Dahoe AE — Hydrogen Material Compatibility Steel
Opening of the document
Hydrogen Material
Compatibility
Steel Embrittlement Dr Arief Dahoe Explosion, Hydrogen Safety and Combustion Scientist ACKNOWLEDGEMENTS Dutch Armed Forces Knowledge Center for Explosion and Hydrogen Safety http://www.explosionsolutions.org/kcehs/
Hydrogen Material Incompatibility: Damage Mechanisms [Dr A.E. Dahoe: Principles of Hydrogen Safety, Knowledge Center for Explosion and Hydrogen Safety]
2
Compatibility
Steel Embrittlement Dr Arief Dahoe Explosion, Hydrogen Safety and Combustion Scientist ACKNOWLEDGEMENTS Dutch Armed Forces Knowledge Center for Explosion and Hydrogen Safety http://www.explosionsolutions.org/kcehs/
Hydrogen Material Incompatibility: Damage Mechanisms [Dr A.E. Dahoe: Principles of Hydrogen Safety, Knowledge Center for Explosion and Hydrogen Safety]
2
Full text, so the search can find this document · 21 kB of text
Hydrogen Phase Diagram
hydrogen
108
liquid
metal
H metal
Pressure [bar]
106
104
H2 gas
102
critical point
100
H2
solid
H2 liquid
triple point
H gas
10−2
100
101
102
103
104
Temperature [K]
105
106
[Dr A.E. Dahoe: Principles of Hydrogen Safety, Knowledge Center for Explosion and Hydrogen Safety]
3
ELECTRONIC STRUCTURE AND CONFIGURATION:
Noble gasses:
He: 1s2 , Ne: 1s2 2s2 2p6 , Ar: 1s2 2s2 2p6 3s2 3p6 ,
Kr: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6
Halogens:
F: 1s2 2s2 2p5 ,
Cl: 1s2 2s2 2p6 3s2 3p5 , Br: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p5
Paramagnetic:
H: 1s1 ,
Diamagnetic:
Be: 1s2 2s2 , Hg: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 4d10 5s2 5p6 6s2 4f14 5d10 , Ag: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s1 4d10 , Au: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 4d10 5s2 5p6 6s1 4f14 5d10
Non-magnetic?
Mn: 1s2 2s2 2p6 3s2 3p6 4s2 3d5 ,
Fe: 1s2 2s2 2p6 3s2 3p6 4s2 3d6 ,
Ni: 1s2 2s2 2p6 3s2 3p6 4s2 3d8
Cu: 1s2 2s2 2p6 3s2 3p6 4s1 3d10
Electron shells are labeled by quantum numbers (n = 1, 2, 3, . . .) or letters (K, L, M, . . .) containing a maximum number of 2n2 electrons. Subshells are designated by small letters (s, p, d, f, . . .) comprising orbitals.
4
5
INTERNAL HYDROGEN EMBRITTLEMENT
Internal Hydrogen Embrittlement [1]: Blistering.
Interior:
Metal:
Exterior:
HCl(g) + H2 O(l) −−→ H3 O+ (aq) + Cl− (aq)
2 H3 O+ (aq) + 2 e− −−→ H2 (g) + 2 H2 O(l) M(s) − βe− + βCl− (aq) −−→ MClβ (s) [surface] βH3 O+ (aq) + βe− −−→ βH· + βH2 O(l) [surface] H· + H· −−→ H2 (g) [bulk] H· + H· −−→ H2 (g)
6
Environmental Hydrogen Embrittlement:
2 H2 O(l) −−→ H3 O+ (aq) + OH− (aq) 2 H3 O+ (aq) + 2 e− −−→ H2 (g) + 2 H2 O(l) M(s) − βe− + βOH− (aq) −−→ M[OH]β (s) βH3 O+ (aq) + βe− −−→ βH· + βH2 O(l) H· + H· −−→ H2 (g) Construction elements of bridges
HYDROGEN ENRICHMENT OF METAL
• Hydrogen Embrittlement (HE), Hydrogen-Induced Cracking (HIC) and High-Temperature Hydrogen Attack (HTHA) of low carbon and low alloy steel pipelines, pressure vessels, and tubes in the power and oil and gas industry • HE of high-strength (titanium) and other hightoughness alloys, including high strength steels, and aluminum alloys used in military aircraft and other equipment • HE of nickel-based alloys and failure of duplex stainless steels for subsea applications in critical components exposed to seawater and other equipment • Hydrogen-induced fractures and HE of martensitic and other advanced high strength steels used by automotive manufacturers to create lightweight, crashworthy cars • HE of precipitation-hardened high-strength steels and copper-based alloys for use in hydrogen refueling stations • HE and HIC of fasteners in marine and other aggressive environments; and Hydride Embrittlement of metallic alloys for nuclear systems
HYDROGEN DAMAGE MECHANISMS [2]
7
Grain Structure of Steel [1]. Without H2 (left). With H2 (right).
