JAEA-Data/Code

Radiation Durability of Polymeric Materials in Solid Polymer
Electrolyzer for Fusion Tritium Plant
Yasunori IWAI, Akihiro HIROKI, Toshihiko YAMANISHI
and Masao TAMADA

Tritium Technology Group
Fusion Research and Development Directorate

February 2009
Japan Atomic Energy Agency

日本原子力研究開発機構

JAEA-Data/Code

2008-027

JAEA-Data/Code
2008-027
JAEA-Data/Code
2008-027

Radiation Durability of Polymeric Materials
in Solid Polymer Electrolyzer for Fusion Tritium Plant
Yasunori IWAI, Akihiro HIROKI+, Toshihiko YAMANISHI and Masao TAMADA+Division of Fusion Energy Technology
Fusion Research and Development Directorate
Japan Atomic Energy Agency
Tokai-mura, Naka-gun, Ibaraki-ken

Received November 5, 2008

This document presents the radiation durability of various polymeric materials
applicable to a solid-polymer-electrolyte (SPE) water electrolyzer to be used in the tritium
facility of fusion reactor. The SPE water electrolyzers are applied to the water detritiation
system (WDS) of the ITER. In the ITER, an electrolyzer should keep its performance during
two years operation in the tritiated water of 9TBq/kg, the design tritium concentration of the
ITER. The tritium exposure of 9TBq/kg for two years is corresponding to the irradiation of noless than 530 kGy. In this study, the polymeric materials were irradiated with -rays or withelectron beams at various conditions up to 1600 kGy at room temperature or at 343 K. Thechange in mechanical and functional properties were investigated by stress-strain measurement,
thermogravimetricanalysis(TGA),

differential

scanning

calorimetry(DSC),

X-ray

photoelectron spectra (XPS), and so on. Our selection of polymeric materials for a SPE waterelectrolyzer used in a radiation environment was Pt + Ir applied Nafion® N117 ion exchange
membrane, VITON® O-ring seal and polyimide insulator.

Keywords: Radiation, Durability, Polymer, SPE, Tritium+

Environment and Industrial Materials Research Division, Quantum Beam Science Directoratei

JAEA- Data/Code
2008-027
JAEA-Data/Code
2008-027

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JAEA-Data/Code 2008-027

Contents
1. Introduction------------------------------------------------------------------------------- 1
2. Experimental Procedures --------------------------------------------------------------- 3
3. Data Tables on Radiation Durability of Various Polymeric Materials ------------ 9
3.1

Nafion N117CS ----------------------------------------------------------- 9

3.2

Nafion N112 ------------------------------------------------------------- 24

3.3

Nafion N115 ------------------------------------------------------------- 25

3.4

Nafion NE1110 ---------------------------------------------------------- 27

3.5

Nafion NE1135---------------------------------------------------------- 29

3.6

Polytetrafluoroethylene (PTFE) ------------------------------------- 31

3.7

PFA 500LP --------------------------------------------------------------- 33

3.8

FEP 750A ---------------------------------------------------------------- 37

3.9

Kapton 500H (Polyimide) --------------------------------------------- 40

3.10 Polyvinyl Chloride HTGA5749---------------------------------------- 43
3.11 VITON -------------------------------------------------------------------- 45
3.12 AFLAS SF ---------------------------------------------------------------- 48
3.13 Neoprene------------------------------------------------------------------ 52
3.14 EPDM --------------------------------------------------------------------- 55
3.15 Kalrez --------------------------------------------------------------------- 57
3.16 Butyl Rubber ------------------------------------------------------------- 62
3.17 Denaturated Polyphenylene Ether ------------------------------------- 64
4. Conclusion------------------------------------------------------------------------------ 67
Acknowledgment ------------------------------------------------------------------------- 67
References --------------------------------------------------------------------------------- 68


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Table Lists
Table 3.1-1

Atomic percentage of Nafion N117CS membrane----------------17

Table 3.1-2

S 2p: results of curve fitting -----------------------------------------21

Table 3.1-3

O 1s: results of curve fitting -----------------------------------------21

Table 3.1-4

C 1s: results of curve fitting -----------------------------------------22

Figure Lists
Figure 1

Structure of the SPE cell ----------------------------------------------- 7

Figure 2

Structure of the TEST STAND for the gamma-rays irradiation - 8

Figure 3.1-1

Tensile strength of γ-irradiated Nafion N117CS
at room temperature---------------------------------------------------10

Figure 3.1-2

Effect of dose rate on deterioration in tensile strength ------------11

Figure 3.1-3

Tensile strength of γ-irradiated Nafion N117CS at 343K ------12

Figure 3.1-4

Permeability coefficient ofγ-irradiated Nafion N117CS
at room temperature---------------------------------------------------13

Figure 3.1-5

Weight loss curve vs. temperature of Na cation exchanged
Nafion N117CS membrane under helium atmosphere------------14

Figure 3.1-6

Weight loss of Na cation exchanged Nafion N117CS membrane
between 473-623K under helium atmosphere----------------------15

Figure 3.1-7

Temperature at 5% of weight loss of Na cation exchanged
Nafion N117CS membrane under helium atmosphere------------15

Figure 3.1-8

DSC curves of acid form Nafion N117CS membrane
under helium atmosphere---------------------------------------------16

Figures 3.1-9

X-ray photoelectron spectrums of Nafion N117CS membrane---18

Figures 3.1-10

High resolution spectrums of the S(2p) and C(1s) peaks --------19

Figures 3.1-11

High resolution spectrums of the F(1s) and O(1s) peaks --------20

Figures 3.1-12 TMA curves of acid form Nafion N117CS membrane ---------23
Figure 3.2-1

Elongation at break of γ-irradiated Nafion N112
at room temperature---------------------------------------------------24v

JAEA-Data/Code 2008-027

Figure 3.3-1

Elongation at break of γ-irradiated Nafion N115
at room temperature---------------------------------------------------25

Figure 3.3-2

Conductivity and electrical resistivity of the water
after irradiation --------------------------------------------------------26

Figure 3.4-1

Tensile strength of γ-irradiated Nafion NE1110
at room temperature---------------------------------------------------27

Figure 3.4-2

Elongation at break of γ-irradiated Nafion NE1110
at room temperature---------------------------------------------------28

Figure 3.4-3

Conductivity and electrical resistivity of the water
after irradiation --------------------------------------------------------28

Figure 3.5-1

Elongation at break of γ-irradiated Nafion NE1135
at room temperature---------------------------------------------------29

Figure 3.5-2

Conductivity and electrical resistivity of the water
after irradiation --------------------------------------------------------30

Figure 3.6-1

Tensile strength of γ-irradiated PTFE at room temperature----31

Figure 3.6-2

Elongation at break of γ-irradiated PTFE at room temperature32

Figure 3.7-1

Tensile strength of γ-irradiated PFA 500LP
at room temperature---------------------------------------------------33

Figure 3.7-2

Elongation at break of γ-irradiated PFA 500LP
at room temperature---------------------------------------------------34

Figure 3.7-3Quantity of dissolved fluorine vs. dose for PFA 500LP
irradiated at room temperature---------------------------------------34

Figure 3.7-4

Conductivity and electrical resistivity of the water
after irradiation --------------------------------------------------------35

Figure 3.7-5

DSC curves of PFA 500LP under helium atmosphere ------------36

Figure 3.8-1

Tensile strength of γ-irradiated FEP 750A
at room temperature---------------------------------------------------37

Figure 3.8-2

Quantity of dissolved fluorine vs. dose for FEP 750A
irradiated at room temperature---------------------------------------38

Figure 3.8-3Conductivity and electrical resistivity of the water
after irradiation --------------------------------------------------------38

Figure 3.8-4

DSC curves of FEP 750A under helium atmosphere--------------39

Figure 3.9-1

Elongation at break of Kapton 500H --------------------------------41
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JAEA-Data/Code 2008-027

