Hydrogen Effects in Materials 1

Hydrogen Effects in Materials
Brian Somerday
Sandia National Laboratories
Livermore, CA, USA
3rd European Summer School on Hydrogen Safety
University of Ulster, Belfast, UK
July 28, 2008
Outline
Introduction
H2 interactions with metal components
Safety concern: hydrogen embrittlement (HE)
Methods to assess material performance

Variables affecting HE
Material
Environmental
Mechanical
Outline
Considerations for materials selection
Component design
Design approach
Material property measurement
Example design analysis
Recommendations
H2 containment components
On-board fuel tanks
Manifold components
H2 containment components
Transport and
stationary tanks
Pipelines
H2 interactions with metal components

H2 gas
1) H2 gas
2) H2 adsorption
3) H2 dissociation to H
4) H absorption
5) H diffusion
Two principal safety concerns

H2 permeation through wall of structure
Effectively results in H2 leak
Hydrogen embrittlement (HE) of structural

metal
Crack propagation through wall of structure
HE mechanisms involve H in solution
Temperatures < 200 oC
Other H-related degradation mechanisms
operate >200 oC
HE enables crack propagation

component
surface
H2
H2
stress
H2
H2 H2
H2
defect
H2H2 H2
H2
H2 H2
H2
H2H2 H2
H H
HH
H absorbs
into surface
stress
H2
H2 H2
H2
H concentrates
at defect
H2H2 H2
H
H
HHH
H HH
H
H2
H2 H2
H2
H causes embrittlement
and crack propagation
H H
H H
H2 H H H2
H2
2 2
H
H H H
Hydrogen embrittlement mechanisms

Hydrides
D. Westlake,
H. Birnbaum
Hydrogen-Enhanced
Localized Plasticity
(H.E.L.P.)
H
H
hydrides
A. Troiano, R. Oriani
particle
1 > 2
2
void
HH H H HH H
HH H HH
H H H
C. Beachem, H. Birnbaum,
I. Robertson, P. Sofronis
Hydrogen-Enhanced
Decohesion
H
H H H
H HH
H
H
H
HH
H
HE due to hydrogen-enhanced decohesion
Barthlmy, 1st ESSHS, 2006
Intergranular HE can be devastating
Material performance: test methods

dl/dt > 0
strength of materials:
u, y, f, RA
S-N
fracture mechanics:
KIH, KTH
da/dN vs K
dl/dt > 0
H2
HH
H
H
H
H
H H2
H2
H2 H H
2
H2
d/dt 0
d/dt 0
H H
H
H
H
H
H H H H
H
H H
H
H
H H
H
H H H
H
H2
H2 H
2
H2 H2 H2
H2
H2
H
HH

H2 gas pressure (MPa)
50
75
100
Stress intensity factor, K (ksi-in1/2)
300
150
X100 ferritic steel
KJIc
300
WOL specimens
C-L orientation
o
25 C
KTH
250
125
200
250
200
150
150
100
100
50
50
0
0
10
15
20
1/2
25
Stress intensity factor, K (MPa-m )
d/dt 0
H2
H2 H
2
H2 H2 H2
H2
25
H2 gas pressure (kpsi)
HE manifested by reduced fracture

toughness
H2
H
HH

10-2
X42 ferritic steel
Fatigue crack growth rate, da/dN (in/cycle)
frequency = 1 Hz
1000 psi H2, R=0.1
1000 psi N2, R=0.1
10-3
10-4
d/dt > 0
H2
H2 H
2
H2 H2 H2
H2
10-5
H2
H
HH
10-6
10-7
10-8
1
10
100
Stress intensity factor range, K (ksiin )