Hydrogen Induced Fracturing [1]. Intergranular Cracking (left). Transgranular Cracking (right).
8
kf
−−
H2 ↽
−⇀
− H· + H·
kb
diffusion
Keq (P, T ) =
kf
p2
= pHH·
kb
2
H· −−−−→ Metal
Hoop Stress and Longitudinal Stress
9
Hydrogen Concentration – Stress - Strain Diagram (700 MPa yield strength steel) [3]
10
kf
−−
H2 ↽
−⇀
− H· + H·
kb
diffusion
Keq (P, T ) =
kf
p2
= pHH·
kb
2
H· −−−−→ Metal
Intergranular Stress Assisted Cracking [1]:
Fracture Propagation Along Grain Boundaries Galvanic (Anodic/Cathodic) Protection Required
11
PROTECTING STEEL FROM GALVANIC CORROSION – CHROME PLATING
Effect of hydrogen on chrome plated steel
12
Hydrogen trapping by titanium carbide
and vanadium carbide precipitates [4].
Hydrogen trapping by carbide precipitates [4]:
(a) titanium carbide, (b) vanadium carbide, (c) titanium carbide, (d) vanadium carbide.
13
HYDROGEN TRAPPING
Hydrogen trapping sites in steels [5, 6].
14
Unified model for synergistic hydrogen embrittlement mechanisms in steels [5].
15
STEEL COMPOSITIONS
Additional refererences: [6–11].
16
EFFECT OF ALLOYING ELEMENTS
TECHNICAL TERMS
Sensitization. When steels, such as austenitic type, are slowly cooled through the range 550 – 850 ◦ C, they frequently become susceptible to intergranular attack in a corrosive medium.
(1) Sensitization occurs only in the temperature range 550 – 850 ◦ C because of the diffusion of the carbon to the grain boundaries.
(2) Fast cooling rate through the sensitizing temperature range does not provide adequate time for the process of sensitizing to occur.
(3) The degree of sensitization increases with increasing carbon content and decreasing chromium content.
(4) Chromium carbide precipitates at the grain boundary. A single carbon atom can tie up almost four chromium atoms.
Stabilized steel. Steels containing stabilizers, such as titanium and niobium, which form carbides that are more stable than chromium carbides, are called stabilized stainless steels.
Chromium depletion. When the concentration of chromium adjacent to the grain boundaries becomes less compared to its concentration away from the grain boundaries, the phenomenon is termed chromium depletion.
Annealing. Slow cooling in the furnace.
Nickel. Decreases susceptibility to sensitization.
Because carbon solubility decreases with increased Ni content.
Molybdenum. The susceptibility of steels to intergranular attack decreases with increased Mo content. Mo also increases the resistance to pitting and crevice corrosion.
Chromium. Generally increases the resistance to sensitization.
Nitrogen. The effect of nitrogen depends upon the amount. N is an austenite stabilizer. Steels containing 18% Cr, 9 – 12% Ni and N which are sensitized at 500 ◦ C for 100 h showed a maximum sensitization resistance at 0.04% N.
Titanium and Niobium. Provide stabilization against harmful precipitates (chromium carbides).
They combine with C and N. To prohibit C and N to precipitate as carbides and nitrides which lead to intergranular fracturing.
Silicon. Increases corrosion resistance in sulfuric acid.
Sulfur and Selenium. Added to increase machinability and malleability. However, corrosion resistance is decreased.
17
MELT POINTS AND BOILING POINTS OF ELEMENTS
Element Fe C Cr Ni Mn Mo Si N S P (white) P (red) Nb Ti V Al Cu B Sn Ca
Melt Point
(◦ C)
1538
3550
1907
1455
1246
2623 1410 – 1414 -210 115 44.1 590 2468 – 2477 1668 1910 660.32 1083 – 1085 2076 – 2350 232 842
Boiling Point
(◦ C)
2862
4827
2671
2913
2061
4639 2355 – 3265 -196 444.6 280.5 – 4742 – 4744 3287 3407 2470 2562 – 2595 3927 – 4273 2602 1484
Alloy
(Steel)
AISI 316
AISI 316L
AISI 304L
X42 X52 X60 X65 X70 X80
18
Melt Point
(◦ C)
1370 – 1400
1375 – 1400
1400 – 1450 1420 – 1500 1425 – 1540 1450 – 1520 1370 – 1530 1370 – 1530 1450 – 1500
STRESS-STRAIN CURVE
Stress-Strain Curve:
(1) True elastic limit: the lowest stress at which dislocation movement begins.
(2) Proportionality limit: maximum value where stress is directly proportional to strain.