Figure 3.9-2

Quantity of dissolved fluorine vs. dose for Kapton 500H
irradiated at room temperature---------------------------------------41

Figure 3.9-3Conductivity and electrical resistivity of the water
after irradiation --------------------------------------------------------42

Figure 3.10-1

Tensile strength of EB-irradiated Polyvinyl Chloride
HTGA5749 at room temperature ------------------------------------43

Figure 3.10-2

Elongation at break of EB-irradiated Polyvinyl Chloride
HTGA5749 at room temperature ------------------------------------44

Figure 3.10-3

Coloring of EB-irradiated Polyvinyl Chloride HTGA5749(0, 100, 160,250, 500, 1000 kGy, vacuum-packed) ---------------44

Figure 3.11-1

Elongation at break VITON ------------------------------------------46

Figure 3.11-2

Quantity of dissolved fluorine vs. dose for VITON
irradiated at room temperature---------------------------------------46

Figure 3.11-3

DSC curves of VITON under helium atmosphere -----------------47

Figure 3.12-1

Tensile strength of AFLAS SF at room temperature --------------49

Figure 3.12-2

Elongation at break of AFLAS SF at room temperature ----------49

Figure 3.12-3

Quantity of dissolved fluorine vs. dose for AFLAS SF
irradiated at room temperature---------------------------------------50

Figure 3.12-4

DSC curves of AFLAS SF under helium atmosphere-------------51

Figure 3.13-1

Elongation at break of Neoprene at room temperature------------53

Figure 3.13-2

Coloring of the water after the irradiation of
Neoprene withγ- rays (0, 160, 500, 850 kGy) --------------------53

Figure 3.13-3

DSC curves of Neoprene under helium atmosphere---------------54

Figure 3.14-1

Tensile strength of EB-irradiated EPDM at room temperature --55

Figure 3.14-2

Elongation at break of EB-irradiated EPDM
at room temperature---------------------------------------------------56

Figure 3.15-1

Tensile strength of γ-irradiated Kalrez at room temperature---57

Figure 3.15-2

Elongation at break of γ-irradiated Kalrez
at room temperature---------------------------------------------------58

Figure 3.15-3

Quantity of dissolved fluorine vs. dose for Kalrez
irradiated at room temperature---------------------------------------58

Figure 3.15-4

Conductivity and electrical resistivity of the water
after irradiation --------------------------------------------------------59
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JAEA-Data/Code 2008-027

Figure 3.15-5

Weight loss curve vs. temperature of Kalrez
under helium atmosphere---------------------------------------------60

Figure 3.15-6

DSC curves of Kalrez-------------------------------------------------61

Figure 3.16-1

Tensile strength of EB-irradiated Butyl Rubber
at room temperature---------------------------------------------------62

Figure 3.16-2

Elongation at break of EB-irradiated Butyl Rubber
at room temperature---------------------------------------------------63

Figure 3.17-1

Tensile strength of Denaturated Polyphenylene Etherat room temperature---------------------------------------------------65

Figure 3.17-2

Elongation at break of Denaturated Polyphenylene Etherat room temperature---------------------------------------------------65

Figure 3.17-3

Conductivity and electrical resistivity of the water
after irradiation --------------------------------------------------------66

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1. Introduction     Solid-polymer-electrolyte (SPE) water electrolysis 1)-3) is attractive in theelectrolytic process of radioactive liquid waste because it can electrolyze liquid waste
directly without alkaline addition. The SPE water electrolyzers are planned to be used in
the water detritiation system (WDS) 4) of the ITER 5), international thermonuclear
experimental reactor. Figure 1 shows a structure of the electrolysis cell, a unit ofelectrolyzer. 6) The polymeric materials used in the commercial SPE water electrolyzer
are an integrated ion exchange membrane, and a set of gaskets and electric insulators.
Hence, the radiation durability of these polymers is a debatable point to use SPE waterelectrolyzers under radiation environment. In the tritium facility of the ITER, eachelectrolyzer is planed to be replaced every two years. Therefore, the electrolyzer should
keep its performance during two years operation in tritiated water of 9TBq/kg that is thedesign value of tritium concentration in the SPE water electrolyzers of the ITER. The
tritium exposure of 9TBq/kg for two years is corresponding to the irradiation dose of
530 kGy. Therefore, the effect of tritium exposure on polymeric materials used in the
SPE water electrolyzers should be carefully investigated.
     The practically used ion exchange membranes are polyperfluorosulfonicacid (PFSA) membrane such as Nafion® (du Pont de Nemours & Co. Inc) because ofhigh proton conductivity, good chemical stability and high mechanical strength.7) ThePFSA membrane consists of a polytetrafluoroethylene (PTFE) backbone withperfluoroalkylether (PFAE) side-chains terminating with -SO3- M+ groups, where M+ isan exchangeable cation.8) There were not systematic data, available for the design of
the SPE electrolyzer applicable to radiation environment, on the radiation deteriorationin the properties of the Nafion membrabe swelling in the water.
has been relatively little published on this aspect.

Surprisingly, there

E.N. Balko and J.T. Chaklos

examined the effect of electron and 60Co -rays radiations in air on the deteriorationin the Nafion properties.9) They concluded that Nafion irradiated in air deteriorated by
the single chain scission, and the deterioration rate was not affected by the hydration
state or by the nature of the exchangeable cation.

A matter for consideration is then acontribution of contained water to the deterioration.

The structure model thatpolymeric ions and water contained in the Nafion membrane are clustered and separated
from surrounding fluorocarbon matrix is generally accepted.10)-11) The clusters areconnected by the short and narrow channels in the hydrated Nafion.
1−−

T. Sakai et al.

JAEA-Data/Code 2008-027

examined the oxygen diffusivities for dry Nafion N117 (H form) and for hydrated
Nafion (H form), and they compared the values with that for PTFE.12)

The

permeability coefficient in the 35 w/o hydrated Nafion was one order magnitude greaterthan that in the dried Nafion. The permeability coefficient in the dried Nafion wasclose to that in PTFE. The diffusion coefficient in the dried Nafion was close to that in
PTFE, whereas that in the hydrated Nafion was 20 times greater than that in the dried
Nafion. The produced radicals in the polymer by irradiation promptly react on oxygen
molecules.

They are probably principal reactions for the deterioration of an

oxygen-diffusible polymer even swelling in the oxygen-saturated water.

Hence, thecontribution of oxygen-induced radical termination reactions to the deterioration in theswelling Nafion properties must be quantified.
PTFE has high electrical insulation as well as a heat resistance and highstability to any chemical solvent. Therefore, PTFE is widely applied for industrial use.
There are a number of reports on the radiation deterioration in PTFE properties. 13)
PTFE has been classified as a typical fragile polymer under radiation environment since
main chain scission is promoted by irradiation.

It is well known that even a small dose

up to a few hundreds kGy leads to the decrease in molecular weight of PTFE either in
air or under vacuum.14) The decrease deteriorates the mechanical properties of PTFE.
Hence, replacing PTFE insulators with high durability insulators such as polyimide
insulators is necessary to use SPE water electrolyzers under radiation environment.
There are many kinds of rubbers available for gaskets.

For the gaskets,

stable mechanical strength, softness and the negligible organic elution against the
exposure to the tritiated water are necessary.

However, there were not systematic dataon the deterioration in the properties of rubbery polymer swelling in the water underradiation environment. The rubbers will be structurally changed with the competition
reactions of chain scission and crosslinking.
In this study, a series of irradiation tests of the candidate polymeric materials
for a SPE water electrolyzer up to 1600 kGy using the 60Co irradiation facility or theelectron beam irradiation facility at the Takasaki Advanced Radiation Research Instituteof Japan Atomic Energy Agency (JAEA) was conducted to research the radiation
durability of the polymeric materials.

