热脱附谱技术在储氢容器材料氢陷阱研究中的应用研究进展

doi:10.16085/j.issn.1000-6613.2016-2274

摘要/Abstract

摘要： 氢能作为重要的二次能源，因其具有来源多样、储运便捷、清洁环保、利用高效等优点受到了各国的青睐。高压储氢容器是氢能的重要储输设备之一，其材料氢脆问题是氢能及其相关技术发展中的瓶颈，并逐渐发展为金属材料科学领域中一个非常重要且活跃的研究方向。热脱附谱（TDS）作为一种研究材料中氢陷阱特性的重要方法，得到了国内外学者的广泛使用。本文首先在综合介绍TDS装置及其测试原理的基础上，讨论了升温热脱过程中可能发生的氢陷阱变化对TDS结果及分析的影响。然后通过对TDS试样预处理技术发展水平及各技术利弊的分析，讨论了充氢技术和参数的选择以及充放氢过程对TDS试验结果的影响。最后，基于TDS数据后处理的现有理论及研究进展，讨论了TDS 3种拟合模型的适用性以及在其处理多陷阱曲线重合问题时反褶积过程的复杂性。

关键词: 热脱附谱技术, 储氢容器, 氢陷阱, 充氢技术, 拟合模型

Abstract: As an important secondary energy,the hydrogen has become very popular in many countries due to its avaialibility,convenient storage and transportation,clean and environmental protection,and efficient usage. High-pressure hydrogen storage vessel is the important storage and transportation equipment of hydrogen energy. The hydrogen embrittlement problem is the bottleneck of hydrogen energy and its related technology development,which has gradually developed into a very crucial and active research area in the metal material science. Thermal desorption spectroscopy(TDS)has become a widely used method to investigate the characteristics of hydrogen traps in metallic materials. First,the effect of the transformation of hydrogen traps during the heating procedure on the experimental results and its analysis of the TDS were discussed including the relatively comprehensive description of the set-up and the complete measurement principle and development history. Then the effect of hydrogen pre-charging and discharging processes on the TDS results were depicted while discussing the sample preprocessing technology and the advantages or disadvantages of TDS. Subsequently,the applicability of the three fitting models and the complexity of the deconvolution process were discussed when the TDS curves of two or more hydrogen traps overlaped with one another. Finally,the state of the art and the outlook for the post-processing theories and research development of TDS data were presented.

Key words: TDS, hydrogen storage vessel, hydrogen trap, hydrogen charging technology, fitting model

中图分类号:

TB303

屈文敏, 花争立, 李雄鹰, 顾超华, 郑津洋, 赵永志. 热脱附谱技术在储氢容器材料氢陷阱研究中的应用研究进展[J]. 化工进展, 2017, 36(11): 4160-4169.

QU Wenmin, HUA Zhengli, LI Xiongying, GU Chaohua, ZHENG Jingyang, ZHAO Yongzhi. Application of TDS technology in the study of hydrogen traps in the materials of hydrogen storage vessels[J]. Chemical Industry and Engineering Progress, 2017, 36(11): 4160-4169.

