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200
0

H2

5
10
Stroke displacement (mm)

1000

800
N2

600
H2

400
200

15

0

JIS-SCM435 at RT
115 MPa gas
CHS = 0.002 mm/s
BN = 843 MPa
BH = 820 MPa
N = 73 %H = 47 %RTS = 0.97
RRA = 0.64

510Stroke displacement (mm)(a) 233 K

Nominal stress,  (MPa)800

Nominal stress,  (MPa)Nominal stress,  (MPa)

1000

800
600
400
200

15

0

N2
H2

JIS-SCM435 at 393 K
115 MPa gas
CHS = 0.002 mm/s
BN = 842 MPa
BH = 835 MPa
N = 72 %H = 47 %RTS = 0.99
RRA = 0.65

510Stroke displacement (mm)(b) RT15(c) 393 K

Slow strain rate tensile (SSRT) properties of Cr-Mo steel JIS-SCM435 ¹ĀĖ8ƲǩǊǴq}åU
ǹ¹ĀīĴćĈơĞĿeǬǘǲHISCGǺ

JIS-SCM 435 at RT
R = 1
HV 256550a

Stress amplitude,  (MPa)600

Proposed criteria for safety factor-based
infinite-life design (Fatigue limit design)

500

400

< There is no degradation in tensile strength
during SSRT testing.

350< There is no degradation in fatigue limit.

450

300
250 2
10

:In air, f = 1 Hz
:In 115MPa H 2 , f = 1 Hz
In 115MPa H 2, f = 0.1 Hz
In 115MPa H 2, f = 0.01 Hz

10

3

10

4

Safety factor: S =
5

10

10

6

7

10

10

8

B
= 3.5 ~ 4
allowableB: Tensile strength, allowable: Allowable stress

Number of cycles to failure, N (cycles)f

S-N data of Cr-Mo steel JIS-SCM435

9ĭĊûĢZOQcÂėĲ¥hxq~[ÑčĻƥļo6©ƭơĞĿe3ļŏƱZMƒŏ

水素構造材料

Ʋ\'ƯĨħƱ«HYDROGENIUS¹Ā°Ľ¤ǘǸǔǤǸǑƾ°úƖƖƖƖƖƖƖ


H

Crack growth rateda/dN(m/cycle)

10 -5

JIS-SCM435

1642, *¯1221ǹ2015.10.27ǺH

H0.49ppm

H
H

H

H

H

H H

HDFF-A34-1

Copying is prohibited


10 -6

Ȃǿ

10 -7

H
0.49ppm
H0.3ppm
H0.47ppm

10 -8

Hydrogen-charged(f=20Hz)0.530.27ppm(f=20Hz)0.490.24ppm(f=2Hz)0.580.49ppm(f=0.2Hz)0.580.49ppm
Uncharged
0.01ppm

10 -9

10 -10102030ƓļtuÎ}ƔÝ5bCÎ}Ɨ
ƕÝ5ơĞĿeÎ}ưōƦƽĪŞǷĩ»ƾæò

H

H

a

da
da
H

Schematic image of the mechanism of effect ofhydrogen and test frequency on fatigue crack growth.

HYDROGENIUS DATA BASE (Tentative) Hydrogen Transport Properties 
No. A34

Data Base on Hydrogen Transport Properties of
SUS 316 (type 316, over 12 mass % Ni) Austenitic Stainless SteelHydrogen-charged(0.56ppm)(0.56ppm)

ũŪŨŹżƂŢǹũŪŨŨ¸LǺƱĵŠL¹ĀǇǑƬƱňf¤ƱvoǘǸǔƭãįƱŒð

K  17MPa m

May, 2011

Research Center for Hydrogen Industrial Use and Storage (HYDROGENIUS),
National Institute of Advanced Industrial Science and Technology (AIST)
Kyushu University

