2012.11
2012.12
20102007
2009.9
(2010.4
2015
H2
4
( from JHFC website)
3
( from Honda website)
6 5
7
or LPGor LPG
8
10 9
国内外から研究者を結集し、水素と材料に関わる先端的な基礎研究を推進。
国内外か 研究者を結集国内外か 研究者を結集
12
HYDROGENIUS
H2
H2
H2
H2 diffusion, Combustion control.
Sensing, Incident analysis
and Education
11
10 20 30 40 50
200
400
600
800
1000
0
Strain, [%]
Stress, [MPa]
SCM435(KC21)115MPa H2 at RT
B = 820MPa = 47%
A
B
C
Proposal of Design Method for Cr-Mo steels: Design by Rule
Slow strain rate tensile (SSRT) properties of Cr-Mo steel JIS-SCM435
S-N data of Cr-Mo steel JIS-SCM435
5 10 15
200
400
600
800
1000
0Stroke displacement (mm)
Nom
inal
str
ess,
(
MP
a)
N2
H2
JIS-SCM435 at RT115 MPa gasCHS = 0.002 mm/s
BN = 843 MPa
BH = 820 MPa
N = 73 %
H = 47 %RTS = 0.97RRA = 0.64
5 10 15
200
400
600
800
1000
0Stroke displacement (mm)
No
min
al s
tres
s,
(M
Pa)
JIS-SCM435 at 233 K115 MPa gasCHS = 0.002 mm/s
BN = 898 MPa
BH = 886 MPa
N = 70 %
H = 36 %RTS = 0.99RRA = 0.51
N2
H2
5 10 15
200
400
600
800
1000
0Stroke displacement (mm)
No
min
al s
tres
s,
(M
Pa)
N2
H2JIS-SCM435 at 393 K115 MPa gasCHS = 0.002 mm/s
BN = 842 MPa
BH = 835 MPa
N = 72 %
H = 47 %RTS = 0.99RRA = 0.65
(a) 233 K (b) RT (c) 393 K
250
300
350
400
450
500
550
600
102
103
104
105
106
107
108
Stress am
plitude,
a (M
Pa)
Number of cycles to failure, Nf (cycles)
:In air, f = 1 Hz
:In 115MPa H2 , f = 1 Hz
In 115MPa H2, f = 0.1 Hz
In 115MPa H2, f = 0.01 Hz
JIS-SCM 435 at RT
R = 1
HV 256Proposed criteria for safety factor-based infinite-life design (Fatigue limit design)
There is no degradation in tensile strength during SSRT testing. There is no degradation in fatigue limit.
S = B
allowable = 3.5 ~ 4 Safety factor:
B: Tensile strength, allowable: Allowable stress
HISCG
HYDROGENIUS
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 Steel
May, 2011
Research Center for Hydrogen Industrial Use and Storage (HYDROGENIUS),
National Institute of Advanced Industrial Science and Technology (AIST)
Kyushu University
HDFF-A34-1
Copying is prohibited
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 Steel
May, 2011
Research Center for Hydrogen Industrial Use and Storage (HYDROGENIUS),
National Institute of Advanced Industrial Science and Technology (AIST)
Kyushu University
HDFF-A34-1
Copying is prohibited
水素構造材料
1642 , 1221 2015.10.27
18
10 10020 30 40 50 60 70809010-10
10-9
10-8
10-7
10-6
10-5
Crack growth rate
da
/dN(m
/cycle)
Stress intensity factor range K(MPa m)
H 0.47ppm
H 0.3ppm
H 0.47ppm
H 0.3ppm
H 0.49ppmH 0.49ppm
(f=0.2Hz) 0.58 0.49ppm
(f=2Hz) 0.58 0.49ppm
Hydrogen-charged
Uncharged0.01ppm
(f=20Hz) 0.49 0.24ppm
(f=20Hz) 0.53 0.27ppm
(f=0.2Hz) 0.58 0.49ppm
(f=2Hz) 0.58 0.49ppm
Hydrogen-charged
Uncharged0.01ppm
(f=20Hz) 0.49 0.24ppm
(f=20Hz) 0.53 0.27ppm
H 0.49ppmH 0.49ppm
H
da
H
HH
H
HH
H
H
H
H
H
a
H
dddadadaaaa
HHH
HHHHHHHHHHHH
HHHHHH
HHHHHH
HHHHH
HHHHHHHHa
HHH
ddaa
HHHHH
H
da
H
HH
H
HH
H
H
H
H
H
a
Schematic image of the mechanism of effect of hydrogen and test frequency on fatigue crack growth.
Uncharged specimen
Hydrogen-charged (0.56ppm) (0.56ppm)
(0.54ppm)
mMPa17K
JIS-SCM435
SCM435R = -1
A 75-736(200712)pp1358-1365
蓄ガス器 Accumulator
ディスペンサー Dispenser
圧縮機 Compressor
燃料電池車 Fuel Cell Vehicle
90MPa 70MPa 圧力差で充填
水素ガス製造設備 Hydrogen Generator
水素ステーション Hydrogen Station
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.