参考文献

[1] 赵永志,蒙波,陈霖新,等. 氢能源的利用现状分析[J]. 化工进展,2015,34(9):3248-3255. ZHAO Y Z,MENG B,CHEN L X,et al. Utilization status of hydrogen energy[J]. Chemical Industry and Engineering Progress,2015,34(9):3248-3255.
[2] ORIANI R A,JOSEPHIC P H. Equilibrium aspects of hydrogen-induced cracking of steels[J]. Scripta Metallurgica,1974,22(9):1065-1074.
[3] PAINTER C L F G S. First principles investigation of hydrogen embrittlement in FeAl[J]. Journal of Materials Research,1991,6(4):719-723.
[4] ORIANI R A,JOSEPHI P H. Equilibrium and kinetic studies of the hydrogen-assisted cracking of steel[J]. Acta Metallurgica,1977,24(9):979-988.
[5] JIANG D E,CARTER E A. First principles assessment of ideal fracture energies of materials with mobile impurities:implications for hydrogen embrittlement of metals[J]. Acta Materialia,2004,52(16):4801-4807.
[6] BEACHEM C D. A new model for hydrogen-assisted cracking (hydrogen "embrittlement")[J]. Metallurgical Transactions,1972,3(3):441-455.
[7] ROBERTSON I M,BIRNBAUM H K. An HVEM study of hydrogen effects on the deformation and fracture of nickel[J]. Acta Metallurgica,1986,34(3):353-366.
[8] LYNCH S P. Environmentally assisted cracking:overview of evidence for an adsorption-induced localised-slip process[J]. Acta Metallurgica,1988,36(10):2639-2661.
[9] BIRNBAUM H K,SOFRONIS P. Hydrogen-enhanced localized plasticity:a mechanism for hydrogen-related fracture[J]. Materials Science & Engineering A,1994,176(1-2):191-202.
[10] PEZOLD J V,LYMPERAKIS L,NEUGEBAUER J. Hydrogen-enhanced local plasticity at dilute bulk H concentrations:the role of H-H interactions and the formation of local hydrides[J]. Acta Materialia,2011,59(8):2969-2980.
[11] SONG J,CURTIN W A. Mechanisms of hydrogen-enhanced localized plasticity:an atomistic study using α-Fe as a model system[J]. Acta Materialia,2014,68:61-69.
[12] SCHLICHTING H,MENZEL D. Techniques for wide range,high resolution and precision,thermal desorption measurements:I. Principles of apparatus and operation[J]. Surface Science,1993,285(3):209-218.
[13] TAYLOR J B. The evaporation of atoms,ions and electrons from caesium films on tungsten[J]. Thermionic Phenomena,1961,44(6):423-458.
[14] SCHLICHTING H,MENZEL D. High resolution,wide range,thermal desorption spectrometry of rare gas layers:sticking,desorption kinetics,layer growth,phase transitions,and exchange processes[J]. Surface Science,1992,272(1):27-33.
[15] YABUMOTO N,MINEGISHI K,KOMINE Y,et al. Water-adsorbed states on silicon and silicon oxide surfaces analyzed by using heavy water[J]. Japanese Journal of Applied Physics,1990,29:490-493.
[16] MENDELSOHN M H,GRUEN D M. Temperature-programmed desorption(TPD)studies of ZrV_1.6Fe_0.4Hy and ZrV_1.2Cr_0.8Hy[J]. Materials Research Bulletin,1981,16(8):1027-1034.
[17] MATSUDA F,NAKAGAWA H,MATSUMOTO T. Dynamic observation with scanning electron microscope(SEM)of hydrogen-induced cracking in high strength steel weldments[J]. Transactions of JWRI,1979,8(2):293-296.
[18] RIGSBEE J M,JUN R B B. A TEM investigation of hydrogen-induced deformation twinning and associated martensitic phases in 304-type stainless steel[J]. Journal of Materials Science,1977,12(2):406-409.
[19] CHEN Q Z,CHU W,QIAO L,et al. TEM in situ observation of brittle cracking of hydrogen charged 310 stainless steel under tension[J]. Acta Metallrugica Sinica,1994,30(6):248-256.
[20] KLIMENKOV M. TEM study of hydrogen-containing precipitates in Al-containing ODS steel[J]. Journal of Nuclear Materials,2011,417(1):197-200.
[21] MINKOVITZ E,TALIANKER M,ELIEZER D. TEM investigation of hydrogen induced ε-hcp-martensite in 316L-type stainless steel[J]. Journal of Materials Science,1981,16(12):3506-3508.