(3) Elastic limit: permanent deformation occurs.
(4) Offset yield strength: plastic deformation begins to occur.
Hydrogen Embrittlement Index (HEI):
∗
ϵ = ∆ℓ =⇒ HEI 1 = ϵϵ ℓ α∗ α = ∆a =⇒ HEI 2 = a α The asterisk (∗) denotes hydrogen charged.
19
STRESS-STRAIN CURVE: DISLOCATION
20
STRESS-STRAIN CURVE: HYDROGEN EMBRITTLEMENT
21
HYDROGEN COMPATIBILITY OF VARIOUS ALLOYS
Hydrogen compatibility of various alloys [12]. All experiments, except one, were conducted at 300 K.
22
MARTENSITE TRANSFORMATION INDUCED HYDROGEN CRACKING
Steel type 304 [13]
Steel type 316L [13]
Martensite transformation induced hydrogen cracking at -60 ◦ C [13].
Steel type 304 = austeno-ferritic Steel type 316L = austenitic
23
THERMAL INSULATION – AEROGEL – LIQUEFIED HYDROGEN
Aerogel [14]. Left: A block of silica aerogel. Middle: A flower resting on a piece of silica aerogel, which is suspended over a flame from a Bunsen burner. Right: A 2.5 kg brick supported by a piece of aerogel with a mass of 2 g.
24
THERMAL CONDUCTIVITY
• STEEL • ALUMINIUM • COPPER • AEROGEL
Thermal Conductivity
Left: Steel, aluminium & copper. Data from NIST [15]. Right: Aerogel [16].
Note Thermal conductivity and electrical resistance are inversely related in metals due to free electrons. Their ratio is proportional to temperature in accordance with the Wiedemann-Franz law [17]. Therefore, good electrical conductors (low resistance) are good thermal conductors (high conductivity), and vice versa.
See also: phonon-electron interaction, superconductivity, Cooper pairs.
25
CLASSIFICATION OF STEELS: AUSTENITIC, FERRITIC, MARTENSITIC
26
DIFFUSION OF CARBON IN STAINLESS STEELS
Concentration gradient [18]:
dc
c
x2
− = √ exp − dx 4IDt πIDt B where ID = A exp − RT
27
DIFFUSION OF HYDROGEN IN STAINLESS STEEL
Composition of two X65 steels and the diffusion coefficient of hydrogen [19].
28
STEEL RADIATION EMISSION - TEMPERATURES AND COLORS
Plutonium 238
Pu
94
Emissive Radiation
29
CLASSIFICATION OF STEELS: AUSTENITIC, FERRITIC, MARTENSITIC
Source: Ref [1]. Strength range refers to Yield Strength.
30
COMPOSITION AND PROPERTIES OF AUSTENITIC STEEL
Type 304 steel is austeno-ferritic. It contains 8 to 20% ferritic steel.
Source: Ref [1].
31
COMPOSITION AND PROPERTIES OF FERRITIC STEEL
Source: Ref [1]. Strength range refers to Yield Strength.
32
COMPOSITION AND PROPERTIES OF MARTENSITIC STEEL
Source: Ref [1]. Strength range refers to Yield Strength.
33
34
IMPLICATIONS FOR THE DUTCH NATURAL GAS TRANSMISSION NETWORK SUPPLEMENTARY LECTURES
• The Dutch Natural Gas Transmission Network
is incompatible with hydrogen. And it cannot be repurposed for hydrogen service!
• Because it is constructed from steel types (X42,..., X70, etc). These are inadequate for hydrogen service. As evidenced by Refs. [6–9, 11, 20]. It are ferritic steels with a composition as summarized on Slide 16.
• Moreover: the hydrogen content may not exceed 0.2 vol% within the current/existing natural gas transmission network • AISI 316L appears to be the only viable option.
And that’s precisely what is applied for the hydrogen gas transmission network on Slide 34 • Hydrogen embrittlement/damage is caused by a multitude of mechanisms. As per Slide 2. Construction materials for hydrogen service must cope with all these mechanisms simultaneously.
• The NIPV [21], KIWA [22], DNVGL [23] and CE Delft [24] reports are scientifically wrong and misleading. And must be deemed invalid • Hyperlink to Artificial Intelligence Evaluation
• Blast Scaling:
Explosion Effects on Equipment, Structures, People and the Environment • Hydrogen Storage: A Concise Overview • Explosions:
Phenomenology, Dynamics and Mitigation
HYNETWORK [25]
DUTCH HYDROGEN BACKBONE
New Pipelines:
L360NE (X52) [26]
L415NE (X60) [27]
Existing Pipelines:
API5L L245 (Grade B) [28]
API5L L360 (X52) [26]
Residual Lifetime:
Calculation Methods [29, 30]
SUPPLEMENTARY REFERENCES
• Refs. [31–45]
35
Bibliography
[1] Ahmad Z. Principles of Corrosion Engineering and Corrosion Control. Butterworth-Heinemann/IChemE Series. Elsevier, Amsterdam, 2006.