40 50 60 708090100

Stress intensity factor rangeK(MPam)ěLFØAňŊSCM435ưƞƣƽÝ5ơĞĿeļoƭ|2WùIƱōƖR = -1

(0.54ppm)
Uncharged specimen

Ƿ¹ĀÕTƬƲƗčĻƥĚņƾƹƩƢƼƟƣƽƭƗÝ5ơĞĿeļoƲ3ļƦƽǽǷ¹ĀưƺƽÝ5ơĞĿeļoƱ3ļưƲŏƠƛƽǽŏ ƲþūŨƬƛƽǽ2 !Éğag%%%%%%ĳďõą³

Ƿ¹ĀÎ}ǘǸǔǤǸǑǷļtuÎ}ǘǸǔǤǸǑǷÝ5bCÎ}ǘǸǔǤǸǑ
ǷÝ5ơĞĿeÎ}ǘǸǔǤǸǑŷŴŷťŢŶżŲŰťŢŴƍžƀſõưģ/ĢâƥƗ¹Ā³FĨħõǷ¹ĀĖ8ƱǫǆǛǒǪOèäñ
Ƿ\'ĨħƱ« ƾéƦOèäñģ/ĢâƥƱ« ƭƯƽĐƝƭǘǸǔƾ

ÙǼ£ŌǼ§gǼ¥Ǽ³ĭAċǼ75-736(200712)pp1358-136518ĔÝ

水素ステーション

90MPa Ɛ圧力差で充填Ƒ 70MPa

Hydrogen Station

水素ガス製造設備
Hydrogen GeneratorĔÝ[ýą

圧縮機

ディスペンサー
燃料電池車
蓄ガス器 Dispenser
Fuel Cell Vehicle

Accumulator

Compressor

配管／バルブ

緊急離脱カップリング

Piping System/Valves

Breakaway Device

高圧水素ホース

ノズル／レセプタクル

Flexible Hydrogen HoseNozzle/Receptacle

水素エネルギーシステムではゴム・樹脂製水素シールが使用される．
Rubber or polymeric materials are used as hydrogen gas seals in hydrogen energy system.
20¨k[ûĢ>wƖƖƖƖƖƖƖƖƖƖƖƖƖƖƖƖƖƖƖ¹ĀŠ+Y¤äñ
対策（Oリング用ゴム材料の対策）
・水素溶解量の低いゴム配合の開発
・硬度が高く，破壊強度が大きい
ゴム配合の開発
・充填材のカーボンブラックは補強効果が高いが水素吸着によりゴムの水素溶解量が増大する．補強効果が高く，水素吸着が小さい充填材を探索

0.5mm

EPDM(Hs70)：H235MPa100℃15hrs.

×¯ĝĉAäñǷǍǪ¤ǘǸǔǤǸǑ

1400

ブリスタ発生1200

NBR–CB50ń

1000
800

EPDM–CB25ń

400

EPDM–WC95ńEPDM
NBR–SC60ń
($ƫƿ0Ưƥ)NBR
EPDM–SC60ń($ƫƿ0Ưƥ) ブリスタ発生せず

200

水素による膨潤のた （Oリング用ゴム材料の対策）
め，ゴム材料の常態 ・水素溶解量の低いゴム配合の開発
値で設計されたOリ ・膨潤による体積増加率の低いゴム
ング溝の断面積を越配合の開発
える体積増加により ・水素溶解量が低いゴム材料の探索
はみ出し破壊に至る．
（Oリング溝設計の対策）
1 mm
10 mm
1 mm
・使用環境（温度，水素圧力など）におけるゴム材料の体積増加を前提とEPDM(Hs70)：H235MPa100℃15hrs.
した充填率設計
・使用環境（温度，水素圧力など）に水素による膨潤のたおけるゴム材料のはみ出し破壊，め，Oリングの円周座屈破壊の限界値を把握
方向に体積膨張が発生し，座屈発生に至
る．

0

0

2

4

6

8

¤ĨħŉǘǸǔǤǸǑĒ¹Ā¤ŋÞǷŃ^
8[+¨»

c)

c)
c)

1H
14H

g) g)

23H
35H

10 mm

8

6

5

e)

f)

4

3

2

1

0

Chemical shift ( in ppm)

8[ǏǡǙǹǺ

¹Ā³F_³ĩ#ĥ¨ǷbCĩ»ĄŁŌǹìǺŠL¹ĀǦǸǑ

d
Unfil
le

Volume Change after H2 exposure (%)Design of
Rubber composition
for high pressure H2