1/2
Cialone and Holbrook,

Met Trans A, 1985
HE manifested by increased fatigue

crack growth rate
Material performance: service experience
Fuel tanks
Aluminum or polymer
lined composite
H2 pressure < 70 MPa
Manifold components
Austenitic stainless
steel
Low material strength
No welds
Material performance: service experience
Storage tanks
Low-alloy ferritic
steel
Limited material
strength
No welds
Pipelines
C-Mn ferritic steel
Low material strength
No pressure cycling
H2 compatibility guidelines for metals

Materials favored for H2 service
austenitic stainless steels, aluminum alloys,
low-alloy ferritic steels, C-Mn ferritic steels,

copper alloys
Materials commonly avoided in H2 service

high-alloy ferritic steels, nickel alloys,
titanium alloys
HE susceptibility can be sensitive

to many variables
Variables affecting HE
All metals can be susceptible to HE
depending on
Material variables
Environmental variables
Mechanical variables
Trends demonstrated from laboratory

test methods
Emphasize fracture mechanics data
Emphasize ferritic steels, austenitic
stainless steels, aluminum
Material variable: strength (hardness)

Yield strength (ksi)
90
120
120
135
Pressure Vessel Steels
150
4130 steel
4145 steel
4147 steel
H2 gas pressure = 41 MPa
100
80
80
60
60
40
40
d/dt 0
KTH (ksi-in1/2)
KTH (MPa-m1/2)
100
105
H2
H2 H
2
H2 H2 H2
H2
H2
H
HH
20
20
0
600
700
800
900
Yield strength (MPa)
1000
0
1100
Loginow and Phelps,

Corrosion, 1975
Strength promotes HE in all materials

Technologically important trend
Material variable: alloy composition

100
Mn=0.02
Si=0.01
P=0.014
S=0.003
KTH (MPa-m1/2)
80
B7
Mn=0.007
Si=0.002
P=0.003
S=0.003
Ni-Cr-Mo ferritic steel

YS = 1450 MPa
110 kPa H2 gas
296 K
Mn=0.09
Si=0.01
P=0.012
S=0.005
Mn=0.02
Si=0.27
P=0.0036
S=0.005
60
40
d/dt 0
B6
Mn=0.72
Si=0.32
P=0.003
S=0.005
B2
Mn=0.68
Si=0.08
P=0.009
S=0.016
H2
H2 H
2
H2 H2 H2
H2
H2
H
HH
20
Mn=0.23
Si=0.01
P=0.009
S=0.005
0
0.0
0.2
0.4
Mn=0.72
Si=0.01
P=0.008
S=0.005
Mn=0.75
Si=0.20
P=0.006
S=0.004
0.6
[Mn + 0.5Si + S + P] (wt%)
0.8
1.0
Bandyopadhyay et al.,
Met Trans A, 1983
Alloy composition affects intergranular

HE in ferritic steels
Material variable: alloy composition

non-charged
316 stainless steels

dl/dt > 0
HH
H
H
H
H
H-precharged
San Marchi et al.,

IJHE, 2008
Nickel affects deformation and/or

martensite formation in stainless steels
Material variable: welding

Weld tested after H2 exposure
Stainless steel weld
base metal
weld
Weld microstructure can promote HE

Hardness, residual stress also affect HE
Environmental variable: H2 pressure

5
10
15
160
140
4130 steel (YS=634 MPa)

150
KTH (MPa-m1/2)
20
d/dt 0
120
120
100
90
80
60
60
KTH (ksi-in1/2)
0
180
H2 gas pressure (ksi)
H2
H2 H
2
H2 H2 H2
H2
H2
H
HH
40
30
20
0
0
30
60
90
120
150
HE more severe at higher H2 pressure

for all materials
Loginow and Phelps,

Corrosion, 1975
Environmental variable: temperature

dl/dt > 0
HH
H
H
H
H
Caskey, Hydrogen
Compatibility Handbook
for Stainless Steels,
1983
HE can be maximum at ambient temperature
Environmental variable: H2 purity