[22] VENEGAS V,CALEYO F,GONZ LEZ J L,et al. EBSD study of hydrogen-induced cracking in API-5 L-X46 pipeline steel[J]. Scripta Materialia,2005,52(2):147-152.
[23] 钟振前,田志凌,杨春. EBSD技术在研究高强马氏体不锈钢氢脆机理中的应用[J]. 材料热处理学报,2015,36(2):77-83. ZHONG Z Q,TIAN Z L,YANG C. Application of EBSD technique in research of hydrogen embrittlement mechanism for high strength martensite stainless steel[J]. Transactions of Materials & Heat Treatment,2015,36(2):77-83.
[24] TSYGEL'NYI I M,VITVITSKⅡ V I,TKACHEV V I,et al. Phase transformations in steel 12Kh18N10T upon low-cycle loading in the presence of hydrogen[J]. Metal Science & Heat Treatment,1984,26(6):419-422.
[25] WEN M,ZHANG L,AN B,et al. Hydrogen-enhanced dislocation activity and vacancy formation during nanoindentation of nickel[J]. Physical Review B,2009,80(9):754-758.
[26] HU Z,FUKUYAMA S,YOKOGAWA K,et al. Hydrogen embrittlement of a single crystal of iron on a nanometre scale at a crack tip by molecular dynamics[J]. Modelling & Simulation in Materials Science & Engineering,1999,7(4):541-551.
[27] SEKI S,MATSUMOTO R,INOUE Y,et al. Development of EAM potential for Fe with pseudo-hydrogen effects and molecular dynamics simulation of hydrogen embrittlement[J]. Journal of the Society of Materials Science Japan,2012,61(2):175-182.
[28] TSUCHIDA Y. Change in state of hydrogen in high strength martensitic steel after hydrogen susceptibility tests of SSRT and CSRT[J]. Journal of Japan High Pressure Institute,2014,52(6):315-322.
[29] XU H,XIA X,HUA L,et al. Evaluation of hydrogen embrittlement susceptibility of temper embrittled 2.25Cr-1Mo steel by SSRT method[J]. Engineering Failure Analysis,2012,19:43-50.
[30] WANG M,AKIYAMA E,TSUZAKI K. Effect of hydrogen on the fracture behavior of high strength steel during slow strain rate test[J]. Corrosion Science,2007,49(11):4081-4097.
[31] HADAM U,ZAKROCZYMSKI T. Absorption of hydrogen in tensile strained iron and high-carbon steel studied by electrochemical permeation and desorption techniques[J]. International Journal of Hydrogen Energy,2009,34(5):2449-2459.
[32] AKIYAMA E,LI S. Electrochemical hydrogen permeation tests under galvanostatic hydrogen charging conditions conventionally used for hydrogen embrittlement study[J]. Corrosion Reviews,2016,34(1-2):103-112.
[33] MOHTADI-BONAB M A,KARIMDADASHI R,ESKANDARI M,et al. Hydrogen-induced cracking assessment in pipeline steels through permeation and crystallographic texture measurements[J]. Journal of Materials Engineering & Performance,2016,25(5):1-13.
[34] ISHIKAWA N,SUEYOSHI H,NAGAO A. Hydrogen microprint analysis on the effect of dislocations on grain boundary hydrogen distribution in steels[J]. ISIJ International,2016,56(3):413-417.
[35] KOYAMA R,ITOH G. Hydrogen emission at grain boundaries in tensile-deformed Al-9%Mg alloy by hydrogen microprint technique[J]. Transactions of Nonferrous Metals Society of China,2014,24(7):2102-2106.
[36] YALÇÌE H K,EDMONDS D V. Application of the hydrogen microprint and the microautoradiography techniques to a duplex stainless steel[J]. Materials Characterization,1995,34(2):97-104.
[37] AOKI M,SAITO H,MORI M,et al. Deformation microstructures of a low carbon steel characterized by tritium autoradiography and thermal desorption spectroscopy[J]. Journal of the Japan Institute of Metals-Nihon Kinzoku Gakkaishi,1994,58(10):1141-1148.
[38] FERNANDEZ J F,CUEVAS F,SANCHEZ C. Simultaneous differential scanning calorimetry and thermal desorption spectroscopy measurements for the study of the decomposition of metal hydrides[J]. Journal of Alloys & Compounds,2000,298(1-2):244-253.
