compression set 2 / 12 Appendix 1 Functions of PFAS, the uses and substitutions of Specialist Equipment Japan Electric Measuring Instruments Manufacturers' Association (JEMIMA) The characteristics and functions of PFAS Summary PFASs have many functions. The characteristics and functions of PFAS which are mainly used in Specialist equipment are described in this section. PFAS has excellent properties such as, chemical resistance, electric insulation, heat resistance, repellency from water and oil, non-adhesion, weatherability, and others. PFASs are used where multiple of these properties are required simultaneously. We recognize that the ability to provide these various properties in a single material is the most important property of PFAS, and at present we do not have information on any other substance with this function other than PFAS. Chemical resistance Fluoropolymers compared to other general-purpose resins Table 1 Classes of Substances at 20 C, Chemical Compatibility Chart - LDPE, HDPE, PP, Teflon Resistance (calpaclab.com) /PUGPSUVCJOHDIFNJDBMSFTJTUBODF FYDFQU17$ &YDFQUGPSPYJEJ[JOHBDJET 4FFPYJEJ[JOHBHFOUT TUSPOH 51&HBTLFUT &YDFMMFOUEBZTPGDPOTUBOUFYQPTVSFDBVTFTOPEBNBHF1MBTUJDNBZUPMFSBUFGPSZFBST (PPE-JUUMFPSOPEBNBHFBGUFSEBZTPGDPOTUBOUFYQPTVSFGPSUIFSFHFOU 'BJS4PNFFGGFDUBGUFSEBZTPGDPOTUBOUFYQPTVSFUPUIFSFBHFOU5IFFGGFDUNBZCFDSB[JOH DSBDLJOH MPTTPGTUSFOHUIPSEJTDPMPSBUJPO /PU SFDPNNFOEFE *NNFEJBUF EBNBHF NBZ PDDVS %FQFOEJOH PO UIF QMBTUJD UIF FGGFDU NBZ CF TFWFSF DSB[JOH DSBDLJOH MPTT PG TUSFOHUI PS EJT DPMPSBUJPO EFGPSNBUJPO EJTTPMVUJPO PS QFSNFBUJPO MPTT 3 / 12 Appendix 1 Functions of PFAS, the uses and substitutions of Specialist Equipment Japan Electric Measuring Instruments Manufacturers' Association (JEMIMA) Table 2 Property Comparison of Fluoro elastomers (FKM) with Other Rubbers1 &YDFMMFOU (PPE 'BJS .BSHJOBM 1PPS "Cleanliness" is defined as the fact that fluoropolymers are not easily eluted by acids, alkalis, or solvents (chemical resistance), do not contain other materials such as plasticizers in the molding process, and do not contain products that would thermally decompose during the material molding process. Ozone resistance Ozone is known to degrade plastic materials in two ways: A: Substances with double bonds (C=C) in their structures (such as natural rubber, chloroprene rubber, butadiene rubber, etc.) undergo decomposition in which ozone reacts with the double bonds to produce ketones, when they come into contact with ozone. B: When ozone exists in water, peroxy radicals are generated. Non-fluorine materials (eg polyethylene, polypropylene, etc.) deteriorate even if they do not have double bonds. Fluoropolymers does not have decomposition pathways such as A and B even if it comes into contact with ozone, so it can be used for a long time without deterioration. 1 https://www.daikinchemicals.com/library/pb_common/pdf/catalog/RC-1L.pdf translated from the document in Japanese. Last accessed on 14 July, 2023 4 / 12 Appendix 1 Functions of PFAS, the uses and substitutions of Specialist Equipment Japan Electric Measuring Instruments Manufacturers' Association (JEMIMA) Thermoplastic resin Ozon Resistance Soft vinyl chloride PVC Rigid vinyl chloride PVC Vinylidene chloride resin PVdC ABS ABS Polyethylene PE Nylon N Acrylic resin PMMA Fluoropolymer resin PTFE Phenolic resin PF Melamine resin PVC Furan resin FF Epoxy resin EP Unsaturated polyester resin UP Table 3 Comparison of ozone resistance properties of plastics Repellency from water and oil / non-adhesion Since the fluoropolymers have a small polarizability, the intermolecular force is small. Because of its characteristics, fluoropolymers have repellency and