Preparation of titanium by hydrogenation and analysis of its energy
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摘要: 以海绵钛为原料，在不同温度、不同时间下制备出氢化钛。根据重量变化分析其反应原理，用X射线衍射仪（XRD）进行结构分析，扫描电镜（SEM）进行形貌分析。结果显示：随反应温度升高，氢化钛质量增加率增大，脆性也变大。当温度高于500 ℃之后，质量增长率变化不大。热力学计算结果发现温度从300 ℃增加到700 ℃时，平衡常数显著下降，表明反应温度过高不利于反应进行。氢化过程的吸附能量计算表明其较优吸附位位于其中心点位。固溶能量分析表明氢原子更倾向于占据八面体间隙。Abstract: Titanium hydride was prepared from sponge titanium at different temperatures and time. Perform structural analysis using X-ray diffraction (XRD) and morphology analysis using scanning electron microscopy (SEM). The results show that with the increase of reaction temperature, the mass growth rate of titanium hydride increases, and the brittleness also increases. When the temperature exceeds 500 ℃, there is little change in the mass growth rate. The thermodynamic calculation results show that when the temperature increases from 300 ℃ to 700 ℃, the equilibrium constant significantly decreases, indicating that a high reaction temperature is not conducive to the reaction. The calculation of adsorption energy in the hydrogenation process shows that the optimal adsorption site is located at its central point. Solid solution energy analysis shows that hydrogen atoms tend to occupy octahedral gaps more.
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Key words:
- titanium hydride /
- sponge titanium /
- reaction temperature /
- prepartion /
- characterization
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图 1 不同温度氢化钛粉SEM形貌
Figure 1. SEM diagram of titanium hydride at different temperatures
(a) 400 ℃； (b) 450 ℃；(c) 500 ℃
图 2 不同温度下氢化钛粉XRD谱
Figure 2. XRD spectra of titanium hydride powder at different temperatures
图 3 钛氢化反应△r$ {H}_{{\mathrm{m}}}^{\theta } $(T)与△r$ {G}_{{\mathrm{m}}}^{\theta } $(T)随温度的变化
Figure 3. △r$ {H}_{{\mathrm{m}}}^{\theta } $(T) and △r$ {G}_{{\mathrm{m}}}^{\theta } $(T) of titanium hydrogenation reaction with temperature
图 4 温度与平衡氢化反应的平衡常数间的关系
Figure 4. Relationship between temperature and equilibrium constant of equilibrium hydrogenation reaction
图 5 H2分子在Ti表面的较优吸附位
（左：俯视；右：正视）
Figure 5. Preferred adsorption sites of H2 molecules on the Ti surface
图 6 H2分子在Ti内部的固溶位置
（a）八面体间隙；（b）四面体间隙
Figure 6. Solid solution positions of H2 molecules inside Ti
表 1 不同温度下质量增长率及脆性
Table 1. Quality growth rate and brittleness at different temperatures
反应温度/℃ 钛质量/g 氢化钛质量/g 质量增加率/% 脆性 400 1.286 1.335 3.8 小 450 2.745 2.858 4.1 小 500 2.225 2.318 4.2 一般 550 2.811 2.929 4.2 大 
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表 2 氢原子占据α-Ti-H 体系八面体和四面体间隙的溶解热计算结果
Table 2. Calculation results of dissolution heat of hydrogen atoms occupying between octahedral and tetrahedral gaps in α-Ti-H system
晶体型 位置 Et/eV ΔH(eV·atom-1) α-Ti(2Ti) − 3212.24528 0 16Ti-H 八面体间隙 − 25714.25413 − 0.4082 8Ti-H 八面体间隙 − 12865.36544 − 0.5007 4Ti-H 八面体间隙 − 6425.06412 − 0.57356 2Ti-H 八面体间隙 − 3212.90524 − 0.65996 16Ti-H 四面体间隙 − 3206.24854 − 0.31926 8Ti-H 四面体间隙 − 12841.24458 − 0.36677 4Ti-H 四面体间隙 − 6428.81731 − 0.43658 2Ti-H 四面体间隙 − 3222.60511 − 0.47292
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表 3 氢原子位于八面体间隙的α-Ti-H 体系的体积变化
Table 3. Volume change of α Ti-H system of hydrogen atoms located in octahedral gaps
% α-Ti(2Ti) 16Ti-H 8Ti-H 4Ti-H 2Ti-H 0 0.17 0.87 1.17 3.84
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