4.0
(da/dN)H +additive / (da/dN)H
2.25 Cr-1 Mo ferritic steel

3.5
3.0
2.5
2.0
YS = 430 MPa
1.1 MPa H2 gas
K = 24 MPam
frequency = 5 Hz
R = 0.1
293 K
d/dt > 0
H2
H2 H
2
H2 H2 H2
H2
1.5
H2
H
HH
1.0
0.5
0.0
O2
CO
SO2
0.10% 0.99% 1.10%
H2O
0.03%
CH4
CO2 CH3SH H2S
0.98% 1.01% 1.04% 0.10%
Fukuyama et al.,
Pressure Vessel
Technology, 1992
Gas impurities can inhibit or intensify

HE in ferritic steels
Environmental variable: H2 purity
d/dt 0
H2
H2 H
2
H2 H2 H2
H2
H2
H
HH
Speidel, Hydrogen Embrittlement

and Stress Corrosion Cracking, 1984
Water vapor promotes HE in

aluminum alloys
Mechanical variable: loading rate

100
4340 ferritic steel
KIH (MPa-m1/2)
80
YS = 1235 MPa
550 kPa H2 gas
297 K
d/dt 0
60
H2
H2 H
2
H2 H2 H2
H2
40
H2
H
HH
20
0
0.1
10
100
1/2
Clark and Landes,

ASTM STP 610, 1976
Loading rate, dK/dt (MPa-m /min)
HE more severe at lower loading rates

in all materials
Mechanical variable: load cycle frequency

100
SA 105 ferritic steel

103 MPa H2 gas
load ratio = 0.1
0.001 Hz
da/dN (m/cycle)
0.01 Hz
0.1 Hz
10
d/dt > 0
H2
H2 H
2
H2 H2 H2
H2
1.0 Hz
H2
H
HH
1.0 Hz
35 MPa He gas
0.1
0
15
30
K (MPa-m )
1/2
45
60
Walter and Chandler, Effect

of Hydrogen on Behavior of
Materials, 1976
HE more severe at lower load cycle

frequency in all materials

1) HE data or service experience should
not be extrapolated
120
120
135
150
4130 steel
4145 steel
4147 steel
H2 gas pressure = 41 MPa
0
180

10
15
160
1/2
60
40
40
KTH (MPa-m1/2)
80
60
140

150
80
20
100
KTH (ksi-in )
1/2
KTH (MPa-m )
100
105
120
120
100
90
80
60
60
40
20
20
0
600
700
800
900
Yield strength (MPa)
1000
0
1100
30
20
0
0
30
60
90
H2 compatibility must be established for

specific conditions
120
150
KTH (ksi-in1/2)
Yield strength (ksi)

90

2) HE can be severe in alloys considered
compatible with H2
316 stainless steels
dl/dt > 0
HH
H
H
H
H
Intersections of variables important

3) Materials selection may balance H2
compatibility with other constraints
Material
Cost
Specific
strength
Temperature
HE resistance
range
austenitic SS
high
low to high
cryogenic to
high
high
C-Mn/lowalloy steels
low
low to high
ambient to
high
low to
intermediate
aluminum
intermediate
intermediate
to high
cryogenic to
low
high

4) Materials must be qualified for H2 service
based on
Material property measurements under
relevant conditions
Material variables
Environmental variables
Mechanical variables
Design approach for component
Design based on fracture mechanics

component
surface
H2
H2
stress ()
local
H2
H2 H2
H2
H2H2 H2
defect
stress ()
local = c
H2
H2 H2
H2
H2
H2 H H H2
2 2
Local stress drives crack extension
Design based on fracture mechanics
K
ij =
f ij ( )
2r
Local stress described by stressintensity factor, K
Crack extension governed by critical
K values
Component design: sustained-load cracking

p
p
N2
N2
N2 a
a
crack in H2
crack in N2
p
H2
H2
H2
a
time
H2 induces time-dependent crack