Exposure H2 pressure
sureMPa
90MPa

100

0MP
Pa
70MPa

Sulfur vulcanized NBR
ƖƖ:unfilled
ƖƖ:filled with silica 30phr
ƖƖ:filled with silica 60phr
ƖƖ:filled with carbon black 25phr
ƖƖ:filled with carbon black 50phr

Pa
50MPa

50

30MPa
10MPa

0
0

1000

2000

3000

4000

Hydrogen Content after H2 exposure (mass.ppm)
phr: weight parts per hundred weight parts of rubber
23_³ĩȅ
ţ(ıŤ¹ĀǄǜǲǉǸ
ĠDäñ
ǓǶǔǸ
ƭƱľ

5-Ə

0-Ə

.--Ə

.-
.

.-

.--

.---

.----

ǱǶǋåUưęƽ3¿LG

Relationship between H2 content and volume

150¹ĀǏǸǲØǱǶǋǱǶǋƱ3¿LĪŞ.--

According to the results of model compounds,
volume change ratio is proportional to its H2 content.
Carbon black can reduce the volume change of thecompounds nevertheless their H2 contents are high.

200

d1

_³ĩ

NEDO技術開発機構の水素先端科学基礎研究事業（平成18年度平成24年度）

250

AG=H  L

³FĨħŉƖƖ:ȅ_Á ƖƖƖ9ȅħ÷ 

a)

d) h)

7

L

ǆǸǧǶǢǰǕǊ$S .- #0-ƏǼ/1Ōb)

55H
UnexpoCrudeNBREPDM(Hs70)：H270MPa100℃3hrs.

¹ĀŇĩ

åU2[Ǭǘǲ¹Ā³FĪǷĩ

¹ĀÎ}ĩ»)ªç¸)š*
ǍǪưÄĥƥƨȁïƱ¹ĀJ

H

.$ǱǶǋĊyǼ$ǱǶǋÃŠƤǼ $ǱǶǋÃj
$ǱǶǋŖðǼ$ǱǶǋÃŖð

10ǢǱǑǔÞÖŏÛ*L, żF, MPa

座屈破壊

AOR

NBR–CB25ń

600

はみ出し破壊hW[ǷNOKǷ£A8[i¯ǆǸǧǶǢǰǕǊ$S 42o¤Ø>ĔùIǱǶǋƪƳƥÒȇ.ǸǾ.ǷǷǷ.-/-8
Ã$SÒȇǾǷǷǷ3-5-8

ǢǱǑǔÞÖ2[Ǭǘǲ

EPDM–CB50ń¹ĀǇǑL2) *

拡大
1 mm

原因
高圧水素曝露時にゴム材料中に溶解した水素が減圧に伴い気化することにより気泡発生からき裂進展に至る．

10MPaưƞƣƽ¹Ā&Ň(ppm)

破壊モード

ブリスタ破壊ŠL¹ĀǇǑǏǸǲØǍǪǷ¹Ā³FØ@ï²ĕ¤Ʋ¹Ā³FƾƝƽǈǸǨǗǱǀǲǍǪǷ²ĕ¤ƱŠL¹ĀưƺƽÍ}ƴƱxŗƱýßƯǘǸǔǼĩ+¨»ƾŢ!ƥǼ×¯ÛŢŢưƞƣƽ¹Ā³FǼĒ¹Ā¤ŋÞƱOèßãĢǼ»ƭƥƫ½Ø¤ŋÞǡǃǸǒƟƻ_³ŋÞƵƬ×¯ÛƭjmƢľƥĒ¹Ā¤Ǽ¹Ā³FŋÞƾĿ¹ĀŇǹ %ǺĖÂėipn>