2−−

JAEA-Data/Code 2008-027

2. Experimental Procedures
The PFSA membranes tested in this study were Nafion NE117CS, Nafion
N112, Nafion N115, Nafion NE1110, Nafion NE1135. Four kinds of materials
candidate for electric insulators were tested which were PTFE, PFA, FEP and polyvinyl
chloride. Six kinds of materials candidate for gasket were tested which were Viton,
AFLAS, Neoprene, EPDM, Kalrez, and Butyl rubber. Denaturated polyphenylene ether
was also tested which is the packing material for an electrolytic conductivity meter.
Some kinds of Nafion membrane in the base form were provided by E. I. du
Pont de Nemours & Co. Inc.

No pretreatment was carried out on the hydrated baseform membrane prior to its use. The structure of the test stand for the irradiation with60

Co -rays at room temperature is illustrated in Fig. 2.

Nafion membrane was cut todumb-bell shape (ASTM D-1822L) specimens for the stress-strain measurement. The
direction for membrane section was decided as specimens had the largest tensile
strength.

A part of the specimens swelled in the oxygen-saturated distilled water.

The authors judged the complete hydration of the Nafion specimens with the periodic
measurements of their weights. It took more than 60 hours to reach the stable swellingof a Nafion specimen.

Six specimens were orderly enclosed with the oxygen-saturated

distilled water of 35.00.1g in a laminate film bag.

Distilled water produced by

Kyouei Pharmaceutical Co., Ltd. was used in the experiments. The concentration ofdissolved oxygen was measured with a DO meter (OE-270AA, DKK-TOA Corp.).
The authors brought specimens into contact with the water in the bag. They were thenirradiated with 60Co -rays at the dose rate of 10 kGy/h at room temperature using the60

Co -ray irradiation No. 2 facility or the 60Co facility for food irradiation in the

Takasaki Advanced Radiation Research Institute of Japan Atomic Energy Agency(JAEA). After the specimens were taken out from a laminate film bag, a series ofstress-strain measurements were carried out using PC-controlled Strograph VE5D
(Toyoseiki Co. Ltd.). The chuck span and the cross head speed adopted were 38.0 mm
and 20 mm/min during the experiment, respectively.
observation of elongation was 0.01mm.

The resolution for the

The pH value, electrolytic conductivity,

electrolytic resistivity, and quantity of dissolved fluorine in the distilled water were
measured with a pH meter (GST-2729C, DKK-TOA Corp.), with an EC meter(CM-21PW, DKK-TOA Corp.) and with a fluoride ion meter (F-2021, DKK-TOA
Corp.), respectively.

Prior to the measurement of the quantity of dissolved fluorine in3−−JAEA-Data/Code 2008-027

the distilled water with a fluoride ion meter, we added the ionic strength adjuster for
fluoride (TISAB-11, DKK-TOA Corp.) into the sample solution at the capacity ratio of
10: 1. The ionic strength adjuster dissolves the complex with metallic ion and makes it
ionized completely as fluoride ion.
titration as follows.

The ion exchange capacity was measured by

A piece of sample was cut from the irradiated specimen, and was

immersed into hydrochloric acid. By replacing the hydrochloric acid several times, asulfonic acid group in the sample was changed from SO3H to SO3-H+ by hydrolyze.
The sample was then washed with distilled water to remove hydrochloric acid. Afterthe washing, the sample was immersed into a solution of NaCl. The ion H+ was
replaced to Na+, and the H+ exuded from the sample to the solution. An amount of H+
was measured by titration with NaOH. The ion exchange capacity was thus evaluatedthrough the above procedures. The water content was then measured. The sample waswashed with distilled water to remove chlorine ion. After the washing, the sample was
wiped off and its weight was measured (W0). The sample was then dehydrated at 473 K
under vacuum. The authors measured the weight of samples dehydrated in desiccator(W1). The water content is evaluated as (W0/ W1 - 1)100.

To investigate the effectof oxygen on the radiation deterioration in Nafion properties, several conditions aretaken up for comparative purpose in addition to the irradiation in the oxygen-saturated
distilled water.

These are the irradiations under atmosphere, under vacuum, underswelling in 35.00.1g of 10wt% Na2SO3 solution, under swelling in 35.00.1g ofabout 30% H2O2 solution (S. S. Grade, Wako Pure Chemical Industries, Ltd.), underatmosphere with an oxygen absorbent (A-500HS, I.S.O. Corp.) and under swelling in
35.00.1g of oxygen-free water. Na2SO3 played a role of the absorber for dissolved
oxygen in the water.

Oxygen adsorbing time using oxygen absorbent was taken for

more than 24h before irradiation. Adsorption of oxygen was checked with an oxygen
indicator.

Oxygen-free water was produced by the procedure that 100cc of distilledwater was supplied in a gas wash bottle, and then dissolved oxygen in the water waspurged off with the 1000 Ncc/min of helium gas for more than 24h.
A test tube with the screw cap was adopted as the enclosure for the irradiationof Nafion specimens with 60Co -rays at 343 K.

The temperature of 343 K wasdetermined with due consideration of actual operating condition of a SPE electrolyzer ina nuclear facility.4)

Six specimens were orderly enclosed with the oxygen-saturated

distilled water in a test tube and the tube was preheated at 343 K for more than 2 hours.
4−−JAEA-Data/Code 2008-027

The test tube was then installed in a PID temperature-controlled heater in the 60Co
irradiation room. They were irradiated with 60Co -rays at the dose rate of 10 kGy/h.
To investigate the effect of oxygen on the radiation deterioration in the Nafion
properties at 343 K, different two conditions are taken up for comparative purpose inaddition to the irradiation in oxygen-saturated distilled water.

These are irradiations

under vacuum and in the oxygen-free water.
The effect was also observed with electron beams at room temperature toconsider whether there is a discrepancy in the deteriorations between 60Co -rays
irradiation and electron beams irradiation. The enclosure and its content are the sameas those for the irradiation with 60Co -rays at room temperature. They were irradiatedwith electron beams at equivalent dose rate to 250 kGy/h using the electron accelerator
No.1 facility of the Cockcroft-Walton type in Takasaki Advanced Radiation ResearchInstitute of JAEA under the conditions of the beam energy of 1.99 MeV and the beam
current of 2.00 mA.

A sufficient long interval for every 50 kGy irradiation was taken

to prevent the temperature rising of the specimens.
As for the gas permeability through the Nafion membrane, the effect of doseon the gas permeability was evaluated using a GTR-20XF (GTR TEC) with the test
procedure of JIS K 7126 B. The gas permeability was measured at 343K with two gas
systems; H2-H2O or O2-H2O. The relative humidity was set at 90% in each gas system.
The effect of the dose rate on the deterioration was examined in addition to
the dose rate of 10 kGy/h. The additional dose rates were 2.5 kGy/h and 0.5 kGy/hwith due consideration of the previous observations that the effect of the dose rate on
the radiation deterioration in the polymer properties is generally negligible at less than
1.0 kGy/h. The elongation at break and the ion exchange capacity for each dose rate
were compared at the dose of 160 kGy.
Thermogravimetric analysis was carried out on a TG-DTA-2000S analyzer(Mac Science) under helium atmosphere to prevent a sample from oxidation andadsorption of moisture. An aluminum pan was used for all the samples, and it was
flamed prior to each analysis. The continuous scan was carried out with a constantrate of 10K/min.
A DSC-3200 differential scanning calorimetry analyzer (Mac Science) wasused to obtain DSC thermograms. Experiments were run from 80K to 893K with aheating rate of 5K/min on about 10- mg sample weight.
5−−

JAEA-Data/Code 2008-027

X-ray photoelectron spectra were obtained using a Kratos Axis Ultra electron
spectrometer. Monochromatic AlK  photons (15kV, 10mA) were used for themeasurement. The analyzer pass energy was set to 160 eV for surver scans and to 20 eV
for high resolution narrow scans. An area of 300x700 micrometers of the sample
surface was analyzed at the normal photoelectron take-off angle for all samples. The
F(1s) peak set at 688.94 eV was used as the binding energy reference for all spectra.
The test procedures to the Nafion membrane were applied to other porimericmaterials.