propagation under static loading
Component design: sustained-load cracking

K
KTH
measured in
laboratory
p
t
H2
H2
a
a
Ri
Ro
K = p * f(a/t,Ri,Ro)
time
Sustained-load cracking proceeds

when K > KTH
Component design: fatigue crack growth

p
p
N2
N2
N2 a
p
a
crack in H2
crack in N2
p
H2
H2
H2
a
Number of pressure cycles, N (time = N/f)
Crack growth under cyclic loading

accelerated by H2
Component design: fatigue crack growth

da/dN
measured in laboratory
N2 gas
p
t
H2
measured in laboratory
H2 gas
H2
Ri
Ro
da/dN = C[K]m
K
Fatigue crack growth rates (da/dN)

are a function of K
Component design analysis

Objective: calculate number of pressure cycles, Nc,
to grow crack to critical length, ac
critical crack depth for
sustained-load cracking
p
t
H2
H2
ac
Ro
cycles to
critical crack depth
Ri
t
Number of pressure cycles, N
Calculation requires material property

measurements: KTH and da/dN vs K
Nc
Measurement: fatigue crack growth
d/dt > 0
H2
H2 H
2
H2 H2 H2
H2
H2
H
HH
Measurement: fatigue crack growth

100
SA 105 ferritic steel
da/dN = C[K]m
103 MPa H2 gas

load ratio = 0.1
0.001 Hz
da/dN (m/cycle)
0.01 Hz
0.1 Hz
10
a = C[p * f(a/t,Ro,Ri)]m
1.0 Hz
a
1.0 Hz
35 MPa He gas
0.1
0
15
30
K (MPa-m1/2)
45
60
Measurement gives crack length vs

number of cycles in design analysis
Measurement: cracking threshold

Wedge Opening Load
(WOL) specimen
Loading bolt
Load cell
Load (P)
13 mm
Po Ko
PTH KTH
Time in H2
Measurement: cracking threshold

10
15
160
ac/t = g(KTH,p,Ro,Ri)
140

150
KTH (MPa-m1/2)
20
ac
120
120
100
90
80
60
60
1/2
180
KTH (ksi-in )
40
30
20
0
0
30
60
90
120
150
Measurement gives critical crack depth

(ac) in design analysis
Nc
Example design analysis for H2 pipeline

Parameters for H2 pipeline
(ASME, Hydrogen Standardization Interim Report, 2005)
X42 ferritic steel

Inner radius, Ri = 15 cm
Wall thickness, t, from 0.5 to 1.3 cm
ao
t
Ri
Ro
Maximum pressure, p = 10 MPa

Existing defect with depth ao
and length parallel to pipe axis

h
cycle 1
K1=f(ao,p,Ro,Ri,t)
a=(2.51x10-12)K16.56
a1=ao+a
p
p
10 MPa
cycle 2
K2=f(a1,p,Ro,Ri,t)
a=(2.51x10-12)K26.56
a2=a1+a
ao
t
Ri
Ro
1 MPa
ao
a1
Case 1: t=0.8 cm (h=65% SMYS) and ao/t=0.10

a2

10-2
0.8
frequency = 1 Hz
-12
6.56
da/dN=(2.51x10 )K
10-3
10
1000 psi H2, R=0.1

1000 psi N2, R=0.1
-4
10-5
10-6
10-7
-11
da/dN=(3.55x10 )K
3.83
crack depth / wall thickness, a/t
X42 ferritic steel
X42 Pipeline
pressure cycle = 1 - 10 MPa
inner diameter = 30 cm
calculated from KIc
0.7
0.6
0.5
0.4

calculated from KTH
nitrogen
t=1.3 cm
h=43% SMYS
hydrogen
t=1.3 cm
h=43% SMYS
0.3
0.2
0.1
0.0
10-8
1
10
100
Stress intensity factor range, K (ksiin1/2)
50000
100000
150000
200000
number of pressure cycles
Material/component performance can