[2] Djukic M.B. Hydrogen Embrittlement and Material Selection. Webinar, September 2022.
[3] McGuire M., Zamanzadeh M., Zolfaghari F., and Chikkam A.K. Hydrogen Measurement and Failure Prediction. Matergenics Inc, Pittsburgh, Pennsylvania, USA, August 2025.
[4] Boot T., Kömmelt P., Brouwer H.J.C., Böttger A., and Popovich V. Effect of titanium and vanadium nanocarbide size on hydrogen embrittlement of ferritic steels. Materials Degradation, 9: Article 2, 2025.
[5] Djukic M.B., Bakic G.M., Zeravcic V.S., Sedmak A., and Rajicic B. The synergistic action and interplay of hydrogen embrittlement mechanisms in steels and iron: Localized plasticity and decohesion. Engineering Fracture Mechanics, 216: Article 106528, 2019.
[6] Koyama M., Akiyama E., , Lee Y.-K., Raabe D., and Tsuzaki K. Overview of hydrogen embrittlement in high-Mn steels. International Journal of Hydrogen Energy, 42:12706–12723, 2017.
[7] Martin M.L., Connolly M.J., DelRio F.W., and Slifka A.J. Hydrogen embrittlement in ferritic steels. Applied Physics Reviews, 7: Article 041301, 2020.
[8] Moro I., Briottet L., Lemoine P., Andrieu E., Blanc C., and Odemer G. Hydrogen embrittlement susceptibility of a high strength steel X80. Materials Science and Engineering A, 527:7252–7260, 2010.
[9] Zhao Z., Qiao G., Tang L., Zhu H., Liao B., and Xiao F. Fatigue properties of X80 pipeline steels with ferrite/bainite dual-phase microstructure. Materials Science and Engineering A, 657:96–103, 2016.
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[10] Örnek C., Reccagni P., Kivisakk U., Bettini E., Engelberg D.L., and Pan J. Hydrogen embrittlement of super duplex stainless steel – Towards understanding the effects of microstructure and strain. International Journal of Hydrogen Energy, 43:12543–12555, 2018.
[11] Raabe D., Sun B., Kwiatkowski Da Silva A., Gault B., Yen H.-W., Sedighiani K., Thoudden Sukumar P., Souza Filho I.R., Katnagallu S., Jägle E., Kürnsteiner P., Kusampudi N., Stephenson L., Herbig M., Liebscher C.H., Springer H., Zaefferer S., Shah V., Wong S.-L., Baron C., Diehl M., Roters F., and Ponge D.
Current challenges and opportunities in microstructure-related properties of advanced high-strength steels.
Metallurgical and Materials Transactions A, 51:5517–5586, 2020.
[12] Zhou X., Tehranchi A., and Curtin W.A. Mechanism and prediction of hydrogen embrittlement in fcc stainless steels and high entropy alloys. Physical Review Letters, 127: Article 175501, 2021.
[13] Motomichi K., Wen Y., Hojo T., Ajito S., Kawamori M., and Akiyama E. Factors controlling transformationinduced hydrogen desorption and hydrogen-reduced transformability in austenitic steels clarified via dynamic hydrogen detection during cryogenic deformation. Scripta Materialia, 265: Article 116749, 2025.
[14] Wikipedia Encyclopedia. Aerogel. Url: https://en.wikipedia.org/wiki/Aerogel.
[15] National Institute of Standards and Technology (NIST). Url: https://en.wikipedia.org/wiki/National _Institute_of_Standards_and_Technology.
[16] He Y.-L. and Xie T. Advances of thermal conductivity models of nanoscale silica aerogel insulation material.
Applied Thermal Engineering, 81:28–50, 2015.
[17] Wikipedia Encyclopedia. Wiedemann-Franz Law. Url: https://en.wikipedia.org/wiki/Wiedemann-Fra nz_law.
[18] Agarwala R.P., Naik M.C., Anand M.S., and Paul A.R. Diffusion of carbon in stainless steels. Journal of Nuclear Materials, 36:41–47, 1970.
37
[19] Koren E., Yamabe J., Lu X., Hagen C.M.H., Wang D., and Johnsen R. Hydrogen diffusivity in X65 pipeline steel: Desorption and permeation studies. International Journal of Hydrogen Energy, 61:1157–1169, 2024.
[20] Hoschke J., Fahdul Wahab Chowdhury Md., Roethig M., Tapia-Bastidas C.V., Venezuela J., Shu Y., Gray E., Djukic M.B., Depover T., Verbeken K., and Atrens A. The influence of subcritical annealing and cold working on the hydrogen embrittlement susceptibility of X65 D pipeline steel. Safety Science, 2025:1–19, 2025.
