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SECOND JOINT EUROPEAN SUMMER SCHOOL FOR FUEL CELL AND HYDROGEN TECHNOLOGY September 17-21, 2012

SECOND JOINT EUROPEAN SUMMER SCHOOL FOR FUEL CELL AND HYDROGEN TECHNOLOGY September 17-21, 2012. HYDROGEN STORAGE TECHNOLOGIES: COMPATIBILITY OF METALLIC MATERIALS. Hervé Barthélémy. HYDROGEN STORAGE TECHNOLOGIES: COMPATIBILITY OF METALLIC MATERIALS WITH HYDROGEN. GENERALITIES.

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SECOND JOINT EUROPEAN SUMMER SCHOOL FOR FUEL CELL AND HYDROGEN TECHNOLOGY September 17-21, 2012

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  1. SECOND JOINT EUROPEAN SUMMER SCHOOL FOR FUEL CELL AND HYDROGEN TECHNOLOGYSeptember 17-21, 2012 HYDROGEN STORAGE TECHNOLOGIES: COMPATIBILITY OF METALLIC MATERIALS Hervé Barthélémy

  2. HYDROGEN STORAGE TECHNOLOGIES: COMPATIBILITY OF METALLIC MATERIALS WITH HYDROGEN GENERALITIES HYDROGEN EMBRITTLEMENT - GENERALITIES REPORTED ACCIDENTS AND INCIDENTS ON HYDROGEN EMBRITTLEMENT TEST METHODS

  3. HYDROGEN STORAGE TECHNOLOGIES: COMPATIBILITY OF MATERIALS WITH HYDROGEN PARAMETERS AFFECTING HYDROGEN EMBRITTLEMENT OF STEELS 5.1. Environmental parameters 5.2. Design and surface conditions 5.3. Materials HYDROGEN EMBRITTLEMENT OF OTHER MATERIALS HYDROGEN ATTACK CONCLUSION - RECOMMENDATION

  4. GENERALITIES • Compatibilty between a gas and metallic materials is affected by chemical reactions and physical influences classified into five categories: 1.1. Corrosion (the most frequent type of expected reaction) 1.2. Hydrogen embrittlement 1.3. Generation of dangerous products through chemical reaction 1.4. Violent reactions (like ignition) 1.5. Embrittlement at low temperature

  5. 1.1. Corrosion Dry corrosion • Is the chemical attack by a dry gas on the cylinder material. The result is a reduction of the cylinder wall thickness. This type of corrosion is not very common, because the rate of dry corrosion is very low at ambient temperature • At high temperature, hydrogen can react with some materials and can form for example hydrides

  6. 1.1. Corrosion Wet corrosion Most common sources of water ingress: • By the customer (retro-diffusion/backfilling or when the cylinder is empty, by air entry, if the valve is not closed) • During hydraulic testing • During filling

  7. 1.1. Corrosion Wet corrosion Different types of “wet corrosion” in alloys: • General corrosion: e.g. by acid gases (CO2, SO2) or oxidizing gases (O2, Cl2). Additionally some gases, even inert ones, when hydrolysed could lead to the production of corrosive products (e.g. SiH2Cl2) • Localised corrosion: e.g. pitting corrosion by wet HCl in aluminium alloys or stress corrosion cracking of highly stressed steels by wet CO/CO2 mixtures • H2 cannot even in wet conditions create such types of corrosion

  8. 1.1. Corrosion Corrosion by impurities Most common polluants: • Atmospheric air, in this case the harmful impurities can be moisture and oxygen (e.g. in liquefied ammonia) • Agressive products contained in some gases, e.g. H2S in natural gas

  9. 1.1. Corrosion Corrosion by impurities • Agressive traces (acid, mercury, etc.) remaining from the manufacturing process of some gases For example, some electrolytic hydrogen can contain traces of mercury (from the diaphragm). Mercury reacts with many metals at room temperature especially aluminium