6−−

JAEA-Data/Code 2008-027

Pt

Ir

H2
H 2O

O2
H 2O

+

H
+

(H 2O)

H 2O

H2



Ion exchange
membraneN afion
Anode : 2H 2O4H ++4e+O 2
Cathode: 4H ++4e2H 2(a) Pri nciple of solid polymer electrolyte
water electrolysis



O2





H 2O


flangeinsulator
main cathodegasketcathode electric supplierion exchange membrane+Pt+Iranode electric supplierbipola platemain anode(b) Exploded view of electrolyzer

Figure 1

Structure of the SPE cell
7
−−



JAEA-Data/Code 2008-027

Laminate Film Bag
triple-layer laminate film of polyester,aluminum and polyethylene
G amma Rays

- barrier function to oxygen and vapor
permeation
N afion Specimen
Oxygen-Saturated Water, etc.
SupportFigure 2

Structure of the TEST STAND for the gamma-rays irradiation

8−−

JAEA-Data/Code 2008-027

3. Data Tables on Radiation Durability of Various Polymeric Materials
3.1 Nafion N117CS 15)-19)㻹㼍㼠㼑㼞㼕㼍㼘

㻺㼍㼒㼕㼛㼚㻌㻺㻱㻝㻝㻣㻯㻿㼀㼔㼕㼏㼗㼚㼑㼟㼟㻔㻰㼡㻌㻼㼛㼚㼠㻌㼐㼑㻌㻺㼑㼙㼛㼡㼞㼟㻌㻒㻌㻯㼛㻚㻌㻵㼚㼏㻕㻜㻚㻝㻤㻡㻌㼙㼙㻌㻔㼍㼟㻌㼟㼣㼑㼘㼘㼕㼚㼓㻌㼕㼚㻌㼣㼍㼠㼑㼞㻕㻵㼞㼞㼍㼐㼕㼍㼠㼕㼛㼚㻌㼏㼛㼚㼐㼕㼠㼕㼛㼚㻢㻜㻌㻯㼛㻌䃒㻙㼞㼍㼥㼟㻦㻌㻝㻜㼗㻳㼥㻛㼔㻾㼛㼛㼙㻌㼀㼑㼙㼜㼑㼞㼍㼠㼡㼞㼑䕔㻦㻿㼣㼑㼘㼘㼕㼚㼓㻌㼕㼚㻌㼛㼤㼥㼓㼑㼚㻙㼟㼍㼠㼡㼞㼑㼠㼑㼐㻌㼣㼍㼠㼑㼞㼃㼍㼠㼑㼞㻦㻌㻟㻡㻚㻜㼼㻜㻚㻝㼓䕿㻦㻭㼠㼙㼛㼟㼜㼔㼑㼞㼑䕕㻌㻦㻌㼂㼍㼏㼡㼡㼙㻙㼜㼍㼏㼗㼑㼐䕦㻌㻦㻌㻿㼣㼑㼘㼘㼕㼚㼓㻌㼕㼚㻌㻝㻜㼣㼠㻑㻌㻺㼍㻞㻿㻻㻟㻌㼟㼛㼘㼡㼠㼕㼛㼚㻿㼛㼘㼡㼠㼕㼛㼚㻦㻌㻟㻡㻚㻜㼼㻜㻚㻝㼓䖃㻦㻌㻿㼣㼑㼘㼘㼕㼚㼓㻌㼕㼚㻌㼍㼎㼛㼡㼠㻌㻟㻜㻑㻌㻴㻞㻻㻞㻌㼟㼛㼘㼡㼠㼕㼛㼚㻌㻿㼛㼘㼡㼠㼕㼛㼚㻦㻌㻟㻡㻚㻜㼼㻜㻚㻝㼓䕧㻦㻭㼠㼙㼛㼟㼜㼔㼑㼞㼑㻌㼣㼕㼠㼔㻌㼛㼤㼥㼓㼑㼚㻌㼍㼎㼟㼛㼞㼎㼑㼚㼠㻹㼑㼍㼟㼡㼞㼑㼙㼑㼚㼠䕰㻦㻿㼣㼑㼘㼘㼕㼚㼓㻌㼕㼚㻌㼛㼤㼥㼓㼑㼚㻙㼒㼞㼑㼑㻌㼣㼍㼠㼑㼞㼃㼍㼠㼑㼞㻦㻌㻟㻡㻚㻜㼼㻜㻚㻝㼓㻿㼠㼞㼑㼟㼟㻙㻿㼠㼞㼍㼕㼚㻌㻹㼑㼍㼟㼡㼞㼑㼙㼑㼚㼠㻰㼡㼙㼎㻙㼎㼑㼘㼘㻌㻿㼔㼍㼜㼑㻦㻌㻭㻿㼀㻹㻌㻰㻙㻝㻤㻞㻞㻸㻯㼞㼛㼟㼟㻌㻴㼑㼍㼐㻌㻿㼜㼑㼑㼐㻦㻌㻞㻜㻚㻜㻌㼙㼙㻛㼙㼕㼚㻯㼔㼡㼏㼗㻌㻿㼜㼍㼚㻦㻌㻟㻤㻚㻜㻌㼙㼙㻵㼛㼚㻌㻱㼤㼏㼔㼍㼚㼓㼑㻌㻯㼍㼜㼍㼏㼕㼠㼥

9−−

JAEA-Data/Code 2008-027













Figure 3.1-1

 
 





Tensile strength of γ-irradiated Nafion N117CS at room temperature10− 10 −

JAEA-Data/Code 2008-027

!2%0)!+!&).- 3.-2$%%,.301.-#

()#*-%11  ,,!114%++)-')-4!2%000!$)!2).-#.-$)2).-

.80!61
 *6( *6(*6(
..,%,/%0!230%4%++)-')-56'%-!230%2%$ !2%0
%!130%,%-2!2%0 7 '20%1120!)-%!130%,%-2
3,""%++(!/%  
0.11%!$/%%$ ,,,)(3#*/!- ,,.-5#(!-'%!/!#)26











 



 













 

Figure 3.1-2 Effect of dose rate on deterioration in tensile strength

−11
11 −

JAEA-Data/Code 2008-027

"3&1*",

"'*/.)*$+.&22

4/.3%&&-/412/.$  --"225&,,*.(*.5"3&1

11"%*"3*/.$/.%*3*/.





/<1"72 +7):5&,,*.(*./67(&.2"341&3&%5"3&1!"3&1

8 (

9 "$44-0"$+&%;5&,,*.(*./67(&.'1&&5"3&1!"3&1 8 (31&2231"*.&"241&-&.34-##&,,)"0& 

&"241&-&.31/22&"%0&&% ---*.
)4$+0". -/.6$)".(&"0"$*37   





"    !






Figure 3.1-3 
 #





Tensile strength of γ-irradiated Nafion N117CS at 343K

−12
12 −

JAEA-Data/Code 2008-027

%6)4-%/

%*-21 !
7216())0274521' 00%558)//-1+-18%6)4

",-'.1)55

44%(-%6-21'21(-6-21  2<4%:5 .:,220")03)4%674)!8)//-1+-129:+)15%674)6)(8%6)4#%6)4  ;  +)40)%&-/-6:2)**-'-)16
"  $" "70-(-6:  ")03)4%674)
)40)%6-214)%  '0)%574)0)16

$! &'#"&!!%!