[21] Spoelstra M.B. and Reinders J. Reactie NIPV op artikel over veilig gebruik van waterstof in bestaande aardgasleidingen. Nederlands Instituut Publieke Veiligheid (NIPV), November 2024.
[22] Hermkens R., Jansma S., Van der Laan M., De Laat H., Pilzer B., and Pulles K. Toekomstbestendige gasdistributienetten. KIWA Report GT-170272, July 2018.
[23] Van den Noort A., Sloterdijk W., and Vos M.
OGNL.151886, July 2017.
Verkenning waterstofinfrastructuur.
DNV GL Report
[24] Jongsma C., Van der Veen R., and Vendrik J. Waterstof voor de gebouwde omgeving. CE Delft Report 20.190307.001, February 2020. Kennisdocument voor de gemeente Nijmegen.
[25] HyNetwork. Conceptvoorstel aanpassing uitrolplan. Consultatiedocument, 2024.
[26] Bouledroua O., Zelmati D., Hafsi Z., and Djukic M.B. Hydrogen embrittlement effects on remaining life and fatigue crack growth rate in API 5L X52 steel pipelines under cyclic pressure loading. Engineering Failure Analysis, 166: Article 108917, 2024.
[27] Faucon L.E., Boot T., Riemslag T., Scott S.P., Liu P., and Popovich V. Hydrogen-Accelerated Fatigue of API X60 Pipeline Steel and its Weld. Metals, 13: Article 563, 2023.
[28] Paiva V.E.L., Vieira R.D., and Freire J.L.F. Fatigue Properties Assessment of API 5L Gr. B Pipeline Steel Using Infrared Thermography. In A. Baldi, S. Quinn, X. Balandraud, and J.M. Dulieu-Barton, editors,
38
Residual Stress, Thermomechanics & Infrared Imaging, Hybrid Techniques and Inverse Problems, volume 7 of Conference Proceedings of the Society for Experimental Mechanics Series, pages 17–23, New York, 2019. The Society for Experimental Mechanics, Inc., River Publishers.
[29] Oesterlin H., Fischer C., and Michler T. Evaluation of lifetime predictions for future hydrogen pipelines by different fracture mechanics-based design codes. Energy Technology, 13: Article 2301012, 2025.
[30] Yang R., Schell C.A., Rayasam D., and Groth K.M. Hydrogen impact on transmission pipeline risk: Probabilistic analysis of failure causes. Reliability Engineering and System Safety, 257A: Article 110825, 2025.
[31] Shtoyko I., Toribio J., Kharin V., and Hredil M. Prediction of the residual lifetime of gas pipelines considering the effect of soil corrosion and material degradation. Procedia Structural Integrity, 16:148–152, 2019.
[32] Gallon N. Hydrogen Pipelines – Design and Material Challenges and Mitigation. EPRG Project 221/2020, European Pipeline Research Group (EPRG), December 2020.
[33] Martin P., Ocko I.B., Esquivel-Elizondo S., Kupers R., Cebon D., Baxter T., and Hamburg S.P. A review of challenges with using the natural gas system for hydrogen. Energy Science and Engineering, 12:3995–4009, 2024.
[34] Turcott S. Decoding Mechanical Failures: The Definitive Guide to Interpreting Fractures. Steel Empire Incorporated, 2020.
[35] American Petroleum Institute (API). Damage Mechanisms Affecting Fixed Equipment in the Refining Industry.
API Recommended Practice 571 (API RP 571), 2020.
[36] American Petroleum Institute (API). Thread Compounds for Casing, Tubing, Line Pipe, and Drill Stem Elements. API Recommended Practice 5A3 (API RP 5A3), 2023.
[37] American Petroleum Institute (API). Recommended Practice for Care and Use of Casing and Tubing. API Recommended Practice 5C1 (API RP 5C1), 2025.
39
[38] American Petroleum Institute (API). Recommended Practice for Conducting Drop-Weight Tear Tests on Line Pipe. API Recommended Practice 5L3 (API RP 5L3), 2025.
[39] American Petroleum Institute (API). Materials and Fabrication of 2.25Cr – 1Mo, 2.25Cr – 1Mo – 0.25V, 3Cr – 1Mo, and 3Cr – 1Mo – 0.25V Steel Heavy-wall Pressure Vessels for High-temperature, High-pressure Hydrogen Service. API Recommended Practice 934-A (API RP 934-A), 2025.
[40] American Society for Testing and Materials (ASTM). Process Piping: ASME Code for Pressure Piping, B31.
ASTM International, 2024. Revision of ASME B31.3-2022.
