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JIMA PFAS APPENDIX01 2023/09/14 Japan Inspection Instruments Manufacturer's Association (JIMA)
Appendix 01
Uses and substitutions of Specialist Equipment
This document is the appendix 01 of the general comment to the Restriction report on Per- and polyfluoroalkyl substances (PFAS) from Japan Inspection Instruments Manufacturers' Association (JIMA) submitted on 14. September 2023
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JIMA PFAS APPENDIX01 2023/09/14 Japan Inspection Instruments Manufacturer's Association (JIMA) Table of content The characteristics and functions of PFAS ................................................................................... 3
Summary.................................................................................................................................... 3 Chemical resistance .................................................................................................................. 3 Ozone resistance ....................................................................................................................... 4 Repellency from water and oil / non-adhesion .......................................................................... 6 Heat resistance .......................................................................................................................... 7 Electric insulation ....................................................................................................................... 7 Low friction, self lubrication ....................................................................................................... 7 Gas barrier properties/Gas permeation properties ................................................................... 8 Low refractive index................................................................................................................. 11 Weatherability .......................................................................................................................... 11 Durability .................................................................................................................................. 12 Resistance to creep / Compression set .................................................................................. 12 Uses of PFAS in Specialist Equipment ....................................................................................... 14 Summary.................................................................................................................................. 14 electric wires and insulation..................................................................................................... 15 Computed Radiography (CR) for Non-Destructive Testing..................................................... 17 Imaging Plate (IP) for Non-Destructive Testing and Medical Image Diagnosis .................... 188
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JIMA PFAS APPENDIX01 2023/09/14 Japan Inspection Instruments Manufacturer's Association (JIMA)
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
Table1 Classes of Substances at 20 C, Chemical Compatibility Chart - LDPE, HDPE, PP, Teflon Resistance (calpaclab.com)1
* Not for tubing chemical resistance (except PVC) ** Except for oxidizing acids (See oxidizing agents, strong) *** TPE gaskets
Excellent: 30 days of constant exposure causes no damage. Plastic may tolerate for 30 years. Good: Little or no damage after 30 days of constant exposure for the regent Fair: Some effect after 7 days of constant exposure to the reagent. The effect may be crazing, cracking, loss of strength or discoloration. Not recommended: Immediate damage may occur. Depending on the plastic, the effect may be severe crazing, cracking, loss of strength or dis coloration, deformation, dissolution or permeation loss.
1 https://www.esaknowledgebase.com/wp-content/uploads/2022/06/PFAS-Article-Valve-World-May-2022.pdf last accessed on 14 July 2023
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Table 1 Property Comparison of Fluoroelastomers (FKM) with Other Rubbers 2 : Excellent : Good : Fair : Marginal : Poor "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.
2 https://www.daikinchemicals.com/library/pb_common/pdf/catalog/RC-1L.pdf translated from the document in Japanese. Last accessed on 14 July, 2023
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JIMA PFAS APPENDIX01 2023/09/14 Japan Inspection Instruments Manufacturer's Association (JIMA)
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 2 Comparison of ozone resistance properties of plastics 3
3 https://www.kkkunii.co.jp/dcms_media/other/%E8%80%90%E6%B2%B9%E6%80%A7%E3%83%BB%E8%80%90%E6%BA %B6%E5%89%A4%E6%80%A7%E3%83%BB%E8%80%90%E8%96%AC%E5%93%81%E6%80%A7%E3% 83%87%E3%83%BC%E3%82%BF.pdf Last accessed on 20 July, 2023
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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 2 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 liquid in contact with a small adhesion energy solid easy to separate from the solid.4
Material name
Contact angle with water (o)
PTFE
114
FEP
115
Silicone resin
90~110
Paraffin
105~106
PE
88
PCTFE
83
PA
77
Phenolic resin
60
Copper(electropolishing)
9.6
Aluminium(electropolishing)
4.6
Table 3 Surface properties of various plastics and metals
Adhesion energy (dyn/cm) 43.1 42.0 47.8~72.7 52.7~53.8 75.2 97.7 109.0 144.2 145.0
4 Japan Fluoropolymers Industry Association(2020), , 14th edition. Page 34 Translated from Japanese.
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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 260
temperature (C)
260
205
150
Table 4 The heat resistance of Fluoropolymer 5
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
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 5 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) 6
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
5 DAIKIN INDUSTRIES, LTD. (2009) Page 4 6 Japan Fluoropolymers Industry Association(2020), , 14th edition. Page 9 Translated from Japanese.