non-adhere properties on the surface. In general, the repellency from various liquids is evaluated by the contact angle, and the larger the contact angle, the higher the repellency. Contact angle Figure 1 Contact angles with water Adhesion energy refers to the amount of work required to pull a liquid contacting a solid away from the solid. The larger the contact angle, the smaller the adhesion energy. It means that a 5 / 12 Appendix 1 Functions of PFAS, the uses and substitutions of Specialist Equipment Japan Electric Measuring Instruments Manufacturers' Association (JEMIMA) liquid in contact with a small adhesion energy solid easy to separate from the solid.2 Material name Contact angle with water (o) Adhesion energy (dyn/cm) PTFE 114 43.1 FEP 115 42.0 Silicone resin 90~110 47.8~72.7 Paraffin 105~106 52.7~53.8 PE 88 75.2 PCTFE 83 - PA 77 97.7 Phenolic resin 60 109.0 Copper(electropolishing) 9.6 144.2 Aluminium(electropolishing) 4.6 145.0 Table 4 Surface properties of various plastics and metals This characteristic is sometimes called "mold releasability". It can also be expressed as antifouling because it does not easy to adhere. Heat resistance Fluoropolymers have high heat resistance as follows. They have higher heat resistance compared to other general-use resins Fluoropolymers Heat resistance : PTFE PFA FEP ETFE maximum operating temperature (C) 260 260 205 150 Table 5 The heat resistance of Fluoropolymer 3 PCTFA 120 PVdF 120 Other general-use resins PP PVC 100 60 Electric insulation When the dielectric constant is low, the insulation in electrical components can be made thinner, leading to downsizing and weight reduction of the equipment.In applications where downsizing and weight reduction are necessary, it is an essential feature 2 Japan Fluoropolymers Industry Association(2020), , 14th edition. Page 34 Translated from Japanese. DAIKIN INDUSTRIES, LTD. (2009) Page 4 6 / 12 Appendix 1 Functions of PFAS, the uses and substitutions of Specialist Equipment Japan Electric Measuring Instruments Manufacturers' Association (JEMIMA) Fluoropolymer PTFE FEP PFA ETFE Dielectric constant 2.1 2.32.8 Non-fluoropolymer PVC PEEK TPI (Thermoplastic Polyolefin Polyimide) Dielectric constant 46 3.24.5 2.83.2 2.34 Table 6 The dielectric constants of various resins Fluorine rubber FKM FEPM 34 2.53.5 Non-fluorine rubber Silicone rubber EPDM 3.210 2.53.5 Low friction, self lubrication Friction coefficient of fluorine resin is lower than that of other resins. It is because polarizability (Mobility of electrons in an electric field) of C-F bonding is low (0.68) and the intermolecular force is weak. (Reference: polarizability of C-Cl bonding is 2.59) 4 Types of plastic Plastic / Plastic Plastic / Steel Steel / Plastic PTFE 0.04 0.04 0.10 PE 0.10 0.15 0.20 PS 0.50 *) 0.30 0.35 PMMA 0.80 *) 0.50 *) 0.45 *) *) indicates occurrence of stick-slip motion. Measurement condition: Bowden-Laden type measurement equipment, load: 9.8-39.2N, sliding speed: 0.01cm/s Plastic/Steel indicates sample material/pin material PE: polyethylene PS: polystyrene PMMA: polymethylmethacrylate Table 7 Comparison of friction coefficient among PTFE and other materials5 As an example of low friction, Table8 shows friction coefficient of PTFE. Type ASTM test Measurement method condition Unit PFA PTEF FEP Coefficient of static friction Against polished steel - 0.05 0.02 0.05 Table 8 Comparison of static friction coefficient among PFA, PTFE and FEP6 One of the characteristics related to friction is "self lubrication". The molecules of PTFE separate from molding of PTFE due to friction. The molecules in crystals of PTFE separate easily because intermolecular forces are weak. PTFE moves and attaches to the friction mating surface and generates friction between them. It lowers friction coefficient. 