Review of Metallic Materials Compatibility with Hydrogen: International Conference 2007

1. INTERNATIONAL CONFERENCE ON HYDROGEN SAFETY S. SEBASTIAN – SPAINSEPTEMBER 11-13TH, 2007 Compatibility of Metallic Materials with HydrogenReview of the Present Knowledge Hervé Barthélémy

2. Compatibility of Metallic Materials with Hydrogen – Review of the present knowledge INTRODUCTION REPORTED ACCIDENTS AND INCIDENTS ON HYDROGEN EQUIPMENT TEST METHODS PARAMETERS AFFECTING HYDROGEN EMBRITTLEMENT OF STEELS - Environment, Design and Material

3. Compatibility of Metallic Materials with Hydrogen – Review of the present knowledge HYDROGEN EMBRITTLEMENT OF OTHER MATERIALS HYDROGEN ATTACK CONCLUSION - RECOMMENDATION

4. GENERALITIES • Internal hydrogen embrittlement • External hydrogen embrittlement

5. GENERALITIES 2 - IN METALLIC SOLUTION : 1 - COMBINED STATE : Hydrogen attack Gaseous hydrogen embrittlement

6. T  200°C Hydrogen embrittlement T  200°C Hydrogen attack GENERALITIES • Important parameter : THE TEMPERATURE

7. CRITICAL CONCENTRATION AND DECOHESION ENERGY GENERALITIES • Reversible phenomena • Transport of H2 by the dislocations • H2 traps

8. FAILURE OF A HYDROGEN TRANSPORT VESSEL IN 1980 REPORTED ACCIDENTS AND INCIDENTS

9. FAILURE OF A HYDROGEN TRANSPORT VESSEL IN 1983. HYDROGEN CRACK INITIATED ON INTERNAL CORROSION PITS REPORTED ACCIDENTS AND INCIDENTS

10. HYDROGEN CYLINDER BURSTS INTERGRANULAR CRACK REPORTED ACCIDENTS AND INCIDENTS

11. VIOLENT RUPTURE OF A HYDROGEN STORAGE VESSEL REPORTED ACCIDENTS AND INCIDENTS

12. H2 VESSEL. HYDROGEN CRACK ON STAINLESS STEEL PIPING REPORTED ACCIDENTS AND INCIDENTS

13. Constant strain rate • Dynamic Fatigue TEST METHODS • Static (delayed rupture test)

14. Fracture mechanic (CT, WOL, …) • Tensile test • Disk test • Other mechanical test (semi-finished products) • Test methods to evaluate hydrogen permeation and trapping TEST METHODS

15. Vessel head • Specimen • O-rings • Vessel bottom • Gas inlet – Gas outlet • Torque shaft • Load cell • Instrumentation feed through • Crack opening displacement • gauge • Knife • Axis • Load application Fracture mechanics test with WOL type specimen TEST METHODS

16. Specimens for compact tension test TEST METHODS

17. Air Liquide/CTE equipment to perform fracture mechanic test under HP hydrogen (up to 1 000 bar) TEST METHODS

18. 10-4 10-5 10-6 10-7 10-8 30 25 20 Influence of hydrogen pressure (300, 150, 100 and 50 bar) - Crack growth rate versus K curves TEST METHODS

19. da mm/cycle dN 10-2 Influence of hydrogen pressure by British Steel 10-3 10-4 152 bar H2 41 bar 1 bar N2 165 bar X 10-5 10 20 30 40 60 80 100 K, MPa Vm TEST METHODS

20. 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) TEST METHODS

21. I = (% RAN - % RAH) / % RAN I = Embrittlement index RAN = Reduction of area without H2 RAH = Reduction of area with H2 TEST METHODS

22. Pseudo Elliptic Specimen Cell for delayed rupture test with Pseudo Elliptic Specimen TEST METHODS

23. Inner notches with elongation measurement strip Tubular specimen for hydrogen assisted fatigue tests TEST METHODS

24. Upper flange • Bolt Hole • High-strength steel ring • Disk • O-ring seal • Lower flange • Gas inlet Disk testing method – Rupture cell for embedded disk-specimen TEST METHODS

25. Example of a disk rupture test curve TEST METHODS

26. I m (MPa) Hydrogen embrittlement indexes (I) of reference materials versus maximum wall stresses (m) of the corresponding pressure vessels TEST METHODS

27. Fatigue test - Principle TEST METHODS

28. Fatigue test - Pressure cycle TEST METHODS

29. nN2 Cr-Mo STEEL 6 nH2 Pure H2 H2 + 300 ppm O2 F 0.07 Hertz 5 4 3 2 nN2 1 nH2 Delta P (MPa) 0 4 5 6 7 8 9 10 11 12 13 Fatigue tests, versus  P curves TEST METHODS

30. Fatigue test Principle to detect fatigue crack initiation TEST METHODS

31. TESTS CHARACTERISTICS Type of hydrogen embrittlement and transport mode

32. TESTS CHARACTERISTICS Practical point of view

33. TESTS CHARACTERISTICS Interpretation of results

34. PARAMETERS AFFECTING HYDROGEN EMBRITTLEMENT OF STEELS 4.1. Environment 4.2. Material 4.3. Design and surface conditions

35. Hydrogen purity • Hydrogen pressure • Temperature • Stresses and strains • Time of exposure 4.1. Environment or “operating conditions”

36. 4.1. Environment or “operating conditions” • Hydrogen purity Influence of oxygen contamination

37. Influence of H2S contamination 4.1. Environment or “operating conditions” • Hydrogen purity

38. Influence of H2S partial pressure for AISI 321 steel 4.1. Environment or “operating conditions” • Hydrogen pressure

39. Influence of temperature - Principle 4.1. Environment or “operating conditions” • Temperature

40. Influence of temperature for some stainless steels 4.1. Environment or “operating conditions” • Temperature

41. 4.1. Environment or “operating conditions” • Hydrogen purity • Hydrogen pressure • Temperature • Stresses and strains • Time of exposure

42. Microstructure • Chemical composition • Heat treatment and mechanical properties • Welding • Cold working • Inclusion 4.2. Material

43. 4.2. Material • Heat treatment and mechanical properties

44. Ferrite content 0 % (No weld) 2.5 % 8 % 25 % Embrittlement index 1.9 1.9 2.0 4.2 4.2. Material • Welding

45. 4.2. Material • Microstructure • Chemical composition • Heat treatment and mechanical properties • Welding • Cold working • Inclusion

46. Stress level • Stress concentration • Surface defects 4.3. Design and surface conditions

47. Crack initiation on a geometrical discontinuity 4.3. Design and surface conditions • Stress concentration

48. Crack initiation on a geometrical discontinuity 4.3. Design and surface conditions • Stress concentration

49. FAILURE OF A HYDROGEN TRANSPORT VESSEL IN 1983. HYDROGEN CRACK INITIATED ON INTERNAL CORROSION PITS 4.3. Design and surface conditions • Surface defects

50. HYDROGEN EMBRITTLEMENT OF OTHER MATERIALS All metallic materials present a certain degree of sensitive to HE Materials which can be used • Brass and copper alloys • Aluminium and aluminium alloys • Cu-Be