be quantified with design analysis
250000

10-2
0.8
frequency = 1 Hz
da/dN=(2.51x10-12)K6.56
10-3
1000 psi H2, R=0.1
10-4
10-5
case 1 initial K
10-6
case 2 initial K
10-7
case 3 initial K
crack depth / wall thickness, a/t
X42 ferritic steel
X42 Pipeline
0.7
H2 gas
0.6
pressure cycle = 1 - 10 MPa

inner diameter = 30 cm
0.5
case 2
t=1.3 cm
h=43% SMYS
0.4
critical crack depths

calculated from KTH
case 3
t=1.3 cm
h=43% SMYS
0.3
case 1
t=0.8 cm
h=65% SMYS
0.2
0.1
0.0
10-8
1
10
100
Stress intensity factor range, K (ksiin1/2)
5000
10000 15000 20000 25000 30000 35000 40000 45000
number of pressure cycles
Performance depends on both material

properties and component design
Recommendations
1) Austenitic stainless steels, aluminum
alloys best candidates for H2 service
Based on service experience and testing
Do not extrapolate performance or test data
Define temperature, alloy composition for
austenitic stainless steels
Define water vapor content of gas for
aluminum alloys
Design analysis can quantify safety margins
Recommendations
2) Ferritic steels are susceptible to HE
under wide range of conditions
Service experience may be adequate but
design analysis required in many cases
Measure properties under specific conditions
Material: strength, alloy composition,
fabrication (e.g., welding)
Environment: H2 pressure, H2 composition,
temperature
Recommendations
3) Nickel alloys, titanium alloys are generally
not recommended for H2 service
Design analysis required
May require other measures such as H2
permeation barrier

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Hydrogen Effects in Materials

Methods to assess material performance

H2 interactions with metal components

Two principal safety concerns

Hydrogen embrittlement (HE) of structural

HE enables crack propagation

Hydrogen embrittlement mechanisms

HE due to hydrogen-enhanced decohesion

Barthlmy, 1st ESSHS, 2006

Intergranular HE can be devastating

Material performance: test methods

Material performance: test methods

Stress intensity factor, K (ksi-in1/2)

X100 ferritic steel

Stress intensity factor, K (MPa-m )

H2 gas pressure (kpsi)

HE manifested by reduced fracture

Material performance: test methods

X42 ferritic steel

Fatigue crack growth rate, da/dN (in/cycle)

Stress intensity factor range, K (ksiin )

Cialone and Holbrook,

HE manifested by increased fatigue

Material performance: service experience

Material performance: service experience

H2 compatibility guidelines for metals

low-alloy ferritic steels, C-Mn ferritic steels,

Materials commonly avoided in H2 service

HE susceptibility can be sensitive

Trends demonstrated from laboratory

Material variable: strength (hardness)

Pressure Vessel Steels

H2 gas pressure = 41 MPa

Yield strength (MPa)

Loginow and Phelps,

Strength promotes HE in all materials

Material variable: alloy composition

Ni-Cr-Mo ferritic steel

[Mn + 0.5Si + S + P] (wt%)

Alloy composition affects intergranular

Material variable: alloy composition

316 stainless steels

San Marchi et al.,

Nickel affects deformation and/or

Material variable: welding

Stainless steel weld

Weld microstructure can promote HE

Environmental variable: H2 pressure

Pressure Vessel Steels

4130 steel (YS=634 MPa)

H2 gas pressure (ksi)

H2 gas pressure (MPa)

HE more severe at higher H2 pressure

Loginow and Phelps,

Environmental variable: temperature

HE can be maximum at ambient temperature

Environmental variable: H2 purity

(da/dN)H +additive / (da/dN)H

2.25 Cr-1 Mo ferritic steel

Gas impurities can inhibit or intensify

Environmental variable: H2 purity

Speidel, Hydrogen Embrittlement

Water vapor promotes HE in

Mechanical variable: loading rate