7 Japan Fluoropolymers Industry Association(2020), , 14th edition. Page 9 Translated from Japanese. Japan Fluoropolymers Industry Association(2020), , 14th edition. Page 24 Translated from Japanese. DAIKIN INDUSTRIES, LTD. (2009) Page 53 Japan Fluoropolymers Industry Association(2020), , 14th edition. Page 24 Translated 7 / 12 Appendix 1 Functions of PFAS, the uses and substitutions of Specialist Equipment Japan Electric Measuring Instruments Manufacturers' Association (JEMIMA) Gas barrier properties/Gas permeation properties Fluoropolymer film are less steam permeability. Figure 2 The degree of steam permeability 8 steam permeability (g/m2/d) from Japanese. DAIKIN INDUSTRIES, LTD. (2009) Daikin Fluoropolymers HandbookPage 109 8 / 12 Appendix 1 Functions of PFAS, the uses and substitutions of Specialist Equipment Japan Electric Measuring Instruments Manufacturers' Association (JEMIMA) Fluorine elastomers are less atmospheric (nitrogen, oxygen) permeability. Material Temperature degree He H2 Celsius O2 N2 CO2 CH Vinyl methyl silicone rubber VMQ 25 N/A 400 400 200 1600 N/A 50 570 500 280 1550 Ethylene 25 16.5 5.90 79.2 propylene rubber N/A N/A N/A EPDM 50 46.6 13.7 183 Perfluoroelastomer FFKM 25 10.3 8.25 2.5 8.1 28.7 3.3 Styrene butadiene 25 rubber SBR 50 17.5 30.5 13 4.8 94 N/A 42 74 34.5 14.5 195 Vinylidene fluoride fluororubber 25 binary FKM 2.95 4.6 1.0 0.8 3.9 0.6 Vinylidene fluoride fluororubber 25 Ternary FKM 2.64 4.13 1.7 0.7 1.6 0.4 Chloroprene 25 Rubber CR 50 nitril-butadiene 25 rubber Mid-high NBR 50 N/A 10.3 3.0 0.89 19.5 2.5 28.5 10.1 3.55 56.5 9.8 9.32 12.1 2.94 0.81 23.5 N/A 23.4 33.7 10.5 3.58 67.9 nitril-butadiene rubber High NBR 25 5.2 5.42 0.73 0.18 5.67 N/A 50 14.2 17.0 3.5 1.08 22.4 butyl rubber IIR 25 6.4 5.5 0.99 0.25 3.94 0.6 50 17.3 17.2 4.03 1.27 14.3 3.2 10,/,sec,atm Table 9 Comparison of gas permeability of elastomer9 Property of Gas Permeability Property N2 O2 Gas permeability H2 Gas Permeability coefficient CO2 CH4 C2H4 Water-vapor permeability Table 10 Water Absorption Gas Permeability of FEP film10 Standard Test method ASTM D1434 JIS Z0208 ASTM D570 Unit /satm g/24h 24h DAIKIN INDUSTRIES, LTD. (2009) Daikin Fluoropolymers HandbookPage 78 DAIKIN INDUSTRIES, LTD. (2009) Daikin Fluoropolymers HandbookPage 78 9 / 12 C2H2 N/A N/A C3H8 10000 or more 91.2 246 N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A 18.9 26.9 68.3 78.3 8.25 11.2 19.8 33.1 1.28 N/A 5.82 FEP film 12010-10 37010-10 1,08010-10 97010-10 6610-10 4410-10 1.6 <0.01 Appendix 1 Functions of PFAS, the uses and substitutions of Specialist Equipment Japan Electric Measuring Instruments Manufacturers' Association (JEMIMA) Fluoropolymers permeate small molecular gases, such as oxygen and nitrogen, conversely, large molecular gases do not permeate. Fluoropolymer properties are used in permeate membranes for measurement and analysis. Gas N2 O2 CO2 CH4 CH3 CH C2H4 FEP 1.210-8 3.710-8 9.710-8 0.6610-8 0.6610-8 0.1110-8 0.4810-8 Gas Permeability PTFE 1.110-8 3.210-8 8.910-8 Low Density Polyethylene 0.7410-8 2.210-8 9.610-8 2.210-8 5.210-8 7.210-8 Temperature: 25 degree Celsius(77F) Units: cm3 (ST P) cm/cm2atm Table 11 Comparison of gas permeability of various materials11 Low refractive index Amorphous fluoropolymer resin has high transmittance. This is utilized for optical components and optical fibres. Wavelength (nm) Figure 3 Comparison of transmittance Weatherability Fluoropolymer resin has high weatherability and can be used outdoors. It does not react to sunlight such as ultraviolet rays. It is not