Ti1.0Cr1.5V1.7合金的氢同位素效应

doi:10.15541/jim20160089

摘要/Abstract

摘要：

采用电弧熔炼的方法, 制备了Ti_1.0Cr_1.5V_1.7合金。通过SEM、EDS和XRD对合金的形貌、组成及其氢化物的结构进行表征。结果表明, 合金组成不均匀, 存在网状的析出相。吸氢过程中的相转变只与吸氢量有关, 而与氢同位素种类无关。分离因子(α_H-D)测试表明, 压力对α_H-D的影响不大, 但氘丰度的增加会导致α_H-D的降低。温度对α_H-D的影响较复杂。α_H-D在213 K时有极大值2.29。当温度高于213 K时, α_H-D的实验值与谐振模型的计算值符合得很好, 且lnα_H-D与1/T之间存在线性关系; 当温度低于213 K时, 实验值与计算值之间存在较大差异。Ti_1.0Cr_1.5V_1.7合金氢化物的DSC分析结果表明, α_H-D在低温时的突变与相转变之间并无直接的联系。

关键词: 氢同位素效应, 分离因子, Ti1.0Cr1.5V1.7合金

Abstract:

Ti_1.0Cr_1.5V_1.7 alloy was prepared by arc melting and then its morphology and constitution were analyzed by SEM and EDS. The observations showed that the alloy was unhomogeneous with some network-shaped precipitates. The structures of the hydrides of Ti_1.0Cr_1.5V_1.7 were determined by XRD. The structures of the hydrides depended only on the hydrogen content, not on the kind of hydrogen isotopes. The dependences of separation factor (α_H-D) on pressure, deuterium concentration and temperature were investigated systematically. Not significantly influenced by pressure, α_H-D decreased with the increase of deuterium concentration. However, the dependence of α_H-D on temperature was complicated. In 213-373 K, α_H-D increased with the decrease of temperature, which agreed with the harmonic oscillator model (HOM). In 77-213 K, the experimental α_H-D was different from the calculated value of HOM. According to the results of DSC measurement for the hydrides of Ti_1.0Cr_1.5V_1.7 alloy, the disagreement between the experiments and the HOM in 77-213 K was not induced by phase transitions. Moreover, the maximum α_H-D reached 2.29 at 213 K.

Key words: hydrogen isotope effects, separation factor, Ti1.0Cr1.5V1.7 alloy

中图分类号:

O643

杨勇彬, 罗德礼, 饶咏初, 郭文胜. Ti_1.0Cr_1.5V_1.7合金的氢同位素效应[J]. 无机材料学报, 2016, 31(12): 1295-1300.

YANG Yong-Bin, LUO De-Li, RAO Yong-Chu, GUO Wen-Sheng. Hydrogen Isotope Effects in Ti_1.0Cr_1.5V_1.7 Alloy[J]. Journal of Inorganic Materials, 2016, 31(12): 1295-1300.

图/表 12

图1 Ti1.0Cr1.5V1.7 合金的SEM照片

Fig. 1 SEM micrograph of alloy Ti1.0Cr1.5V1.7 alloy

表1 EDS分析的Ti1.0Cr1.5V1.7合金组成/at%

Table 1 Chemical composition of Ti1.0Cr1.5V1.7 analyzed by EDS/at%

	B			A
	1	2	3	4	5	6
Ti	35.62	43.24	56.26	16.86	18.53	16.36
V	33.05	26.88	21.07	45.94	44.75	46.28
Cr	31.33	29.87	22.67	37.20	36.72	37.36

图 2 Ti1.0Cr1.5V1.7合金的XRD图谱

Fig. 2 XRD pattern of Ti1.0Cr1.5V1.7 alloy

图3 不同氢含量的Ti1.0Cr1.5V1.7合金氢化物的XRD图谱

Fig. 3 XRD patterns of the hydrides of Ti1.0Cr1.5V1.7 with different hydrogen contents

图4 压力对αH-D的影响(303 K, D3%)

Fig. 4 Dependence of αH-D on pressure (303 K, D 3%)

图5 氘丰度对αH-D的影响(303 K, 0.3 MPa)

Fig. 5 Dependence of αH-D on deuterium concentration (303 K, 0.3 MPa)

表2 不同温度下的分离因子(0.3 MPa, D 3%)

Table 2 Separation factors with different temperature (0.3 MPa, D 3%)

Temperature /K	77	103	133	155	173	183	193	203	213	243	273	303	333	373
α_H-D	1.02	1.21	1.13	1.05	1.54	1.81	1.93	2.05	2.29	1.89	1.6	1.41	1.3	1.17

图6 lnαH-D与1/T的关系(213~373 K)

Fig. 6 Dependence of lnαH-D on 1/T (213-373 K)

表3 不同材料A与B的值

Table 3 Values of A and B for different materials

Materials	Temperature /K	A	B	Reference
Pd	175-330	-0.023	-202	[19]
TiMn_1.5	195-296	-0.75	295	[19]
LaNi₅	223-323	-0.53	193	[19]
ZrMn₂	240-300	-0.477	240	[19]
ZrCr₂	273-373	-1.5	580	[19]
Ti_1.0Cr_1.5V_1.7	213-373	-0.74	335	This work