  10. 1.2. Hydrogen embrittlement • Embrittlement by dry gas can occur at ambient temperature in the case of certain gases and under service conditions with stresses the cylinder material. The best know example is embrittlement caused by hydrogen • The type of stress cracking phenomenon can, under certain conditions, lead to the failure of gas cylinders (or other metallic components) containing hydrogen, hydrogen mixtures and hydrogen bearing compounds including hydrides

  11. 1.2. Hydrogen embrittlement • The risk of hydrogen embrittlement only occurs if the partial pressure of the gas and the stress level of the cylinder material is high enough • This compatibility issue is one of the most important and well described in details in the following

  12. 1.3. Generation of dangerous products • In some cases, reactions of a gas with a metallic material can lead to the generation of dangerous products. Examples are the possible reaction of C2H2 with copper alloys containing more than 70 % copper and of CH3Cl in aluminium cylinders • No case known with hydrogen

  13. 1.4. Violent reactions (e.g. ignition) • In principle, such types of gas/metallic material reactions are not very common at ambient temperatures, because high activation energies are necessary to initiate such reactions. In the case of some non-metallic materials, this type of reaction can occur with some gases (e.g. O2, Cl2)

  14. 1.5. Embrittlement at low temperature • Ferritic steels are known to be sensitive to this phenomenon • Liquid hydrogen is very cold (20 K). In such cases, materials having good impact behaviour at low temperature (aluminium alloys, austenitic stainless steels) shall be used and carbon or low alloyed steels shall be rejected

  15. HYDROGEN EMBRITTLEMENT - GENERALITIES • Internal hydrogen embrittlement • External hydrogen embrittlement

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

  17. T  200°C Hydrogen embrittlement T  200°C Hydrogen attack HYDROGEN EMBRITTLEMENT - GENERALITIES • Important parameter : THE TEMPERATURE

  18. CRITICAL CONCENTRATION AND DECOHESION ENERGY HYDROGEN EMBRITTLEMENT - GENERALITIES • Reversible phenomena • Transport of H2 by the dislocations • H2 traps

  19. FAILURE OF A HYDROGEN TRANSPORT VESSEL IN 1980 REPORTED ACCIDENTS AND INCIDENTS ON HYDROGEN EMBRITTLEMENT

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

  21. HYDROGEN CYLINDER BURSTS INTERGRANULAR CRACK REPORTED ACCIDENTS AND INCIDENTS ON HYDROGEN EMBRITTLEMENT

  22. VIOLENT RUPTURE OF A HYDROGEN STORAGE VESSEL REPORTED ACCIDENTS AND INCIDENTS ON HYDROGEN EMBRITTLEMENT

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

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

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

  26. 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

  27. Specimens for compact tension test TEST METHODS

  28. 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

  29. 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

  30. 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

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

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

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

  34. 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

  35. Example of a disk rupture test curve TEST METHODS

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

  37. Fatigue test - Principle TEST METHODS

  38. Fatigue test - Pressure cycle TEST METHODS

  39. 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

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

  41. TESTS CHARACTERISTICS Type of hydrogen embrittlement and transport mode

  42. TESTS CHARACTERISTICS Practical point of view

  43. TESTS CHARACTERISTICS Interpretation of results

  44. PARAMETERS AFFECTING HYDROGEN EMBRITTLEMENT OF STEELS 5.1. Environment 5.2. Design and surface conditions 5.3. Material

  45. Hydrogen purity • Hydrogen pressure • Temperature • Stresses and strains • Time of exposure 5.1. Environment or “operating conditions”

  46. 5.1. Environment or “operating conditions” • Hydrogen purity Influence of oxygen contamination

  47. Influence of H2S contamination 5.1. Environment or “operating conditions” • Hydrogen purity

  48. Influence of H2S partial pressure for AISI 321 steel 5.1. Environment or “operating conditions” • Hydrogen pressure

  49. Influence of temperature - Principle 5.1. Environment or “operating conditions” • Temperature

  50. Influence of temperature for some stainless steels 5.1. Environment or “operating conditions” • Temperature

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