[41] Tao P., Zhou W., Miao X., Peng P., Liu P., and Liu W. Review of characterization on hydrogen embrittlement by micro-sample testing methods. Metals, 13: Article 1753, 2023.
[42] Luo H., Sohn S.S., Lu W., Li L., Li X., Soundararajan C.K., Krieger W., Li Z., and Raabe D. A strong and ductile medium-entropy alloy resists hydrogen embrittlement and corrosion. Nature Communications, 11: Article 3081, 2020.
[43] Weihrauch M., Patel M., and Patterson E.A. Measurements and predictions of diffusible hydrogen escape and absorption in catholically charged 316LN austenitic stainless steel. Scientific Repports, 13: Article 10545, 2023.
[44] Mabho N., Bergers K., Flock J., and Telgheder U. Determination of diffusible and total hydrogen concentration in coated and uncoated steel using melt and solid extraction techniques: Part I. Talanta, 82:1298–1305, 2010.
[45] Bergers K., Camisaõ de Souza E., Thomas I., Mabho N., and Flock J. Determination of hydrogen in steel by thermal desorption mass spectrometry. Steel Research International, 81:499–507, 2010.
40
hydrogen
108
liquid
metal
H metal
Pressure [bar]
106
104
H2 gas
102
critical point
100
H2
solid
H2 liquid
triple point
H gas
10−2
100
101
102
103
104
Temperature [K]
105
106
[Dr A.E. Dahoe: Principles of Hydrogen Safety, Knowledge Center for Explosion and Hydrogen Safety]
3
ELECTRONIC STRUCTURE AND CONFIGURATION:
Noble gasses:
He: 1s2 , Ne: 1s2 2s2 2p6 , Ar: 1s2 2s2 2p6 3s2 3p6 ,
Kr: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6
Halogens:
F: 1s2 2s2 2p5 ,
Cl: 1s2 2s2 2p6 3s2 3p5 , Br: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p5
Paramagnetic:
H: 1s1 ,
Diamagnetic:
Be: 1s2 2s2 , Hg: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 4d10 5s2 5p6 6s2 4f14 5d10 , Ag: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s1 4d10 , Au: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 4d10 5s2 5p6 6s1 4f14 5d10
Non-magnetic?
Mn: 1s2 2s2 2p6 3s2 3p6 4s2 3d5 ,
Fe: 1s2 2s2 2p6 3s2 3p6 4s2 3d6 ,
Ni: 1s2 2s2 2p6 3s2 3p6 4s2 3d8
Cu: 1s2 2s2 2p6 3s2 3p6 4s1 3d10
Electron shells are labeled by quantum numbers (n = 1, 2, 3, . . .) or letters (K, L, M, . . .) containing a maximum number of 2n2 electrons. Subshells are designated by small letters (s, p, d, f, . . .) comprising orbitals.
4
5
INTERNAL HYDROGEN EMBRITTLEMENT
Internal Hydrogen Embrittlement [1]: Blistering.
Interior:
Metal:
Exterior:
HCl(g) + H2 O(l) −−→ H3 O+ (aq) + Cl− (aq)
2 H3 O+ (aq) + 2 e− −−→ H2 (g) + 2 H2 O(l) M(s) − βe− + βCl− (aq) −−→ MClβ (s) [surface] βH3 O+ (aq) + βe− −−→ βH· + βH2 O(l) [surface] H· + H· −−→ H2 (g) [bulk] H· + H· −−→ H2 (g)
6
Environmental Hydrogen Embrittlement:
2 H2 O(l) −−→ H3 O+ (aq) + OH− (aq) 2 H3 O+ (aq) + 2 e− −−→ H2 (g) + 2 H2 O(l) M(s) − βe− + βOH− (aq) −−→ M[OH]β (s) βH3 O+ (aq) + βe− −−→ βH· + βH2 O(l) H· + H· −−→ H2 (g) Construction elements of bridges
HYDROGEN ENRICHMENT OF METAL
• Hydrogen Embrittlement (HE), Hydrogen-Induced Cracking (HIC) and High-Temperature Hydrogen Attack (HTHA) of low carbon and low alloy steel pipelines, pressure vessels, and tubes in the power and oil and gas industry • HE of high-strength (titanium) and other hightoughness alloys, including high strength steels, and aluminum alloys used in military aircraft and other equipment • HE of nickel-based alloys and failure of duplex stainless steels for subsea applications in critical components exposed to seawater and other equipment • Hydrogen-induced fractures and HE of martensitic and other advanced high strength steels used by automotive manufacturers to create lightweight, crashworthy cars • HE of precipitation-hardened high-strength steels and copper-based alloys for use in hydrogen refueling stations • HE and HIC of fasteners in marine and other aggressive environments; and Hydride Embrittlement of metallic alloys for nuclear systems
HYDROGEN DAMAGE MECHANISMS [2]
7
Grain Structure of Steel [1]. Without H2 (left). With H2 (right).