图7 不同材料中lnαH-D与1/T的关系

Fig. 7 Dependence of lnαH-D on 1/T for varied materials

图8 lnαH-D与1/T的关系

Fig. 8 Dependence of lnαH-D on 1/T

图9 MH1.1、MD1.1和MH1.1D0.03的DSC曲线

Fig. 9 DSC curves for MH1.1, MD1.1, and MH1.1D0.03 heat desorption is expressed as the positive direction

参考文献 21

[1]	KOU HUA-QIN, HUANG ZHI-YONG, LUO WEN-HUA,et al. Experimental study on full-scale ZrCo and depleted uranium beds applied for fast recovery and delivery of hydrogen isotopes . Appl. Energy, 2015, 145: 27-35.
[2]	LUO DE-LI, SONG JIANG-FENG, HUANG GUO-QIANG,et al. Progress of China’s TBM tritium technology. Fusion Eng. Des., 2012, 87(7/8): 1261-1267.
[3]	FUKADA S, FUCHINOUE K, NISHIKAWA M.Isotope separation factor and isotopic exchange rate between hydrogen and deuterium of palladium.J. Nucl. Mater., 1995, 226(3): 311-318.
[4]	LUO WEI-FANG, COWGILL D F.Separation factors for hydrogen isotopes in palladium hydride.J. Phys. Chem. C, 2013, 117(27): 13861-13871.
[5]	WISWALL R H, REILLY J J.Inverse hydrogen isotope effects in some metal hydride systems.Inorg. Chem., 1972, 11(7): 1691-1696.
[6]	ALDRIDGE F T.Gas chromatographic separation of hydrogen isotopes using metal hydrides. J.Less-Common Met., 1985, 108: 131-150.
[7]	ANDREEV B M, MAGOMEDBEKOV E, SELIVANENKO I L.Separation of isotopes of light elements in a gas-solid phase system. 1. Isotope effects in a hydrogen-metal hydride and intermetallic-compound hydride system.Atom. Energy, 1998, 84(2): 114-121.
[8]	SICKING G, MAGOMEDBEKOV E, HEMPELMANN R.Tracer experiments on the exchange equilibrium of tritium between hydrogen gas and the hydrogen-storage material TiMnl.5-hydride.Ber. Bunsenges . Phys. Chem., 1981, 85: 686-692.
[9]	JAT R A, SAWANT S G, RAJAN M B,et al.Hydrogen isotope effect on storage behavior of U2Ti and UZr2.3. J. Nucl. Mater., 2013, 443: 316-320.
[10]	TANAKA J, WISWALL R H, REILLY J J.Hydrogen isotope effects in titanium alloy hydrides.Inorganic Chemistry, 1978, 17(2): 498-500.
[11]	KUMAR A, SHASHIKALA K, BANERJEE S,et al. Effect of cycling on hydrogen storage properties of Ti2VCr alloy. Int. J. Hydrogen Energy, 2012, 37(4): 3677-3682.
[12]	AOKI M, NORITAKE T, ITO A,et al. Improvement of cyclic durability of Ti-V-Cr alloy by Fe substitution. Int. J. Hydrogen Energy, 2011, 36(19): 12329-12332.
[13]	KURIIWA T, MARUYAMA T, KAMEGAWA A,et al. Effects of V content on hydrogen storage properties of V-Ti-Cr alloys with high desorption pressure. Int. J. Hydrogen Energy, 2010, 35(17): 9082-9087.
[14]	AKIBA E, IBA H.Hydrogen absorption by laves phase related BCC solid solution.Intermetallics, 1998, 6(6): 461-470.
[15]	PEI P, SONG X P, LIU J,et al. The effect of rapid solidification on the microstructure and hydrogen storage properties of V35Ti25Cr40 hydrogen storage alloy. Int. J. Hydrogen Energy, 2009, 34(19): 8094-8100.
[16]	LIN H C, LIN K M, WU K C,et al. Cyclic hydrogen absorption- desorption characteristics of TiCrV and Ti0.8Cr1.2V alloys. Int. J. Hydrogen Energy, 2007, 32(18): 4966-4972.
[17]	YU X B, CHEN J Z, WU Z,et al. Effect of Cr content on hydrogen storage properties for Ti-V based BCC-phase alloys. Int. J. Hydrogen Energy, 2004, 29(13): 1377-1381.
[18]	YANG YONG-BIN, LUO DE-LI, GUO WEN-SHEN,et al. Hydrogen isotope effects in Ti-V-Cr alloy hydrides. J. Phys. Chem. C, 2015, 119(7): 3481-3487.
[19]	ANDREEV B M, MAGOMEDBEKOV E P, SICKING G H.Interaction of Hydrogen Isotopes with Transition Metals and Intermetallic Compounds. Springer-Verlag: Berlin, Heidelberg, NY, 1996.
[20]	SAZONOV A B, MAGOMEDBEKOV E P.Concentration dependence of the separation factor of hydrogen isotopes in ternary and pseudoternary systems H2-H-X-Y-H.Atom. Energy, 1999, 87(1): 519-525.
[21]	UREY H C, RITTENBERG D.Some thermodynamic properties of the (HH2)-H-1, (HH2)-H-2 molecules and compounds containing the H-2 atom.J. Chem. Phys., 1933, 1(2): 137-143.