高圧水素シールに用いたOリングの破壊状況を調査・解析し，Oリングの破壊はブリスタ破壊，はみ出し破壊，
座屈破壊の3種類の破壊モードに分類することが出来た．それぞれの破壊モードの原因を追求し対策を検討した．

vf}o>[ýą22¹ĀǙǰǂǧǴǐǸŠL¹ĀǂǶǡǰưƞƣƽǙǰǂǧǴǐǸġĀ


Solid surfaces
contaminant
adsorbed layeroxide layer+631

deformed layer
metal substrate

ǠǑǙǶǱǶǋǾǰǂǚǸ

7ßǷŕßǏǸǲØ
Š+Y¤Ʊ ł8“God created the solids, the devil their surfaces”.
Wolfgang E. Pauli

7ßǏǸǲƗŕßǏǸǲ

ĸ=ķƠƼĦưƞƣƽ¹ĀĴHƱ#Ŏ¶

x`ohwQªßN
m*js*gùĦ/%?,9>

ǝǲǢƯƮƗĦ7ńDǷēƱǙǰǂǧ¤Ʊł8³ċQ¶¬º(ÁęºPDD\Znz^u·ğQ½Ô
26

Tribology in hydrogen gas

Proper operation and lives of hydrogen systems relies greatly on
friction and wear of components such as valves, bearings, dynamic
seals (packing) and ring/liners.

Sliding tests
in highly controlled gas environmentFriction and wear of materials are not their intrinsic
properties but depend on surrounding gas
O2
H2O

H2

0.8

1.0E-070.7
0.6

1.0E-08

0.5
0.4
0.3

1.0E-09wear

COF

Solid

Solid



0.1

1.0E-100.1

Loss of boundary film
Surface degradation

Tribo-design for hydrogenŢ1

0.2

Coefficient of frictionSurfacelayersH2

SolidSpecific wear
, mm^2/N

Solid

H
H22O
O
O2
O2

1
0.9

HydrogenAir
Freshsurface

1.0E-06

0100

10Water concentration,
 ppm, ppm

Variation of specific wear rate of 316L with water concentrationin hydrogen: pin-on-disk tests, 10N, 0.063 m/s, 126 m

Trace oxygen and water
Generation of hydrogen(Fukuda et al., 2010)
27



!*   !.-,++ !
!!

Friction and wear of pure PTFE slid
against AISI316L in various gas; 50 N
(1.8 MPa), 100 mm/s, 4000 m, 323 K   ( !* ' &"'29

"








-%2
!!
"


(Sawae et al., 2010)"




 



$2 

水素物性Ƿ¹ĀƱÍ} ǘǸǔƲ¹ĀǄǜǲǉǸĝƾƝƽOà~QǷÛ-ƭƯƽŠÀŠL¹ĀÍ}ǘǸǔǤǸǑƱýßƯ!ƾ_Ƿ¹ĀƱÍ} ƲǼ¹Āōľ³FƱĨħƱOà~QǷŠüoƟƪŠř}Ʊ³FĨħưƲǼŠüoƱÍ}Ơ{ġ>´ǽǷǄǶǐǛǀưƗ³FĨħư{ġƯÍ} ưƪƜƫƗØùIƸüoƾ+ƟƼƸƦƜwƬƱƭĹư&ƬơƽÕT!Ơ{ġǽƎƖƑƖ¹ĀÍ}ǘǸǔǤǸǑǹŮƈƈŢƆƉŢũŢŰűǺƖƖƖƖƖƖƑƖŹžŦŲƌƃƄƈÌ¹ĀÍ}ǰǂǢǰǱÂė[ěÊ·[ýą

HYDROGENIUS
1""5'

6(.9&
(EOS)

PVTC

#%
 

"!/4 

EA

B
-7;)
>
> 

<',
4$8

"!/4
":/4

2?%

  ,

D3

ŔÈ

EA

0=5'   ,All in 1 CDFMS-EXCEL

4*+8

ěLF

LČ³

¹ĀƱÍ}

EOS@$Ȇ¹ĀÍ}ǘǸǔǤǸǑƱĲÑȈ
\'Ƭ(·Ư¹Ā$S¹ĀǑǗǸǏǯǶ/zł,ĨħưƺƽŠ6Ò8ǷǌǑǙ¿ǱǑǊƱł, Áǹ¹ĀÆ¼õǺ

ƲLČǷ$SǣǴǓǑƱħ÷ư>´

32

ÉğÙº

ŠL¹ĀÍ}Á^»ƭğĎ
ƱŋÞ



¹ĀÍ}ǘǸǔħÁ
ƭÔsƱŋÞ^`ðsPVTğĎ
(100MPa, 500C)