Hydrogen Induced Fracturing [1]. Intergranular Cracking (left). Transgranular Cracking (right).
8
kf
−−
H2 ↽
−⇀
− H· + H·
kb
diffusion
Keq (P, T ) =
kf
p2
= pHH·
kb
2
H· −−−−→ Metal
Hoop Stress and Longitudinal Stress
9
Hydrogen Concentration – Stress - Strain Diagram (700 MPa yield strength steel) [3]
10
kf
−−
H2 ↽
−⇀
− H· + H·
kb
diffusion
Keq (P, T ) =
kf
p2
= pHH·
kb
2
H· −−−−→ Metal
Intergranular Stress Assisted Cracking [1]:
Fracture Propagation Along Grain Boundaries Galvanic (Anodic/Cathodic) Protection Required
11
PROTECTING STEEL FROM GALVANIC CORROSION – CHROME PLATING
Effect of hydrogen on chrome plated steel
12
Hydrogen trapping by titanium carbide
and vanadium carbide precipitates [4].
Hydrogen trapping by carbide precipitates [4]:
(a) titanium carbide, (b) vanadium carbide, (c) titanium carbide, (d) vanadium carbide.
13
HYDROGEN TRAPPING
Hydrogen trapping sites in steels [5, 6].
14
Unified model for synergistic hydrogen embrittlement mechanisms in steels [5].
15
STEEL COMPOSITIONS
Additional refererences: [6–11].
16
EFFECT OF ALLOYING ELEMENTS
TECHNICAL TERMS
Sensitization. When steels, such as austenitic type, are slowly cooled through the range 550 – 850 ◦ C, they frequently become susceptible to intergranular attack in a corrosive medium.
(1) Sensitization occurs only in the temperature range 550 – 850 ◦ C because of the diffusion of the carbon to the grain boundaries.
(2) Fast cooling rate through the sensitizing temperature range does not provide adequate time for the process of sensitizing to occur.
(3) The degree of sensitization increases with increasing carbon content and decreasing chromium content.
(4) Chromium carbide precipitates at the grain boundary. A single carbon atom can tie up almost four chromium atoms.
Stabilized steel. Steels containing stabilizers, such as titanium and niobium, which form carbides that are more stable than chromium carbides, are called stabilized stainless steels.
Chromium depletion. When the concentration of chromium adjacent to the grain boundaries becomes less compared to its concentration away from the grain boundaries, the phenomenon is termed chromium depletion.
Annealing. Slow cooling in the furnace.
Nickel. Decreases susceptibility to sensitization.
Because carbon solubility decreases with increased Ni content.
Molybdenum. The susceptibility of steels to intergranular attack decreases with increased Mo content. Mo also increases the resistance to pitting and crevice corrosion.
Chromium. Generally increases the resistance to sensitization.
Nitrogen. The effect of nitrogen depends upon the amount. N is an austenite stabilizer. Steels containing 18% Cr, 9 – 12% Ni and N which are sensitized at 500 ◦ C for 100 h showed a maximum sensitization resistance at 0.04% N.
Titanium and Niobium. Provide stabilization against harmful precipitates (chromium carbides).
They combine with C and N. To prohibit C and N to precipitate as carbides and nitrides which lead to intergranular fracturing.
Silicon. Increases corrosion resistance in sulfuric acid.
Sulfur and Selenium. Added to increase machinability and malleability. However, corrosion resistance is decreased.
17
MELT POINTS AND BOILING POINTS OF ELEMENTS
Element Fe C Cr Ni Mn Mo Si N S P (white) P (red) Nb Ti V Al Cu B Sn Ca
Melt Point
(◦ C)
1538
3550
1907
1455
1246
2623 1410 – 1414 -210 115 44.1 590 2468 – 2477 1668 1910 660.32 1083 – 1085 2076 – 2350 232 842
Boiling Point
(◦ C)
2862
4827
2671
2913
2061
4639 2355 – 3265 -196 444.6 280.5 – 4742 – 4744 3287 3407 2470 2562 – 2595 3927 – 4273 2602 1484
Alloy
(Steel)
AISI 316
AISI 316L
AISI 304L
X42 X52 X60 X65 X70 X80
18
Melt Point
(◦ C)
1370 – 1400
1375 – 1400
1400 – 1450 1420 – 1500 1425 – 1540 1450 – 1520 1370 – 1530 1370 – 1530 1450 – 1500
STRESS-STRAIN CURVE
Stress-Strain Curve:
(1) True elastic limit: the lowest stress at which dislocation movement begins.
(2) Proportionality limit: maximum value where stress is directly proportional to strain.
(3) Elastic limit: permanent deformation occurs.
