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FIRST EUROPEAN SUMMER SCHOOL FIRST EUROPEAN SUMMER SCHOOL ON HYDROGEN SAFETY ON HYDROGEN SAFETY
BELFAST BELFAST –– AUGUST 15AUGUST 15--2424THTH, 2006 , 2006
Compatibility of Metallic Materials with Hydrogen
Hervé Barthélémy
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Compatibility of Metallic Materials with Hydrogen – Review of the present knowledge
1. GENERALITIES
2. REPORTED ACCIDENTS AND INCIDENTS ON HYDROGEN EQUIPMENT
3. TEST METHODS
4. PARAMETERS AFFECTING HYDROGEN EMBRITTLEMENT OF STEELS- Environment, Material and Design
3The world leader in industrial and medical gases
Compatibility of Metallic Materials with Hydrogen – Review of the present knowledge
5. HYDROGEN EMBRITTLEMENT OF OTHER MATERIALS
6. HYDROGEN ATTACK
7. CONCLUSION - RECOMMENDATION
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1.GENERALITIES
Internal hydrogen embrittlement
External hydrogen embrittlement
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1.GENERALITIES
1 - COMBINED STATE :
Hydrogen attack
2 - IN METALLIC SOLUTION :
Gaseous hydrogen embrittlement
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1.GENERALITIES
Important parameter : THE TEMPERATURE
T < 200°C Hydrogen embrittlement
T ≥ 200°C Hydrogen attack
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Reversible phenomenaTransport of H2 by the dislocations
CRITICAL CONCENTRATION
AND DECOHESION
ENERGY
1.GENERALITIES
H2 traps
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2.REPORTED ACCIDENTS AND INCIDENTS
FAILURE OF A HYDROGEN TRANSPORT
VESSEL IN 1980
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2.REPORTED ACCIDENTS AND INCIDENTS
FAILURE OF A HYDROGEN
TRANSPORT VESSEL IN 1983. HYDROGEN
CRACK INITIATED ON INTERNAL
CORROSION PITS
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HYDROGEN CYLINDER BURSTS INTERGRANULAR CRACK
2.REPORTED ACCIDENTS AND INCIDENTS
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2.REPORTED ACCIDENTS AND INCIDENTS
VIOLENT RUPTURE OF A HYDROGEN STORAGE VESSEL
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2.REPORTED ACCIDENTS AND INCIDENTS
H2 VESSEL. HYDROGEN CRACK ON STAINLESS STEEL PIPING
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3.TEST METHODS
Static (delayed rupture test)
Constant strain rate
Fatigue
Dynamic
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3.TEST METHODS
Fracture mechanic (CT, WOL, …)
Tensile test
Disk test
Other mechanical test (semi-finished products)
Test methods to evaluate hydrogenpermeation and trapping
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3.TEST METHODS
Fracture mechanics test with WOL type specimen
1. Vessel head2. Specimen3. O-rings4. Vessel bottom5. Gas inlet – Gas outlet6. Torque shaft7. Load cell8. Instrumentation feed through9. Crack opening displacement
gauge10. Knife11. Axis12. Load application
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3.TEST METHODS
Specimens for compact tension test
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3.TEST METHODS
Influence of hydrogen pressure (300, 150, 100 and 50 bar) - Crack growth rate versus K curves
10-4
10-5
10-6
10-7
10-820 25 30
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3.TEST METHODS
X
152 bar
41 bar
1 bar
165 bar
H2
N2
K, MPa Vm
Influence of hydrogen pressure
by British Steel
10-2
10-3
10-4
10-5
10 20 30 40 60 80 100
dadN
mm/cycle
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3.TEST METHODS
Tensile specimen for hydrogen tests (hollow tensile specimen) (can also be performed with specimens cathodically charged or with tensile spencimens in
a high pressure cell)
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3.TEST METHODS
I = (% RAN - % RAH) / % RAN
I = Embrittlement index
RAN = Reduction of area without H2
RAH = Reduction of area with H2
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3.TEST METHODS
Cell for delayed rupture test with Pseudo Elliptic Specimen
Pseudo EllipticSpecimen
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3.TEST METHODS
Tubular specimen for hydrogen assisted fatigue tests
Inner notches with elongationmeasurement
strip
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3.TEST METHODS
Disk testing method – Rupture cell for embedded disk-specimen
1. Upper flange2. Bolt Hole3. High-strength steel ring4. Disk5. O-ring seal6. Lower flange7. Gas inlet
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3.TEST METHODS
Example of a disk rupture test curve
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3.TEST METHODS