 



Figure 3.1-4





#%' 

Permeability coefficient ofγ-irradiated Nafion N117CS
at room temperature

−13
13 −

JAEA-Data/Code 2008-027

#4'2+#-

#(+0/ 
50/4&''.05230 /%
..#337'--+/)+/7#4'2

!*+%,/'33

22#&+#4+0/%0/&+4+0/  0;2#93 ,9 *00.!'.1'2#452'
7'--+/)+/089)'/3#452'4'&7#4'2"#4'2 :)'#352'.'/4!*'2.0)2#6+.'42+%#/#-93+3!
!!
#% %+'/%'
#.1-'.)#4+0/37'2''8%*#/)'&+/40#
$'(02'4*'!
!'.1 2#4'  .+/52)')#3' %% .+/ 




 
 




     

Figure 3.1-5

Weight loss curve vs. temperature of Na cation exchanged Nafion
N117CS membrane under helium atmosphere

−14
14 −

 !


JAEA-Data/Code 2008-027

Figure 3.1-6


















 





Weight loss of Na cation exchanged Nafion N117CS membrane 
"

between 473-623K under helium atmosphere

Figure 3.1-7

 
 
 

















 !
Temperature at 5% of weight loss of Na cation exchanged Nafion
N117CS membrane under helium atmosphere15− 15 −

JAEA-Data/Code 2008-027

0#.')$',+ 1,+0"##*,1./,+!
&'!(+#//  **//2#))'+%'+20#..."'0',+!,+"'0',+ )#!0.,+ #*/ (3-//(3&
,,*#*-#.01.#
!11*-!(#"
#/1.#*#+0
'$$#.#+0')/!++'+%!),.'*#0.3!!'#+!#*-)# *%#*-.0# *'+1.%#%/# !!*'+Figure 3.1-8

DSC curves of acid form Nafion N117CS membrane
under helium atmosphere16− 16 −

JAEA-Data/Code 2008-027

&7*5.&0"-.(/2*6655&).&7.32
(32).7.32

&+.32 !
8327)**1385632( 11&66:*00.2,.2:&7*5
3?5&<6/<-331"*14*5&785*/<&6*+351
 /<#2)*5&71364-*5*:.7-3;<,*2&'635'*27

*&685*1*27 %5&<4-373*0*(753264*(75&%!
5&736;.6#075&*0*(753264*(7531*7*55&736323(-531&7.(0>4-37326 /$ 1
2&0<=*54&66*2*5,<  *$+356859*56(&26*$+35-.,-5*63087.32
2&553:6(&26351&04-373*0*(75327&/*3++&2,0*
.2).2,*2*5,<5*+*5*2(* 64*&/&7 *$
!&140&&5*&;

1.(531*7*56

Results
Table 3.1-1


Atomic percentage of Nafion N117CS membrane





  
 

−17
17 −



 



 

JAEA-Data/Code 2008-027

F 1s

Intensity [CPS]

10x105
8x105
6x105
4x105

F KLL

2x105

S 2s
C 1s S 2p

O KLL

0x105

1000

O 1s

800

600

F 2s

400

Binding Energy [eV]F 1s

10x105Intensity [CPS]

0 kGy

200

0

850kGy

8x105
6x105
4x105

F KLL
O KLL

2x105
0x105

S 2s
C 1s S 2p
O 1s

1000

Figures 3.1-9

800

600

F 2s

400

Binding Energy [eV]200

X-ray photoelectron spectrums of Nafion N117CS membrane

−18
18 −

0

JAEA-Data/Code 2008-027

Figures 3.1-10

High resolution spectrums of the S(2p) and C(1s) peaks

19− 19 −

JAEA-Data/Code 2008-027

Figures 3.1-11

High resolution spectrums of the F(1s) and O(1s) peaks

20− 20 −

JAEA-Data/Code 2008-027

 !"#%$# %"&$$#! 
! #$ 
'



(
(
(
(
(
(




    

 




Split span of S2p3/2 and S 2p1/2 was set as 1.18 eV. Intensity ratio of of S2p3/2 and S2p1/2
was set as 2:1. Half width of S2p3/2 and S 2p1/2 was set as same value.
O2: -SO3, O3: -OCF3

  $#$&%$!&#'%% $"









! ) )





 


 




"!$%! 

)

 





( )
)

 
 

 


 
 

 )





 

−21−





JAEA-Data/Code 2008-027

  $#$&%$!&#'%% $"











! 

)
 




 )

 


 
"!$%!  )           )        (
)
 
 



 )
 
 
 


! 
"!$%! 
(

$"











)
 )

 
 




 








)
         )      
 
)

 
 

 )

 



   
C1: C-C, C2: C*-C-CF2, C3: O-C*-CF2, C4: C-F, C5: COO, C6: O-C-F, C7: CF2, C8:
OCF2, C9: CF3, C10: OCF3

−22
22 −

JAEA-Data/Code 2008-027

$5(3,$.

$),10!

6105'((/163410&
33$',$5,10&10',5,10 &,'13/ -9
33$',$5('7,5+(.(&5310%($/414(

-9

14(3$5(-92$44-9+

11/"(/2(3$563(!7(..,0*,089*(0!$563(5('#$5(3"+,&-0(44#$5(3  ;  *  // -9

($463(/(05   //
-9
"+(3/1/(&+$0,&$.0$.94,4"" !+,/$':6
6/%%(..!+$2( //8//

1$'  *"(/23$5( /,0+6&-!2$0  //
63*(*$4,531*(0&&/,0 



0kGy
Acid form





EB 1250kGy
Room Temp.
Acid form




       
Figures 3.1-12 TMA curves of acid form Nafion N117CS membrane23− 23 −

JAEA-Data/Code 2008-027

3.2 Nafion N112 18)

!2%0)!+!&).-3.-2$%%,.301.-#

()#*-%11

00!$)!2).-#.-$)2).-,,!115%++)-')-5!2%0.90!71 *7(

..,%,/%0!230%5%++)-')-67'%-!230%2%$ !2%0
!2%0 8 '20%1120!)-%!130%,%-2

%!130%,%-2

3,""%++(!/% 0.11%!$/%%$ ,,,)(3#*/!- ,,,.3-2.&)11.+4%$+3.0)-%)-2(%5!2%0
.-$3#2)4)27.&2(%5!2%0
+%#20)#!+%1)12)4)27.&2(%5!2%0 

















 

  
Figure 3.2-1

Elongation at break of γ-irradiated Nafion N112 at room temperature24− 24 −

JAEA-Data/Code 2008-027

3.3 Nafion N115 18)

"3&1*",

"'*/.
4/.3%&&-/412/.$)*$+.&2211"%*"3*/.$/.%*3*/.

--"226&,,*.(*.6"3&1/:1"82 +8)
//- &-0&1"341&
6&,,*.(*.78(&."341&3&%!"3&1!"3&1 9 (&"241&-&.3

31&2231"*.&"241&-&.34-##&,,)"0&  1/22&"%0&&% ---*.
)4$+0". --/4.3/'*22/,5&%,4/1*.&*.3)&6"3&1
/.%4$3*5*38/'3)&6"3&1
,&$31*$",&2*23*5*38/'3)&6"3&1

 















 

  
Figure 3.3-1

Elongation at break of γ-irradiated Nafion N115 at room temperature25− 25 −

JAEA-Data/Code 2008-027

 

  "!








Figure 3.3-2

   Conductivity and electrical resistivity of the water after irradiation

26− 26 −

JAEA-Data/Code 2008-027

3.4 Nafion NE1110 18)

#4'2+#-

#(+0/*+%,/'33

50/4&''.05230/%
  ..#337'--+/)+/7#4'2=22#&+#4+0/%0/&+4+0/

..#36#%55.1#%,'&<0>2#93 ,9*

00. '.1'2#452'=:7'--+/)+/89)'/#452'4'&"#4'2"#4'2 ; )<!#%55.1#%,'&
42'3342#+/'#352'.'/4

'#352'.'/4

5.$$'--*#1'   2033'#&1''& ...+/*5%,1#/ ..
.05/40(+330-6'&-502+/'+/4*'7#4'2
0/&5%4+6+490(4*'7#4'2
-'%42+%#-'3+34+6+490(4*'7#4'2






















 

 
Figure 3.4-1

Tensile strength of γ-irradiated Nafion NE1110 at room temperature27− 27 −

JAEA-Data/Code 2008-027

 


















 

  
Elongation at break of γ-irradiated Nafion NE1110

Figure 3.4-2

at room temperature 
  "!