[39] 李阳,张永健,惠卫军,等. 1500MPa级高强度钢42CrMoVNb的氢吸附行为[J]. 金属学报,2011,32(4):423-428. LI Y,ZHANG Y J,HUI W J,et al. Hydrogen absorption behavior of 1500 MPa grade high strength steel 42CrMoVNb[J]. Acta Metallurgica Sinica,2011,32(4):423-428.
[40] 张永健,惠卫军,董瀚. 一种低碳Mn-B系超高强度钢板热成形后的氢致延迟断裂行为[J]. 金属学报,2013,34(10):1153-1159. ZHANG Y J,HUI W J,DONG H. Hydrogen induced delayed fracture behavior of a low-carbon Mn-B type ultra-high strength steel sheet after hot stamping[J]. Acta Metallurgica Sinica,2013,34(10):1153-1159.
[41] 郭昀静,王春芳,李建锡,等. 利用TDS研究二次硬化钢中氢的扩散行为[J]. 航空材料学报,2012,32(3):5-9. GUO J J,WANG C F,LI J X,等. Study on diffusion behavior of hydrogen in secondary hardened steel by TDS[J]. Journal of Aeronautical Materials,2012,32(3):5-9.
[42] 孙永伟,陈继志,刘军. 1000MPa级0Cr16Ni5Mo钢的氢脆敏感性研究[J]. 金属学报,2015,36(11):1315-1324. SUN Y W,CHEN J Z,LIU J. Study on hydrogen embrittlement susceptibility of 1000 MPa grade 0Cr16Ni5Mo steel[J]. Journal of Aeronautical Materials,2015,36(11):1315-1324.
[43] NAGUMO M,TAKAI K,OKUDA N. Nature of hydrogen trapping sites in steels induced by plastic deformation[J]. Journal of Alloys & Compounds,1999,293-295(99):310-316.
[44] BARBE L,SAMEK L,VERBEKEN K,et al. Neutron diffraction analysis of martensite ageing in high-carbon FeCMnSi steel[J]. International Journal of Materials Research,2006,97(8):1123-1129.
[45] BANERJEE K,CHATTERJEE U K. Hydrogen permeation and hydrogen content under cathodic charging in HSLA 80 and HSLA 100 steels[J]. Scripta Materialia,2001,44(2):213-216.
[46] BENTLEY A P,SMITH G C. Phase transformation of austenitic stainless steels as a result of cathodic hydrogen charging[J]. Metallurgical & Materials Transactions A,1986,17(9):1593-1600.
[47] YAN M,WENG Y. Study on hydrogen absorption of pipeline steel under cathodic charging[J]. Corrosion Science,2006,48(2):432-444.
[48] MIZUNO M,ANZAI H,AOYAMA T,et al. Determination of hydrogen concentration in austenitic stainless steels by thermal desorption spectroscopy[J]. Materials Transactions,1994,35(10):703-303
[49] MINE Y,HORITA Z,MURAKAMI Y. Effect of hydrogen on martensite formation in austenitic stainless steels in high-pressure torsion[J]. Acta Materialia,2009,57(10):2993-3002.
[50] BECHTLE S,KUMAR M,SOMERDAY B P,et al. Grain-boundary engineering markedly reduces susceptibility to intergranular hydrogen embrittlement in metallic materials[J]. Acta Materialia,2009,57(14):4148-4157.
[51] NIBUR K A,SOMERDAY B P,BALCH D K,et al. The role of localized deformation in hydrogen-assisted crack propagation in 21Cr-6Ni-9Mn stainless steel[J],Acta Materialia,2009,55(13):3795-3809.
[52] ESCOBAR D P,DUPREZ L,ATRENS A,et al. Influence of experimental parameters on thermal desorption spectroscopy measurements during evaluation of hydrogen trapping[J]. Journal of Nuclear Materials,2014,450(1-3):32-41.
[53] WEI F G,TSUZAKI K. Quantitative analysis on hydrogen trapping of TiC particles in steel[J]. Metallurgical and Materials Transactions A,2006,37(2):331-353.
[54] BHARGAVA G,GOUZMAN I,CHUN C M,et al. Characterization of the "native" surface thin film on pure polycrystalline iron:a high resolution XPS and TEM study[J]. Applied Surface Science,2007,253(9):4322-4329.
[55] BRUNDLE C R,CHUANG T J,WANDELT K,et al. Core and valence photoemission studies of iron oxide surfaces and the oxidation of iron[J]. Surface Science,1977,68(1):459-468.
[56] LIN T C. A consistent method for quantitative XPS peak analysis of thin oxide films on clean polycrystalline iron surfaces[J]. Applied Surface Science,1997,119(1):83-92.