susceptible to oxidizing effects of atmospheric oxygen and other substances (see "chemical resistance"). It can be used in a wide temperature range from low to high (see "heat resistance"). It has high water repellency and does not absorb water, so it is not affected by humidity changes. It can be said that fluoropolymer resin has high weather resistance because it has the above points. DAIKIN INDUSTRIES, LTD. (2009) Daikin Fluoropolymers HandbookPage 80 10 / 12 Appendix 1 Functions of PFAS, the uses and substitutions of Specialist Equipment Japan Electric Measuring Instruments Manufacturers' Association (JEMIMA) Fluoropolymer resin PTFE PFA FEP ETFE PCTFE PVdF Weatherability Excellent, Good Not very good Needs attention Not good Table 12 Fluoropolymer resin weatherability comparison 12 General resin PP PVC Regarding the graph below, it can be seen from the accelerated weatherability test with the Sunshine Weather Meter that the gloss retention rate decreases by no more than 10% even after 4000 hours of exposure. 13 Fluoropolymer resin paint Urethane paint Acrylic silicone paint Figure 4 Accelerated weatherability test of paint Gloss retention rate of paint film (%) Tensile strength (MPa) Exposure time by weather meter(h) Figure 5 Outdoor exposure test Comparison of tensile strength between ETFE and other materials 14 DAIKIN INDUSTRIES, LTD. (2009) Page 4 13 https://www.kyoeishoji.co.jp/business/chemical/fusso_toryo.html translated from the document in Japanese. Last accessed on 21 July, 2023 14 https://www.taiyokogyo.co.jp/feature/etfe_film.html translated from the document in Japanese. Last accessed on 21 July, 2023 11 / 12 Appendix 1 Functions of PFAS, the uses and substitutions of Specialist Equipment Japan Electric Measuring Instruments Manufacturers' Association (JEMIMA) Durability *UNFBOTUIBUJUDBOCFVTFEGPSBMPOHUJNF%VFUPJUTIJHIDIFNJDBMSFTJTUBODFBOE IJHIXFBUIFSBCJMJUZ 1'"4DBOBDIJFWFIJHIEVSBCJMJUZ Resistance to creep / Compression set When a constant load is applied to a polymeric material, creep occurs, in which deformation progresses over time. Similarly, compression set occurs where the deformation does not recover when the force is removed. Both properties are known to be correlated. When rubber materials are used in elastic applications such as packings or diaphragms, it is required to minimize the effects of both properties. Experimental examples of "30% creep time (Hour)" for major rubber materials are shown below. Creep is known to be worse at higher temperatures, Experiments have shown that FKM and silicon exhibit good properties. NR SBR CR NBR IIR FKM Silicon 50 degree Celsius 190 1250 4200 3900 Table 13 70 degree Celsius 103 203 550 380 100 degree Celsius 3.8 14 45 41 2.7 1650 120 degree Celsius 7.4 12.2 305 1550 150 degree Celsius 180 190 Quoted from the journal of "the Society of Rubber Science and Technology, Japan", 1960(Vol33), P882-892, "Stress relaxation and creep properties of various vulcanized rubbers". Examples of compression set test results are shown below. In general, it is difficult to quantitatively compare materials because the measured values differ depending on the compounding and hardness of the rubber. Here, the compression set of the materials was compared by comparing the minimum value of each material in the database. FKM and silicon showed relatively good properties, showing the same tendency as creep. NR SBR CR NBR IIR EPDM FKM Silicon Compression set JISK6301 100 degree Celsius70h Min 20 Min 23 Min 9 Min 23 Min 11 Min 6 Table 14 The minimum value of each material was quoted from the data described in "Material Database / Organic Materials" (1989), The Nikkan Kogyo Shimbun". 12 / 12