Figure 3.4-3







Conductivity and electrical resistivity of the water after irradiation28− 28 −

JAEA-Data/Code 2008-027

3.5 Nafion NE1135 18)

!2%0)!+!&).-()#*-%113.-2$%%,.301.-# ,,!115%++)-')-5!2%000!$)!2).-#.-$)2).-

.90!71 *7(
..,%,/%0!230%5%++)-')-67'%-!230%2%$ !2%0
!2%0 8 '%!130%,%-2

20%1120!)-%!130%,%-2
3,""%++(!/%  
0.11%!$/%%$ ,,,)(3#*/!- ,,,.3-2.&)11.+4%$+3.0)-%)-2(%5!2%0
.-$3#2)4)27.&2(%5!2%0
+%#20)#!+%1)12)4)27.&2(%5!2%0 

















 

  
Figure 3.5-1

Elongation at break of γ-irradiated Nafion NE1135
at room temperature29− 29 −

JAEA-Data/Code 2008-027 !

 !#"

















 !
Figure 3.5-2

Conductivity and electrical resistivity of the water after irradiation30− 30 −

JAEA-Data/Code 2008-027

3.6 Polytetrafluoroethylene (PTFE)

 1$/( *-*61$1/ %*2-/-$1'6*$,$
-/.  ++

'("),$00
// #( 1(-,"-,#(1(-,-;/ 60)6'
--+$+.$/ 12/$8 "22+. ")$#
*$"1/-,!$ +0)6. 00--+$+.$/ 12/$71+-0.'$/$
9$/--56&$, 1+-0.'$/$
4(1'-56&$, !0-/!$,1)6':(&'3 "22+*-4$/1' , 1-//
1/$001/ (,$ 02/$+$,1
2+!!$**' .$

/-00$ #.$$# +++(,'2"). , ++$ 02/$+$,1 











Figure 3.6-1



 Tensile strength of γ-irradiated PTFE at room temperature31− 31 −

JAEA-Data/Code 2008-027

     










Figure 3.6-2



  Elongation at break of γ-irradiated PTFE at room temperature32− 32 −

JAEA-Data/Code 2008-027

3.7 PFA 500LP 18)
$5(3,$.

 
6105'((/163410&

+,&-0(4433$',$5,10&10',5,10

//



1?3$:4 -:+11/ (/2(3$563(=8(..,0*,09:*(0$563(5('"$5(3"$5(3 ; *<!$&66/2$&-('>#(3119:*(0$5/142+(3(8,5+19:*(0$%413%(0553(4453$,0($463(/(056/%%(..+$2(   3144($'2((' ///,0($463(/(05+6&-2$0 ///16051),441.7('.613,0(,05+(8$5(310'6&5,7,5:1)5+(8$5(3.(&53,&$.(4,45,7,5:1)5+(8$5(3











Figure 3.7-1

 
  

Tensile strength of γ-irradiated PFA 500LP at room temperature33− 33 −

JAEA-Data/Code 2008-027

 










      Elongation at break of γ-irradiated PFA 500LP at room temperature 

Figure 3.7-2









Figure 3.7-3 
 





Quantity of dissolved fluorine vs. dose for PFA 500LP
irradiated at room temperature34− 34 −

JAEA-Data/Code 2008-027 !

 !#"







Figure 3.7-4 
 !





Conductivity and electrical resistivity of the water after irradiation

35− 35 −

JAEA-Data/Code 2008-027

"2%0)"+

()#*-%11

3.-2$%%,.301.-# ,,

00"$)"2).-#.-$)2).-

.80"61*6(.., %,/%0"230%4%++)-')-56'%-"230%2%$!"2%0%"130%,%-2!"2%0  7  ')&&%0%-2)"+1#"--)-'#"+.0),%206


"##)%-#%
",/+% ,'%,/0"2% ,)30'%'"1%

Figure 3.7-5

##,)-

DSC curves of PFA 500LP under helium atmosphere36− 36 −

JAEA-Data/Code 2008-027

3.8 FEP 750A 18)
#4'2+#-

 50/4&''.05230/%

!*+%,/'33

 ..

22#&+#4+0/%0/&+4+0/0;2#93 ,9*
00.!'.1'2#452'
7'--+/)+/89)'/ #452'4'&"#4'2"#4'2

'#352'.'/4

: )

42'33 42#+/'#352'.'/4
5.$$'-- *#1' ! 2033'#& 1''& ...+/*5%, 1#/ ..
.05/40(+330-6'&-502+/'+/4*'7#4'2
0/&5%4+6+490(4*'7#4'2
-'%42+%#-'3+34+6+490(4*'7#4'2



















 

 
Figure 3.8-1

Tensile strength of γ-irradiated FEP 750A at room temperature37− 37 −

 

JAEA-Data/Code 2008-027


















 
Quantity of dissolved fluorine vs. dose for FEP 750A

Figure 3.8-2

irradiated at room temperature !

 !#"






Figure 3.8-3 
 !





Conductivity and electrical resistivity of the water after irradiation38− 38 −

JAEA-Data/Code 2008-027

#3&1*#,!)*$+.&22 4/.3%&&-/412/.$  --11#%*#3*/.$/.%*3*/.  /91#72 +7)
//-!&-0&1#341&
5&,,*.(*.67(&. #341&3&%"#3&1"#3&1  8  (&#241&-&.3
*''&1&.3*#,2$#..*.($#,/1*-&317  
#$ $*&.$&
#-0,& -(!&-01#3& -*.
41(&(#2&

Figure 3.8-4

$$-*.

DSC curves of FEP 750A under helium atmosphere39− 39 −

JAEA-Data/Code 2008-027

3.9 Kapton 500H (Polyimide) 16)

$5(3,$.

$2510 1.:,/,'(6105'((/163410&!+,&-0(4433$',$5,10&10',5,10



//

1A3$:4 -:+11/!(/2(3$563(@ 8(..,0*,09:*(0 $563(5('#$5(3#$5(3 ; *=5/142+(3(> 8(..,0*,09:*(0 $563(5('#$5(3#$5(3 ; *.(&5310%($/4 -:2$44
11/!(/2(3$563(

-:+?"$&66/2$&-('
($463(/(05<5/142+(3(53(44 53$,0($463(/(056/%%(.. +$2( ! 3144($' 2((' ///,0
+6&- 2$0 ///16051),441.7('.613,0(,05+(8$5(340− 40 −

JAEA-Data/Code 2008-027
















   !!#"  $ 

Figure 3.9-1

Elongation at break of Kapton 500H








Figure 3.9-2













!$
Quantity of dissolved fluorine vs. dose for Kapton 500H
irradiated at room temperature41− 41 −

JAEA-Data/Code 2008-027 !

 !#"

















 !
Figure 3.9-3Conductivity and electrical resistivity of the water after irradiation42− 42 −

JAEA-Data/Code 2008-027

3.10 Polyvinyl Chloride HTGA5749

.#,%'*'10%)1'$'*,%"#
!$%''#-*,+

$%!&)#--





((

,,"%.%*)!*)"%.%*) '#!.,*) #(-&1+--&1$**(#(+#,./,#
3!//(+!&#"
2.(*-+$#,#
.,#--.,%)#-/,#(#).
/(  #''$+# ,*--#"+##" (((%)

#-/,#(#).