[57] MATHIEU H J,DATTA M,LANDOLT D. Thickness of natural oxide films determined by AES and XPS with/without sputtering[J]. Journal of Vacuum Science & Technology A,1985,3(2):331-335.
[58] ARONNIEMI M,LAHTINEN J,HAUTOJ RVI P. Characterization of iron oxide thin films[J]. Surface & Interface Analysis,2004,36(8):1004-1006.
[59] LEE S M,LEE J Y. The trapping and transport phenomena of hydrogen in nickel[J]. Metallurgical & Materials Transactions A,1986,17:181-187.
[60] ONO K,MESHⅡ M. Hydrogen detrapping from grain boundaries and dislocations in high purity iron[J]. Acta Metallurgica Et Materialia,1992,40(6):1357-1364.
[61] TURNBULL A,HUTCHINGS R B,FERRISS D H. Modelling of thermal desorption of hydrogen from metals[J]. Materials Science & Engineering A,1997,238(2):317-328.
[62] KISSINGER H E. Reaction kinetics in differential thermal analysis[J]. Analytical chemistry,2002,29(11):1702-1706.
[63] CHOO W Y,LEE J Y. Thermal analysis of trapped hydrogen in pure iron[J]. Metallurgical & Materials Transactions A,1981,13(1):135-140.
[64] WILSON K L,BASKES M I. Deuterium trapping in irradiated 316 stainless steel[J]. Journal of Nuclear Materials,1978,76(1-2):291-297.
[65] WEI F G,HARA T,TSUZAKI K. Precise determination of the activation energy for desorption of hydrogen in two Ti-added steels by a single thermal-desorption spectrum[J]. Metallurgical & Materials Transactions B,2004,35:587-597.
[66] ORIANI R A. The diffusion and trapping of hydrogen in steel[J]. Acta Metallurgica,1970,18(1):147-157.
[67] LEE J L,LEE J Y. Hydrogen trapping in AISI 4340 steel[J]. Metal Science,2013,17(9):426-432.
[68] LEE J Y. Hydrogen trapping phenomena in metals with B.C.C. and F.C.C. crystal structures by thermal analysis technique[J]. Zeitschrift Für Physikalische Chemie,1985,146(2):242.
[69] SUN Y W,CHEN J Z,LIU J. Hydrogen trapping in high strength 0Cr16Ni5Mo martensitic stainless steel[J]. Journal of Central South University,2015,22(11):4128-4136.
[70] DIETZEL W. Gaseous hydrogen embrittlement of materials in energy technologies[M]. Cambridge:Woodhead Publishing,2012:41.
[71] OUDRISS A,CREUS J,BOUHATTATE J,et al. Grain size and grain-boundary effects on diffusion and trapping of hydrogen in pure nickel[J]. Acta Materialia,2012,60(19):6814-6828.
[72] OUDRISS A,CREUS J,BOUHATTATE J,et al. The diffusion and trapping of hydrogen along the grain boundaries in polycrystalline nickel[J]. Scripta Materialia,2012,66(1):37-40.
[73] IZUMI T,ITOH G,HORIKAWA S. Thermal desorption spectroscopy study on the hydrogen trapping states in a pure aluminum[J]. Materials Transactions,2011,52(2):130-134.
[74] SAITOH H,ⅡJIMA Y,HIRANO K. Behaviour of hydrogen in pure aluminium,Al-4 mass% Cu and Al-1 mass% Mg 2 Si alloys studied by tritium electron microautoradiography[J]. Journal of Materials Science,1994,29(21):5739-5744.
[75] OUTLAW R A,PETERSON D T,SCHMIDT F A. Diffusion of hydrogen in pure large grain aluminum[J]. Scripta Metallurgica,1982,16:287-292.
[76] ANYALEBECHI P N. Hydrogen diffusion in Al-Li alloys[J]. Metallurgical and Materials Transactions B,1990,21(4):649-655.
[77] SMITH S W,SCULLY J R. The identification of hydrogen trapping states in an Al-Li-Cu-Zr alloy using thermal desorption spectroscopy[J]. Metallurgical & Materials Transactions A,2000,31:179-193.
[78] FRAPPART S,FEAUGAS X,CREUS J,et al. Study of the hydrogen diffusion and segregation into Fe-C-Mo martensitic HSLA steel using electrochemical permeation test[J]. Journal of Physics & Chemistry of Solids,2010,71(10):1467-1479.
[79] AKIYAMA E,LI S,SHINOHARA T,et al. Hydrogen entry into Fe and high strength steels under simulated atmospheric corrosion[J]. Electrochimica Acta,2011,56(4):1799-1805.