Hydrogen embrittlement indexes (I) of reference materials versus maximum wall stresses (σm) of
the corresponding pressure vessels
σm (MPa)
I
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3.TEST METHODS
Fatigue test - Principle
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3.TEST METHODS
Fatigue test - Pressure cycle
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3.TEST METHODS
Fatigue tests, versus ∆ P curvesnN2nH2
0
1
2
3
4
5
6
4 5 6 7 8 9 10 11 12 13
Delta P (MPa)
Cr-Mo STEELPure H2H2 + 300 ppm O2F 0.07 Hertz
nN2nH2
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3.TEST METHODS
Fatigue test Principle to detect fatigue crack initiation
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TESTS CHARACTERISTICSType of hydrogen embrittlement and transport modeType of hydrogen embrittlement and transport mode
LOCATION OF HYDROGENTESTS TRANSPORT MODE
Disk rupture test External Dislocations
F % test External + Internal Diffusion + Dislocation
Hollow tensile specimen test External Dislocations
Fracture mechanics tests External Dislocations
P.E.S. test External Dislocations
Tubular specimen test External Dislocations
Cathodic charging test External Diffusion
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Practical point of viewPractical point of viewTESTS CHARACTERISTICS
TESTSSPECIMEN
(Size-complexity)CELL
(Size-complexity)COMPLEMENTARY
EQUIPMENT NEEDED
Disk rupture test Small size and very simpleSmall size and very simple
Hydrogen compressor and high pressure vessel
Tensile machine
Fatigue tensile machine for fatigue test only
--
Large hydrogen source at high pressure
Electrochemical equipment
(potentiostat)
Tensile test Relatively small size Large size
Fracture mechanics test
Relatively large size and complex
Very large size and complex
P.E.S. testAverage size and very easy to take from a pipeline
Average size
Tubular specimen test
Large size and complex No cell necessary
Cathodic charging test
Small size and simple
Small size and very simple
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TESTS CHARACTERISTICSInterpretation of resultsInterpretation of results
PRACTICAL DATA TO
PREDICT IN SERVICE
PERFORMANCE
POSSIBILITY OF RANKING
MATERIALS
SELECTION OF MATERIALS –
EXISTING CRITERIA
TESTS SENSIBILITYTESTS
YesPHe/PH2 Fatigue life
Treshold stress
- KIH- Crack growth
rate
- KIH
Critical hydrogen concentration
Yes/No
No, but maximum allowable KIH could
be defined
No
No
No
Disk rupture High sensitivity Possible
Tensile test Good/Poor sensitivity Possible/Difficult
Fracture mechanics
Good sensitivity Possible
P.E.S. test Poor sensitivity Difficult
Tubular specimen test
Good sensitivity Difficult
Cathodic charging
Good sensitivity
Possible but difficult in practice
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4. PARAMETERS AFFECTING HYDROGEN EMBRITTLEMENT OF STEELS
4.1. Environment
4.2. Material
4.3. Design and surface conditions
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4.1. Environment or “operating conditions”
Hydrogen purity
Hydrogen pressure
Temperature
Stresses and strains
Time of exposure
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4.1. Environment or “operating conditions”
Hydrogen purity
Influence of oxygen contamination
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4.1. Environment or “operating conditions”
Influence of H2S contamination
Hydrogen purity
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4.1. Environment or “operating conditions”
Hydrogen pressure
Influence of H2S partial pressure for AISI 321 steel
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4.1. Environment or “operating conditions”
Temperature
Influence of temperature - Principle
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4.1. Environment or “operating conditions”
Temperature
Influence of temperature for some stainless steels
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4.1. Environment or “operating conditions”
Hydrogen purity
Hydrogen pressure
Temperature
Stresses and strains
Time of exposure
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4.2. Material
Microstructure
Chemical composition
Heat treatment and mechanical properties
Welding
Cold working
Inclusion
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4.2. Material
Heat treatment and mechanical properties
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4.2. Material
Welding
4.22.01.91.9 Embrittlement index
25 %8 %2.5 %0 %
(No weld)Ferrite content
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4.2. Material
Microstructure
Chemical composition