$/!&+) ((










Figure 3.10-1

 
 





Tensile strength of EB-irradiated Polyvinyl Chloride HTGA5749
at room temperature43− 43 −

JAEA-Data/Code 2008-027

 









Figure 3.10-2

 
  





Elongation at break of EB-irradiated Polyvinyl Chloride HTGA5749
at room temperature

Figure 3.10-3

Coloring of EB-irradiated Polyvinyl Chloride HTGA5749(0, 100, 160,250, 500, 1000 kGy, vacuum-packed)

44− 44 −

JAEA-Data/Code 2008-027

3.11 VITON 16)-17)

%6)4-%/",-'.1)55
44%(-%6-21'21(-6-21#"
&-,%4% 7&&)4243 00

2C4%;5 .;,220")03)4%674)
B!9)//-1+-1:;+)1!%674)6)($%6)4$%6)4 < +>60253,)4)
?!9)//-1+-1%&276   52/76-21!2/76-21 < +)%574)0)16@!9)//-1+-1:;+)1!%674)6)($%6)4$%6)4 < +/)'6421&)%05 .;3%55 .;,
220")03)4%674)
A#%'7703%'.)(=60253,)4)
!64)55!64%-1)%574)0)16
70&&)//!,%3)!"  
4255)%(!3))( 000-1
,7'.!3%1 00
027162*-552/8)(/724-1)-16,)9%6)445− 45 −

JAEA-Data/Code 2008-027

 













!  "

Figure 3.11-1

    

Elongation at break of VITON









Figure 3.11-2





 "





Quantity of dissolved fluorine vs. dose for VITON
irradiated at room temperature46− 46 −

JAEA-Data/Code 2008-027

!2%0)!+

")(!0!3""%0.0/ ,,

()#*-%11
00!$)!2).-#.-$)2).-

.80!61 *6(

..,%,/%0!230%4%++)-')-56'%-!230%2%$ !2%0
%!130%,%-2!2%0 7 ')&&%0%-2)!+1#!--)-'#!+.0),%206
!##)%-#%
!,/+% ,'
%,/0!2% ,)30'%'!1% ##,)-Figure 3.11-3

DSC curves of VITON under helium atmosphere47− 47 −

JAEA-Data/Code 2008-027

3.12 AFLAS SF 16) 17) 19)

$5(3,$.

  

!+,&-0(44 132//

33$',$5,10&10',5,10



1A3$:4 -:+11/!(/2(3$563(? 8(..,0*,09:*(0 $563(5('#$5(3#$5(3 ; *=5/142+(3(>"$&66/2$&-('@ 8(..,0*,0 85$ 41.65,10

1.65,10 ; *.(&5310%($/4 -:2$44
11/!(/2(3$563(
B"$&66/2$&-('<5/142+(3(($463(/(05-:+53(44 53$,0($463(/(056/%%(.. +$2( ! 3144($' 2((' ///,0
+6&- 2$0 ///16051),441.7('.613,0(,05+(8$5(348− 48 −

JAEA-Data/Code 2008-027


















   

Tensile strength of AFLAS SF at room temperature

Figure 3.12-1







 
 










Figure 3.12-2

  

Elongation at break of AFLAS SF at room temperature49− 49 −

 !  

JAEA-Data/Code 2008-027








Figure 3.12-3













!
Quantity of dissolved fluorine vs. dose for AFLAS SF
irradiated at room temperature50− 50 −

JAEA-Data/Code 2008-027

#3&1*#,


/10--)*$+.&22
11#%*#3*/.$/.%*3*/.

/;1#72 +7)
//- &-0&1#341&:5&,,*.(*.67(&.#341&3&%"#3&1"#3&1 8 (9!#$44-0#$+&%

&#241&-&.3

*''&1&.3*#,2$#..*.($#,/1*-&317
 #$$*&.$&
#-0,& -(&-01#3& -*.
41(&(#2& $$-*.

Figure 3.12-4

DSC curves of AFLAS SF under helium atmosphere51− 51 −

JAEA-Data/Code 2008-027

3.13 Neoprene16)-17)

"2&0)"+

&./0&-&
#)("0"3##&0.0/

()$*-&11,,

00"%)"2).-$.-%)2).-

.<0"61 *6(
..,&,/&0"230&:4&++)-')-56'&-"230&2&%!"2&0!"2&0 7 '92,.1/(&0&;4&++)-')- 42"  1.+32)..+32).- 7 '+&$20.-#&",1 *6/"11
..,&,/&0"230&*6(= "$33,/"$*&%
82,.1/(&0&&"130&,&-2

20&1120")-&"130&,&-2
3,##&++("/& 0.11&"%/&&% ,,,)(3$*/"- ,,52− 52 −

JAEA-Data/Code 2008-027

 










Figure 3.13-1

Figure 3.13-2




    

Elongation at break of Neoprene at room temperature

Coloring of the water after the irradiation of Neoprene withγ- rays
(0, 160, 500, 850 kGy)

53

− 53 −

JAEA-Data/Code 2008-027

0#.')#,-.#+#

&'!(+#//

 '&.1 **.."'0',+!,+"'0',+#.,.-,6.4/ (4&,,*#*-#.01.#
2#))'+%'+34%#+01.#0#"0#.
0#.
#/1.#*#+05 %

'$$#.#+0')/!++'+%!),.'*#0.4
 !!'#+!#*-)# *%
#*-.0# *'+1.%#%/# !!*'+Figure 3.13-3

DSC curves of Neoprene under helium atmosphere54− 54 −

JAEA-Data/Code 2008-027

3.14 EPDM

16)+ )"$"!), )')(

!"#& ** %%))"+"'&'&"+"'& $ +)'& %* #-(**

#-!

''% %( )+,). ,,%(# +) **+)"& *,) % &+,% $$!( 

 *,) % &+)'** (  %%%"&!,#(& %%













Figure 3.14-1





 Tensile strength of EB-irradiated EPDM at room temperature55− 55 −

JAEA-Data/Code 2008-027

    









Figure 3.14-2





  Elongation at break of EB-irradiated EPDM at room temperature

56− 56 −

JAEA-Data/Code 2008-027

3.15 Kalrez

&7*5.&0

&05*=
"  314382) 
8 327 *5+351&2(*0&6731*5631

11@%  1155&).&7.32(32).7.32

3?5&<6 /<-!331#*14*5&785*":*00.2,.2;<,*2"&785*7*)$&7*5$&7*5 > ,*&685*1*27"75*66"75&.2*&685*1*27
81''*00"-&4*5.2,
5366*&)"4**) 111.2
-8(/"4&2 11
138273+.66309*)0835.2*.27-*:&7*532)8(7.9.7<3+7-*:&7*5
0*(75.(&0!*6.67.9.7<3+7-*:&7*5

 













Figure 3.15-1

 
 





Tensile strength of γ-irradiated Kalrez at room temperature

57− 57 −

JAEA-Data/Code 2008-027

 











  

Figure 3.15-2

 
  





Elongation at break of γ-irradiated Kalrez at room temperature














Figure 3.15-3





 





Quantity of dissolved fluorine vs. dose for Kalrez
irradiated at room temperature

58− 58 −

JAEA-Data/Code 2008-027

 !

 !#"








Figure 3.15-4

 
 !





Conductivity and electrical resistivity of the water after irradiation

59− 59 −

JAEA-Data/Code 2008-027

%5(3,%.

1/

%.3(;
! 1/2160' 
6105(3)13/%0&(.%451/(34//>$  //

33%',%5,10&10',5,10 1=3%:4 -:+11/"(/2(3%563(!8(..,0*,09:*(0!%563(5('#%5(3#%5(3 < *(%463(/(05"+(3/1*3%7,/(53,&%0%.:4,4""" !%&!&,(0&(!%/2.( /*"(/23%5( /,063*(*%4( &&/,0Figure 3.15-5

Weight loss curve vs. temperature of Kalrez under helium atmosphere60− 60 −

JAEA-Data/Code 2008-027

#3&1*#,

#,1&8 /-0/4.% 
4/.3&1'/1-#.$&,#23/-&12/---;"  --

11#%*#3*/.$/.%*3*/.

