几种金属及其锂合金的吸放氢效应研究
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摘要
钛、锆、钒基储氢合会以其储氢量大,吸放氢速度快等优点而成为目前储氢合金研究领域的一大热点。在中子物理实验研究中,中子发生器是常用的中子源之一。这类中子源常采用钛、钒和锆吸收氢的同位素作靶,通过恰当的核反应得到中子。因此,开展钛、锆、钒吸氢性能的系统研究对研制这类靶基材料有着指导意义。同时,找到一种增加靶基材料吸氢量的简便方法,对增大发生器的中子产额,延长靶的寿命有着现实的应用价值。
本论文在调研了相关文献的基础上,首次采用热扩散的方法形成钛、锆、钒.的锂合金,然后对钛、锆、钒与钛、锆、钒的锂合金进行了不同条件下的吸放氢实验,对其吸放氢性能进行了比较,研究了锂对钛、锆、钒的最大吸氢量的影响;最后,对样品进行分析测试:用X射线衍射(XRD)做物相分析,用扫描电子,显微镜(SEM)做表观形貌分析,用二次离子质谱(SIMS)做相对含量分析。得出结论如下:
1、不论是钛、锆、钒还是钛、锆、钒的锂合金,在相同的充氢压,不同的温度下吸氢后,最大放氢量会随着吸氢温度的升高而增大,放氢速率也随之增大;同样,钛、锆、钒与钛、锆、钒的锂合金在相同温度,不同充氢压下吸氢后,最大放氢量随着吸氢温度升高而增大。在相同吸放氢条件下,它们锂合金的最大吸放氢量大于纯钛、锆、钒。
2、XRD分析结果显示:钛为密排六方结构,吸氢后产生的钛的氢化物TiH_2的结构是体心四方结构,放氢后TiH_2分解产生了具有四方结构的TiH。钒为体心立方结构;吸氢后为面心立方结构;放氢后是体心四方和面心立方结构共存;吸放氢使锆的晶格常数增加,晶胞体积增大;在锂合金的XRD图上有Li(锂)和LiH的峰出现,说明锂成功地扩散。
3、SEM分析的结论是:未吸氢的样品表面比较致密,裂纹比较少:吸放氢后裂纹增多;高放大倍数下观察发现,裂纹周围粉化很严重,说明吸放氢循环会使样品粉化,在其表面产生很多的氢出入通道。
4、SIMS分析的结论是:吸氢后的钛、锆、钒样品中有H元素,说明吸氢实验是成功的。
钛中氢的深度分布在1.2微米,钒中氢的深度分布在2.7微米,锆中氢的深度分布在2.8微米以内的分布基本是均匀的,满足中子发生器的氚靶厚度要求。
Titanium、Zircouium and vanadium-based solid solution Hydrogen storage alloys become studying hotspot because of their high Hydrogen storage capacity and high velocity of Hydrogcn absorption and desorption.Titanium,Zirconium and vanadium have the properties of high Tritium storage density,high temperature of desorbing Hydrogen,strong ability of keeping Helium and low rate of droping powder, it meets the need of neutron generator's Tritium target,thus it can be used for Tritium target.
The first time,we prepared the Ti-Li,Zr-Li and V-Li alloy were prepared by using thermal diffusion technology.And then,we did the experiment of Ti、Zr andV and Ti-Li、Zr-Li andV-Li alloy Hydrogen absorption and desorption under different conditions,and we did some research on the influence of Hydrogen absorption capability to Vananium.Finally,we did some tests on the experiment samples.We did X-ray diffraction(XRD) analyse for the phase-structure of samples,scanning electron microscope(SEM) analyse for the shape of exterior,secondary ion mass spectroscopy (SIMS) analyse for the comparative content.The results we get as following:
(1) Both Titanium,Zirconium and Vanadium and Ti-Li、Zr-Li andV-Li alloy,absorbing Hydrogen in the same pressure and different temperature,the maximum Hydrogen desorption and the analytic velocity increase with the increasing of temperature.Both Vanadium and V-Li alloy,absorbing Hydrogen in the same temperature and different pressure,the maximum Hydrogen desorption increase with the increasing of pressure.Absorbing Hydrogen in the same condition,the maximum Hydrogen desorption of Li allay is more than Titanium、Zirconium and Vanadium.