(4) Offset yield strength: plastic deformation begins to occur.
Hydrogen Embrittlement Index (HEI):
∗
ϵ = ∆ℓ =⇒ HEI 1 = ϵϵ ℓ α∗ α = ∆a =⇒ HEI 2 = a α The asterisk (∗) denotes hydrogen charged.
19
STRESS-STRAIN CURVE: DISLOCATION
20
STRESS-STRAIN CURVE: HYDROGEN EMBRITTLEMENT
21
HYDROGEN COMPATIBILITY OF VARIOUS ALLOYS
Hydrogen compatibility of various alloys [12]. All experiments, except one, were conducted at 300 K.
22
MARTENSITE TRANSFORMATION INDUCED HYDROGEN CRACKING
Steel type 304 [13]
Steel type 316L [13]
Martensite transformation induced hydrogen cracking at -60 ◦ C [13].
Steel type 304 = austeno-ferritic Steel type 316L = austenitic
23
THERMAL INSULATION – AEROGEL – LIQUEFIED HYDROGEN
Aerogel [14]. Left: A block of silica aerogel. Middle: A flower resting on a piece of silica aerogel, which is suspended over a flame from a Bunsen burner. Right: A 2.5 kg brick supported by a piece of aerogel with a mass of 2 g.
24
THERMAL CONDUCTIVITY
• STEEL • ALUMINIUM • COPPER • AEROGEL
Thermal Conductivity
Left: Steel, aluminium & copper. Data from NIST [15]. Right: Aerogel [16].
Note Thermal conductivity and electrical resistance are inversely related in metals due to free electrons. Their ratio is proportional to temperature in accordance with the Wiedemann-Franz law [17]. Therefore, good electrical conductors (low resistance) are good thermal conductors (high conductivity), and vice versa.
See also: phonon-electron interaction, superconductivity, Cooper pairs.
25
CLASSIFICATION OF STEELS: AUSTENITIC, FERRITIC, MARTENSITIC
26
DIFFUSION OF CARBON IN STAINLESS STEELS
Concentration gradient [18]:
dc
c
x2
− = √ exp − dx 4IDt πIDt B where ID = A exp − RT
27
DIFFUSION OF HYDROGEN IN STAINLESS STEEL
Composition of two X65 steels and the diffusion coefficient of hydrogen [19].
28
STEEL RADIATION EMISSION - TEMPERATURES AND COLORS
Plutonium 238
Pu
94
Emissive Radiation
29
CLASSIFICATION OF STEELS: AUSTENITIC, FERRITIC, MARTENSITIC
Source: Ref [1]. Strength range refers to Yield Strength.
30
COMPOSITION AND PROPERTIES OF AUSTENITIC STEEL
Type 304 steel is austeno-ferritic. It contains 8 to 20% ferritic steel.
Source: Ref [1].
31
COMPOSITION AND PROPERTIES OF FERRITIC STEEL
Source: Ref [1]. Strength range refers to Yield Strength.
32
COMPOSITION AND PROPERTIES OF MARTENSITIC STEEL
Source: Ref [1]. Strength range refers to Yield Strength.
33
34
IMPLICATIONS FOR THE DUTCH NATURAL GAS TRANSMISSION NETWORK SUPPLEMENTARY LECTURES
• The Dutch Natural Gas Transmission Network
is incompatible with hydrogen. And it cannot be repurposed for hydrogen service!
• Because it is constructed from steel types (X42,..., X70, etc). These are inadequate for hydrogen service. As evidenced by Refs. [6–9, 11, 20]. It are ferritic steels with a composition as summarized on Slide 16.
• Moreover: the hydrogen content may not exceed 0.2 vol% within the current/existing natural gas transmission network • AISI 316L appears to be the only viable option.
And that’s precisely what is applied for the hydrogen gas transmission network on Slide 34 • Hydrogen embrittlement/damage is caused by a multitude of mechanisms. As per Slide 2. Construction materials for hydrogen service must cope with all these mechanisms simultaneously.
• The NIPV [21], KIWA [22], DNVGL [23] and CE Delft [24] reports are scientifically wrong and misleading. And must be deemed invalid • Hyperlink to Artificial Intelligence Evaluation
• Blast Scaling:
Explosion Effects on Equipment, Structures, People and the Environment • Hydrogen Storage: A Concise Overview • Explosions:
Phenomenology, Dynamics and Mitigation
HYNETWORK [25]
DUTCH HYDROGEN BACKBONE
New Pipelines:
L360NE (X52) [26]
L415NE (X60) [27]
Existing Pipelines:
API5L L245 (Grade B) [28]
API5L L360 (X52) [26]
Residual Lifetime:
Calculation Methods [29, 30]
SUPPLEMENTARY REFERENCES
• Refs. [31–45]
35
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