配管/バルブ Piping System/Valves
緊急離脱カップリング Breakaway Device
ノズル/レセプタクル Nozzle/Receptacle
高圧水素ホース Flexible Hydrogen Hose
20
22
8 7 6 5 4 3 2 1 0Chemical shift ( in ppm)
Unexpo
35H
23H
14H1H
CrudeNBR
g)
b)
f)
a)
e)
g)
d) h)
c)c)
c)
55H
NOK
, F, MPa
10M
Pa
(ppm
)
ブリスタ発生せず
EPDM–CB25
EPDM–CB50
NBR–CB50
EPDM–SC60
NBR–SC60
ブリスタ発生
NBR–CB25
EPDM–WC95 EPDM ( )
NBR ( )
0 2 4 6 8 100
200
400
600
800
1000
1200
1400
H d1AOR
AG=H LL
破壊モード 原因 対策 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.
(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
水素による膨潤のため,ゴム材料の常態値で設計されたOリング溝の断面積を越える体積増加によりはみ出し破壊に至る.
(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 ・膨潤による体積増加率の低いゴム 配合の開発 ・水素溶解量が低いゴム材料の探索 (Oリング溝設計の対策) ・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 した充填率設計 ・使用環境(温度,水素圧力など)に おけるゴム材料のはみ出し破壊, 座屈破壊の限界値を把握
水素による膨潤のため,Oリングの円周方向に体積膨張が発生し,座屈発生に至る.
EPDM(Hs70):H2 35MPa 100℃ 15hrs.
EPDM(Hs70):H2 70MPa 100℃ 3hrs.
はみ出し破壊
座屈破壊
EPDM(Hs70):H2 35MPa 100℃ 15hrs. 1 mm
ブリスタ破壊
0.5mm
拡大
10 mm
1 mm 1 mm 10 mm
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.
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)
23
Relationship between H2 content and volume
0
50
100
150
200
250
0 1000 2000 3000 4000
Exposure H2 pressure 90MPa
70MPa
50MPa
30MPa
10MPa
Un
filled
Hydrogen Content after H2 exposure (mass.ppm)
Vo
lum
e C
ha
ng
e a
fte
r H
2 e
xp
osu
re (
%)
0MP
Pa
sure MPa
Pa
Unn
Pa Sulfur vulcanized NBR :unfilled
:filled with silica 30phr :filled with silica 60phr
:filled with carbon black 25phr :filled with carbon black 50phr
phr: weight parts per hundred weight parts of rubber
According to the results of model compounds, volume change ratio is proportional to its H2 content. Carbon black can reduce the volume change of the compounds nevertheless their H2 contents are high.
Design of Rubber composition for high pressure H2
Solid surfaces
“God created the solids, the devil their surfaces”.
Wolfgang E. Pauli
contaminant adsorbed layer oxide layer deformed layer metal substrate
26
Sliding tests in highly controlled gas environment
(Fukuda et al., 2010)
Variation of specific wear rate of 316L with water concentration in hydrogen: pin-on-disk tests, 10N, 0.063 m/s, 126 m
1.0E-10
1.0E-09
1.0E-08
1.0E-07
1.0E-06
0.1 1 10 100
, ppm
, m
m^2
/N
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
COF
wear
Co
eff
icie
nt
of
fric
tio
n
Sp
ecific
we
ar
Water concentration, ppm
27
Air
Surfacelayers Solid
SolidO2
H2O
Hydrogen
Solid
Solid
H2
Air
Freshsurface
Solid
Solid O2
H2O
Solid
SolidO2
H2O
Hydrogen
H2
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.
Tribo-design for hydrogen
Friction and wear of materials are not their intrinsic properties but depend on surrounding gas
Loss of boundary film Surface degradation
Trace oxygen and water Generation of hydrogen
Tribology in hydrogen gas
Friction and wear of pure PTFE slid against AISI316L in various gas; 50 N (1.8 MPa), 100 mm/s, 4000 m, 323 K
(Sawae et al., 2010) 29
EOSHYDROGENIUS
(EOS)
All in 1 CD MS-EXCEL
PVT
32
水素物性
IEA AFCIA / 2012.10.31
2016.2.3~4
~
34
PVT ( 100MPa, 200 C)
PVT ( 100MPa, 500 C)
( 100MPa, 500 C)
20 40 60 80 100 [MPa]
-100°C
PVT
5050 100100100 150150 200200
14
16
18
200
Pressure, P MPaP
ity,
µPas
HYHYDRDROROGEN ExperimentalROGT:29696.15K15KK5K
NabNabizadzadeadeh (1999)adehT:298.15KK
Michels (s (19595353)953) Gracki (1969)69)) Barua (1964) Golubev (1953) Kuss(1952)
T:299.15K Rudenko (1968) Present correlation
REFPRO
PP
McCartyty ( 72))(1972)(1972)
Hanley (1972)
Michels (1953)
953)
( 100MPa, 250 C)
1 5 10 50 100-0.4-0.2
00.20.4
400 - 500 K
433.15 K
473.15 K
P , MPa
1 5 10 50 100-0.4-0.2
00.20.4
220 - 350 K
300 K250 K
1 5 10 50 100-0.4-0.2
00.20.4
350 - 400 K
393.15 K
353.15 K
100( -
virial EOS) /
virial EOS
33