&#241&-&.3/:1#72 +7)
//- &-0&1#341&
5&,,*.(*.67(&.#341&3&%!#3&1!#3&1 9 (*''&1&.3*#,2$#..*.($#,/1*-&317
#$$*&.$&
#-0,& -(&-01#3& -*.
41(&(#2$$-*.

Figure 3.15-6

DSC curves of Kalrez61− 61 −

JAEA-Data/Code 2008-027

3.16 Butyl Rubber+ )"$,+-$, )"!), )')(

!"#& **%%))"+"'&'&"+"'& $ +)'& %* #-(**''% %( )+,)#-!. ,,%(#  *,) % &++) **+)"& *,) % &+,% $$!( 
)'** (   %%%"& 

!,#(& 

%%


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
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Figure 3.16-1


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 Tensile strength of EB-irradiated Butyl Rubber at room temperature62− 62 −

JAEA-Data/Code 2008-027

     










Figure 3.16-2



  Elongation at break of EB-irradiated Butyl Rubber at room temperature63− 63 −

JAEA-Data/Code 2008-027

3.17 Denaturated Polyphenylene Ether#3'1*#,

'.#341#3'&/,70)'.7,'.'3)'1)*%+.'22

 2434*,#23*%/10  --11#&*#3*/.%/.&*3*/.

/=1#72 +7)
//- '-0'1#341';5',,*.(*.67('.#341'3'&"#3'1"#3'1 8 (:3-/20)'1'<5',,*.(*. 53#  2/,43*/.
/,43*/. 8 (,'%31/.$'#-2 +70#22 +7)
//- '-0'1#341'>!#%44-0#%+'&
93-/20)'1''#241'-'.3

31'2231#*.'#241'-'.34-$$',,)#0'  1/22'#&0''& ---*.
)4%+0#. --64− 64 −

JAEA-Data/Code 2008-027

 











Figure 3.17-1

 
 





Tensile strength of Denaturated Polyphenylene Etherat room temperature









Figure 3.17-2





 





Elongation at break of Denaturated Polyphenylene Etherat room temperature65− 65 −

JAEA-Data/Code 2008-027 !
 !#"








Figure 3.17-3

 
 !





Conductivity and electrical resistivity of the water after irradiation

66− 66 −

JAEA-Data/Code 2008-027

4. Conclusion
Solid-polymer-electrolyte (SPE) water electrolysis is attractive in the electrolytic
process of the tritiated water in the Water Detritiation System (WDS) of a fusion reactor,
whereas polymer durability in the electrolyzer under radiation is an important point. The
radiation durability of the polymers was investigated from various viewpoints. The
conclusions are summarized as follows.
1.

A series of -ray irradiation tests of the Nafion® N117 ion exchange membrane
beyond the ITER-WDS requirement (530kGy) indicated that the Nafion® N117
membrane had sufficient radiation durability up to 1600 kGy with regard tomechanical strength and ion exchange capacity.

2.

To maintain the electrolysis function of the SPE cell up to 530 kGy, we suggest
replacing the Teflon insulator with a polyimide insulator. Any serious degradationin the tensile strength of the Kapton polyimide up to 1500 kGy was not observed ina -ray irradiation test series.

3.

Regarding the selection of rubber material for the O-ring seal, we observed that the
VITON rubber swelling in the water maintained a constant tensile strength value
up to 1500 kGy. Moreover, organic elution was not observed from VITON soaking.
With regard to stable strength and negligible organic elution, VITON rubber issuitable for the O-ring seal.

The test for verifying the tolerability of the polymers to tritium exposure is planned
using tritiated water. The test should determine whether there are any different
damaging effects promoted by the decay of isotopically exchanged tritium withinmaterials.
Acknowledgment
The authors wish to thank Mr. Toshiaki YAGI of JAEA for supporting theirradiation experiments and the useful discussion, Dr. Naotsugu NAGASAWA of JAEA
for the useful discussion, and also the staffs of irradiation service division of the Japan
Atomic Energy Agency, Takasaki.

67− 67 −

JAEA-Data/Code 2008-027

References
1)

L. J. Nuttall, J. H. Russell, Solid polymer electrolyte water electrolysis development status, International Journal of Hydrogen Energy, 5 (1980) pp.75-84.

2)

H. Takenaka, E. Torikai, Y. Kawami, et al., Solid Polymer Electrolyte Water
Electrolysis, International Journal of Hydrogen Energy, 7 (1982) pp.397-403.

3)

P. Millet, M. Pineri, R. Durand, New Solid Polymer Electrolyte Composites for
Water Electrolysis, Journal of Applied Electrochemistry, 19 (1989) pp.162-166.

4)

Y. Iwai, Y. Misaki, T. Hayashi, et al, The water detritiation system of the ITER
tritium plant, Fusion Sci. Technol., 41 (2002) pp.1126-1130.

5)

Summary of the ITER Final Design Report, ITER EDA Document Series No.22,
IAEA, Vienna (2001).

6)

H. Oshiro, H. Tatsumi, K. Nagaya, et al., Development of New Type Water
Electrolyzer, Hitachi Zosen Gihou, 59 (1998) pp.68-72, [in Japanese].

7)

H. L. Yeager, A. Eisenberg, editors. Perfluorinated Ionomer Membranes,
Symposium Series 180. Washington. DC: American Chemical Society; 1982.

8)

D. J. Connolly, W. F. Gresham, US Patent 3,282,875 (1966).

9)E. N. Balko, J. T. Chaklos, Effects of Ionizing Radiation on Perfluorosulfonic
Acid Ion-Exchange Polymer, Journal of Applied Polymer science, 26 (1981)
pp.1519-1531.

10)

S. C. Yeo, A. Eisenberg, Physical Properties and Supermolecular Structure of
Perfluorinated Ion-containing (Nafion) Polymers, J. Appl, Polym. Sci., 21 (1977)
pp.875-898.

11)

W. Y. Hsu, T. D. Gierke, Ion-transport and Clustering in Nafion PerfluorinatedMembrane J. Memb, Sci., 13 (1983) pp.307-326.

12)

T. Sakai, H. Takenaka, E. Torikai, Gas Diffusion in the Dried and Hydrated
Nafions, J. Electrochem. Soc., 133 (1986) pp.88-92.

13)

J. S. Forsythea, D. J. T. Hill, The radiation chemistry of fluoropolymers, Progress
in Polymer Science, 25 (2000) pp.101-136.

14)

M. Dole, The Radiation Chemistry of macromolecules Vol. II (Edited by M.
Dole), Academic Press, New York (1973) pp.167-178.

15)

Y. Iwai, A. Hiroki, M. Tamada, T. Yamanishi, Radiation detritiation inmechanical properties and ion exchange capacity of Nafion N117 swelling inwater, J. Membrane Sci., 322 (2008) pp.249-255.
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JAEA-Data/Code 2008-027

16)

Y. Iwai, A. Hiroki, T. Yagi, M. Tamada, T. Yamanishi, Experimental Durability
Studies of Electrolysis Cell Materials for a Water Detritiation System, Fusion Eng.
Des., 83 (2008) pp.1410-1413.

17)

Y. Iwai, T. Yamanishi, A. Hiroki, T. Yagi, M. Tamada, Solid-Polymer-Electrolyte
Ttitiated Water Electrolyzer for Water Detritiation System, Fusion Sci. Technol.,
54 (2008) pp.458-461.

18)

Y. Iwai, T. Yamanishi, K. Isobe, M. Nishi, T. Yagi, M. Tamada, Distinctive
radiation durability of an ion exchange membrane in the SPE water electrolyzer
for the ITER water detritiation system, Fusion Eng. Des., 81 (2006) pp.815-820.

19)

Y. Iwai, T. Yamanishi, K. Isobe, M. Nishi, T. Yagi, M. Tamada, Durability of
Irradiated Polymers in Solid-Polymer-Electrolyte Water Electrolyzer, J. Nucl. Sci.
Technol., 42 (2005) pp.636-642.

69− 69 −

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