100( - virial EOS) / virial EOS

220 - 350 K

āøsû}Á^ğĎ(100MPa, 250C)

0.4
0.2
0
-0.2
-0.4
1

300 K
250 K

5

10

50

100

350 - 400 K

0.4
0.2
0
-0.2
-0.4
1

353.15 K
393.15 K

5

10

50

100

400 - 500 K

0.4
0.2
0
-0.2
-0.4
1

473.15 K

433.15 K

5

10

50

100

P , MPaPVTǘǸǔƭÏîsƱŋÞ)'SMYVU   MÞY[K¼æD $ C_W[" u>s[Ĝ<ze ëïĄá[£<" '$4$$.'6+2+$,504/$ C
D $ C_W[į·Ü¿[Ĝ;Oa]ÇĜò§á[£<($352(-(.4$.'02('+&4+/.
(15$4+/.)/26+3&/3+48504/$$.' C
D $ C_W[ěĈíè[Ĝ;Oa]ÇĜò§á[£<($352(-(.4$.'02('+&4+/.
(15$4+/.)/24*(2-$,&/.'5&4+6+48
504/ $$.' CDÂėÊ·u>s|>p,,+. 
7&(,ĥ[£<(6(,/0-(.4/) 4*(2-/0*83+&$,02/0(248'$4$%$3(kȀȄlƟƻŋ"ƥȀǿGáŢôȀǿGƖ2016.2.3~4
ŅǈǭǶǞǑ
®¢ĮPƖƖƖƖƖ

^\]ba`êgǞǟǱǅǶƱńƭƥƫŴƁűŽŻųŲźŵƀĂƭƧƱ©Ʊ;ţŪŨũŭŧūŧŪ~ŬƗ¦ȓȔȍȏǎǂǙǺǝǸǜǕǙsPVTğĎ ÊdÒÁ^ğĎ(100MPa, 200C) (100MPa, 500C)

C

16
14

95
3)
(1
ls
he
ic

18

OP
PR
REF
(1972)
HanleyMcCartyty ((1972)
72))

20

Ð1ßƯğĎŋÞƭŠüoÁ^

40



60
[MPa]

80

ÊdÒÔs

100

50
100
150
Pressure, P MPa

200¹ĀǂǶǡǰOè
ĨħǖǸǲƭƥƫ
×¯ÛưĲÑ

/ǷĨ!ǷŘėǷ©Ʊ$_ƴƱşơƱV"&1!Z ; C 8 ? > : 9 = < B @ [ )LQWNYG,4%Z _ c A ? D 7 [ ,Ç¼5:<7½¡-'G) (Z)'SMYVU[(%)ĹµĶį,ĸãä%®²´Ĥ÷Ě-,Z* +E-+E5[# .Z)OJXE)RIJKI[(£Å);,Ý -,645  ¾ñ-%%%ƖƖƖƖƖƖƖƖƖƖƖƖƖƖƖƖƖƖƖƖƖƖƖƖ$ )LQWNY /FG0û}Ôs33

 

32VTPHY6Ƿ &      &ȐȎȒŢȓȔȑȔȍȒŢǹ/-..%.-%.ǺǷ IEA%óËœº_9^ǹAFCIAǺ/ȐȎȒŢȓȔȑȔȍȒǹ2012.10.31ǺǷȋȌȊȉǷǗǊǛǆǲǖǀǸǹ/-.0%..%/5ǺMity,  µPas
-100°





)2
20
0
HYDRO
HYDR
ROGEN Experimental
ROG
T:296
96.15K
15K
5K
K
NabizadNabzadeadeh (1999)
T:298.15K
K
Michelss ((195
953
953)
53)
Gracki (1969)
69))
Barua (1964)
Golubev (1953)
Kuss(1952)
T:299.15K
Rudenko (1968)
Present correlationÛƱ¹ĀōđƱƙņġƯ ¾ƱRƚưÞe34