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Plastic/Steel indicates sample material/pin material PE: polyethylene PS: polystyrene PMMA: polymethylmethacrylate
Table 6 Comparison of friction coefficient among PTFE and other materials7
As an example of low friction, Table8 shows friction coefficient of PTFE.
Type
ASTM test Measurement
Unit
PFA
PTEF
FEP
method
condition
Coefficient -
Against
-
0.05
0.02
0.05
of static
polished steel
friction
Table 7 Comparison of static friction coefficient among PFA, PTFE and FEP8
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. 9
Gas barrier properties/Gas permeation properties Fluoropolymer film are less steam permeability.
steam permeability (g/m2/d)
7 Japan Fluoropolymers Industry Association(2020), , 14th edition. Page 24 Translated from Japanese. 8 DAIKIN INDUSTRIES, LTD. (2009) Page 53 9 Japan Fluoropolymers Industry Association(2020), , 14th edition. Page 24 Translated from Japanese.
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Figure 3 The degree of steam permeability 10 Fluorine elastomers are less atmospheric (nitrogen, oxygen) permeability.
Temperature
Material
degree
He
H2
O2
N2
Celsius
Vinyl methyl silicone rubber
VMQ
25
400
400 200
N/A
50
570
500 280
Ethylene
25
16.5 5.90
propylene rubber
N/A
N/A
EPDM
50
46.6 13.7
Perfluoroelastomer FFKM
25
10.3 8.25
2.5
8.1
Styrene butadiene
25
rubber
SBR
50
17.5 30.5
13
4.8
42
74
34.5 14.5
Vinylidene fluoride
fluoro rubber
25
binary FKM
2.95
4.6
1.0 0.8
Vinylidene fluoride
fluoro rubber
25
Ternary FKM
Chloroprene
25
Rubber
CR
50
nitril-butadiene
25
rubber
Mid-high NBR
50
2.64 4.13
1.7
0.7
10.3
3.0 0.89
N/A
28.5 10.1 3.55
9.32 12.1 2.94 0.81
23.4 33.7 10.5 3.58
nitril-butadiene rubber
High NBR
25
5.2
5.42 0.73 0.18
50
14.2 17.0
3.5 1.08
butyl rubber
25
6.4
5.5
0.99 0.25
IIR
50
17.3 17.2 4.03 1.27
10,/,sec,atm
Table 8 Comparison of gas permeability of elastomer11
CO2
1600 1550 79.2 183
28.7
94 195
3.9
1.6
19.5 56.5 23.5 67.9 5.67 22.4 3.94 14.3
CH N/A N/A 3.3 N/A
0.6
0.4 2.5 9.8 N/A
N/A 0.6 3.2
C2H2 C3H8
10000
N/A
or
more
91.2 N/A
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
10 DAIKIN INDUSTRIES, LTD. (2009) Daikin Fluoropolymers HandbookPage 109 11 DAIKIN INDUSTRIES, LTD. (2009) Daikin Fluoropolymers HandbookPage 78
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Property of Gas Permeability
Property
N2
O2
Gas permeability
H2
coefficient
CO2
Gas Permeability
CH4
C2H4
Water-vapor permeability
Table 9
Water Absorption
Gas Permeability of FEP film12
Standard Test method
ASTM D1434
JIS Z0208 ASTM D570
Unit
/satm g/24h 24h
FEP film
12010-10 37010-10 1,08010-10 97010-10 6610-10 4410-10
1.6 <0.01
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 10 Comparison of gas permeability of various materials13
12 DAIKIN INDUSTRIES, LTD. (2009) Daikin Fluoropolymers HandbookPage 78 13 DAIKIN INDUSTRIES, LTD. (2009) Daikin Fluoropolymers HandbookPage 80
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Low refractive index Amorphous fluoropolymer resin has high transmittance. This is utilized for optical components and optical fibers.