Heat treatment and mechanical properties
Welding
Cold working
Inclusion
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4.3. Design and surface conditions
Stress level
Stress concentration
Surface defects
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4.3. Design and surface conditionsStress concentration
Crack initiation on a geometrical discontinuity
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4.3. Design and surface conditionsStress concentration
Crack initiation on a geometrical discontinuity
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4.3. Design and surface conditionsSurface defects
FAILURE OF A HYDROGEN
TRANSPORT VESSEL IN 1983. HYDROGEN
CRACK INITIATED ON INTERNAL
CORROSION PITS
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5.HYDROGEN EMBRITTLEMENT OF OTHER MATERIALS
1) All metallic materials present a certain degree of sensitive to HE
2) Materials which can be used
Brass and copper alloys
Aluminium and aluminium alloys
Cu-Be
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5.HYDROGEN EMBRITTLEMENT OF OTHER MATERIALS3) Materials known to be very sensitive to HE :
Ni and high Ni alloysTi and Ti alloys
4) Steels : HE sensitivity depend on exact chemical composition, heat or mechanicaltreatment, microstructure, impurities and strength
Non compatible material can be used at limited stress level
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6. HYDROGEN ATTACKMain parameters summarized on the « Nelson curves » :
Influence of P, T, Cr and MoTi and W have also a beneficial effectC, Al, Ni and Mn (excess) have adetrimental effect
Other parameters :
Heat treatment
Stress level, welding procedure
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6. HYDROGEN ATTACK
Nelson curves
Legend :Surface decarburizationInternal decarburization(Hydrogen attack)
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7. CONCLUSION - RECOMMENDATION1) The influence of the different parameters shall
be addressed.
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7. CONCLUSION - RECOMMENDATION1) The influence of the different parameters shall
be addressed.2) To safely use materials in presence of
hydrogen, an internal specification shall cover the following :
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7. CONCLUSION - RECOMMENDATION1) The influence of the different parameters shall
be addressed.2) To safely use materials in presence of
hydrogen, an internal specification shall cover the following :• The « scope », i.e. the hydrogen pressure,
the temperature and the hydrogen purity
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7. CONCLUSION - RECOMMENDATION1) The influence of the different parameters shall
be addressed.2) To safely use materials in presence of
hydrogen, an internal specification shall cover the following :• The « scope », i.e. the hydrogen pressure,
the temperature and the hydrogen purity• The material, i.e. the mechanical properties,
chemical composition and heat treatment
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7. CONCLUSION - RECOMMENDATION1) The influence of the different parameters shall
be addressed.2) To safely use materials in presence of
hydrogen, an internal specification shall cover the following :• The « scope », i.e. the hydrogen pressure,
the temperature and the hydrogen purity• The material, i.e. the mechanical properties,
chemical composition and heat treatment• The stress level of the equipment
58The world leader in industrial and medical gases
7. CONCLUSION - RECOMMENDATION1) The influence of the different parameters shall
be addressed.2) To safely use materials in presence of
hydrogen, an internal specification shall cover the following :• The « scope », i.e. the hydrogen pressure,
the temperature and the hydrogen purity• The material, i.e. the mechanical properties,
chemical composition and heat treatment• The stress level of the equipment• The surface defects and quality of finishing
59The world leader in industrial and medical gases
7. CONCLUSION - RECOMMENDATION1) The influence of the different parameters shall
be addressed.2) To safely use materials in presence of
hydrogen, an internal specification shall cover the following :• The « scope », i.e. the hydrogen pressure,
the temperature and the hydrogen purity• The material, i.e. the mechanical properties,
chemical composition and heat treatment• The stress level of the equipment• The surface defects and quality of finishing• And the welding procedure, if any
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