Wavelength (nm) Figure 3 Comparison of transmittance 14
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.
Table 11 Fluoropolymer resin weatherability comparison 15
Fluoropolymer resin
PTFE PFA FEP ETFE PCTFE PVdF
Weatherability
Excellent, Good Not very good Needs attention Not good
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. 16
14 https://www.agc-chemicals.com/file.jsp?id=file/Cytop_tech14_EN.pdf . Last accessed on 11 Augst, 2023 15 DAIKIN INDUSTRIES, LTD. (2009) Page 4 16 https://www.kyoeishoji.co.jp/business/chemical/fusso_toryo.html translated from the document in Japanese. Last accessed on 21 July, 2023
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Gloss retention rate of paint film (%)
JIMA PFAS APPENDIX01 2023/09/14 Japan Inspection Instruments Manufacturer's Association (JIMA)
Fluoropolymer resin paint
Urethane paint
Acrylic silicone paint
Figure 4 AcceElexrpaotesudrewetimatehebryawbieliatythteersmt eotfepr(ahi)nt
Tensile strength (MPa)
Figure 5 Outdoor exposure test Comparison of tensile strength between ETFE and other materials 17
Durability It means that it can be used for a long time. Due to its high chemical resistance and high weatherability, PFAS can achieve high durability.
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.
17 https://www.taiyokogyo.co.jp/feature/etfe_film.html translated from the document in Japanese. Last accessed on 21 July, 2023
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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
Table 12
50 degree Celsius 190 1250 4200 3900
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 13
The minimum value of each material was quoted from the data described in "Material Database / Organic Materials" (1989), The Nikkan Kogyo Shimbun".
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Uses of PFAS in Specialist Equipment
Summary PFAS are a very important group of substances for Specialist Equipment, which depends on these uses to maintain safety, as they are highly effective in chemical resistance, Repellency from water and oil, and electric insulation. PFAS polymer resins are two to ten times more expensive than other commodity plastics. There is no use other than where the equipment does not work without the use of PFAS. General electronics components are not covered in this document. However, since our equipment also uses common electronic circuit parts, we also use parts common to information equipment and general consumer EEE. For usage and non-substitutable information for such parts, please refer to Japan 4EE Opinion RCOM21, No.4543 and additional Opinion Information and Non-Substitutable Information to be submitted in September 2023. Semiconductors are also used in our products. Many PFASs are used in semiconductors and semiconductor manufacturing equipment. Comments on most of the items in this section have been submitted by industry associations that specialize in the respective items. We hope that dossier submitters consider the manufacturer's opinions.
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electric wires and insulation An electric wire is a linear member for transmitting electricity. Metal, which is a good conductor, is used for the part that transmits electricity, and plastic resin that has electric insulation is used around the wire in order to block the influence on anything other than the transmission destination of electricity.
Conductor
Figure 6
Sheath
Polyvinyl chloride is generally used for covering parts where plastic resin is used, which is called as sheath, but PTFE, PFA, FTPE, etc. are selected depending on the suitability of use and electric insulation requirements. Since these are more expensive than polyvinyl chloride, they are used only when it is difficult to use other materials such as polyvinyl chloride.
PFAS functions required by PFAS wires and availability of alternatives. Wires using PFAS for coating have high electrical insulation when the coating is thin (100 m or less). PFAS also has a high heat resistance of 150-200C. In addition, PFAS wires can be used even when there are chemicals around the device because PFAS has chemical resistance.
Examples of devices equipped with electric wire and insulation Medical cables of probe cable for ultrasound diagnostic equipment
Photo3
Photo1
Photo2
Cross-sectional view of one coaxial wire
Figure 7 The ultrasonic diagnostic device is shown in Photo 1 and consists of an image analysis unit and a cable with a transducer.
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JIMA PFAS APPENDIX01 2023/09/14 Japan Inspection Instruments Manufacturer's Association (JIMA)
The cable with transducer shown in Photo 2 is composed of about 200 coaxial wires in order to transmit and receive about 200 signals. The inside of the red circle cable in Photo 2 is as shown in Photo 3. Photo 4 shows a cross-sectional view of one of Photo 3. The performance required for these coaxial wires is (electric insulation / low dielectric constant), heat resistance, and extrusion suitability. PFA/FEP is used as a material that satisfies these three elements.
Table 15 Comparison with alternative candidate material PEEK shows the comparison results with the alternative candidate material PEEK. In order to obtain a diagnostic image with high accuracy, the attenuation of coaxial wire must be 2 dB / m or less in terms of the size shown in Table 15 Comparison with alternative candidate material PEEK, and the required performance is not satisfied unless PFA/FEP is applied.
In order to satisfy the attenuation, it is necessary to reduce the capacitance, and for this purpose, the dielectric constant must be 2.1 or less. The cross-sectional view of one coaxial wire is shown in Photo 4, and the red arrow part is the insulating layer and the green arrow part is the outer skin layer. Both layers require thickness control of 0.05 mm or less, and PEEK cannot be controlled, especially for the outer layer because it does not stretch.
In order to evenly cover the outer layer without destroying the shield layer, stretching is necessary. PEEK meets only heat resistance requirements.
Table 14 Comparison with alternative candidate material PEEK
Photo4
Figure 8 Cross-sectional view of one coaxial wire
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JIMA PFAS APPENDIX01 2023/09/14 Japan Inspection Instruments Manufacturer's Association (JIMA) Computed Radiography (CR) for Non-Destructive Testing CR generates an X-ray image by converting the X-ray information recorded on an imaging plate (IP), a type of X-ray detector used in X-ray photography, into an electrical signal by exciting it with a laser beam. PTFE is used for the sliding bearings in IP transport unit inside CR. PTFE is used to coat the plunger of the solenoid motor and the bobbin pipe in the mechanism that locks the IP cassette that stores IP in CR. The durable life of CR is about 6 years. In order to achieve this, it must be durable enough to withstand 64 million times of IP cassette loading from the assumed frequency of use of CR. PTFE's low friction property is essential, and replacing it with nickel plating reduces the durability to about 1/6, reducing the durable life of the equipment from 6 years to 1 year.
IP
Figure 9 Computed Radiography (CR)
Figure 10 The bobbin pipe in the mechanism that locks the IP cassette that stores IP in CR
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Imaging Plate (IP) for Non-Destructive Testing Imaging plate (IP) is an X-ray image conversion panel used in Computed Radiography (CR). When performing X-ray photography, the radiation that passes through the inspection object is temporarily recorded in the IP in the form of electronic energy distributed over the entire surface in proportion to the dose. The CR reads the X-ray information recorded in the IP and generates an X-ray image. After reading with CR, the X-ray information recorded on the IP is erased by irradiating it with white light, and the IP can be used repeatedly.
The layer structure of the imaging plate (IP) is shown in Figure 11. A phosphor is coated on a polyethylene terephthalate (PET) base approximately 350 m thick, which has excellent flatness and flexibility. A transparent "front protective layer" is applied to the surface of the phosphor layer to prevent dirt and scratches from sticking to the phosphor layer. Fluoropolymer is used for "front protective layer". The role of the surface protective layer is to prevent dirt and scratches on the IP surface due to repeated transport of the IP within the CR. Dirt and scratches on the surface of the IP will cause defects in X-ray images, making accurate inspections and diagnoses impossible. Therefore, the "front protective layer" on IP surface is required to be antifouling and low-friction. Fluoropolymer is the only material that satisfies the following property (antifouling, low-friction) and manufacturing suitability for coating.
surface
front protective layer Phosphor layer undercoat layer
PET base
back side
Figure 101 The layer structure of the imaging plate (IP)
back protective layer
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Figure 112 The Special Cut IP System Figure 123 Imaging Example
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Figure 134 Example of applying IP to welded pipe
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