(2) The XRD analyse reveals that the structure of Titanium before hydrogen-absorption is close-packed hexagonal,the TiH_2 that formed via hydrogen-absorption is body-centered tetragonal,and the TiH that formed due to hydrogen-desertion of TiH_2 is cubic.The phase-structure of pure Vanadium is body centered cubic.It turns into face centured cubic after absorbing Hydrogen. It's body centered tetragonal and face centured cubic coexist after dcsorbing Hydrogen.After absorbing and desorbing Hydrogen,their lattice parameters increas,and the lattice volumes also increas.The peak of Lithium and LiH appear in the picture of XRD,which is proved that Lithium diffusing successfully.
(3) By SEM analyse,it's compact and flawless for Vanadium before absorbing Hydrogen.There are many flaws after absorbing and desorbing Hydrogen.It's observed that the flaw pulverize badly by high degree miscoscope.It can be concluded that the shape of sample pulverize badly and appear some passages for Hydrogen after absorbing and desorbing Hydrogen.
(4) By SIMS analyse,the depth of Hydrogen in Titanium、Zirconium and Vanadium is more than 1.2μm、2.8μm and 2.7μm,it meets the need of Tritium target's depth,so they can be used for Tritium target.
本论文在调研了相关文献的基础上,首次采用热扩散的方法形成钛、锆、钒.的锂合金,然后对钛、锆、钒与钛、锆、钒的锂合金进行了不同条件下的吸放氢实验,对其吸放氢性能进行了比较,研究了锂对钛、锆、钒的最大吸氢量的影响;最后,对样品进行分析测试:用X射线衍射(XRD)做物相分析,用扫描电子,显微镜(SEM)做表观形貌分析,用二次离子质谱(SIMS)做相对含量分析。得出结论如下:
1、不论是钛、锆、钒还是钛、锆、钒的锂合金,在相同的充氢压,不同的温度下吸氢后,最大放氢量会随着吸氢温度的升高而增大,放氢速率也随之增大;同样,钛、锆、钒与钛、锆、钒的锂合金在相同温度,不同充氢压下吸氢后,最大放氢量随着吸氢温度升高而增大。在相同吸放氢条件下,它们锂合金的最大吸放氢量大于纯钛、锆、钒。
2、XRD分析结果显示:钛为密排六方结构,吸氢后产生的钛的氢化物TiH_2的结构是体心四方结构,放氢后TiH_2分解产生了具有四方结构的TiH。钒为体心立方结构;吸氢后为面心立方结构;放氢后是体心四方和面心立方结构共存;吸放氢使锆的晶格常数增加,晶胞体积增大;在锂合金的XRD图上有Li(锂)和LiH的峰出现,说明锂成功地扩散。
3、SEM分析的结论是:未吸氢的样品表面比较致密,裂纹比较少:吸放氢后裂纹增多;高放大倍数下观察发现,裂纹周围粉化很严重,说明吸放氢循环会使样品粉化,在其表面产生很多的氢出入通道。
4、SIMS分析的结论是:吸氢后的钛、锆、钒样品中有H元素,说明吸氢实验是成功的。
钛中氢的深度分布在1.2微米,钒中氢的深度分布在2.7微米,锆中氢的深度分布在2.8微米以内的分布基本是均匀的,满足中子发生器的氚靶厚度要求。
Titanium、Zircouium and vanadium-based solid solution Hydrogen storage alloys become studying hotspot because of their high Hydrogen storage capacity and high velocity of Hydrogcn absorption and desorption.Titanium,Zirconium and vanadium have the properties of high Tritium storage density,high temperature of desorbing Hydrogen,strong ability of keeping Helium and low rate of droping powder, it meets the need of neutron generator's Tritium target,thus it can be used for Tritium target.
The first time,we prepared the Ti-Li,Zr-Li and V-Li alloy were prepared by using thermal diffusion technology.And then,we did the experiment of Ti、Zr andV and Ti-Li、Zr-Li andV-Li alloy Hydrogen absorption and desorption under different conditions,and we did some research on the influence of Hydrogen absorption capability to Vananium.Finally,we did some tests on the experiment samples.We did X-ray diffraction(XRD) analyse for the phase-structure of samples,scanning electron microscope(SEM) analyse for the shape of exterior,secondary ion mass spectroscopy (SIMS) analyse for the comparative content.The results we get as following:
(1) Both Titanium,Zirconium and Vanadium and Ti-Li、Zr-Li andV-Li alloy,absorbing Hydrogen in the same pressure and different temperature,the maximum Hydrogen desorption and the analytic velocity increase with the increasing of temperature.Both Vanadium and V-Li alloy,absorbing Hydrogen in the same temperature and different pressure,the maximum Hydrogen desorption increase with the increasing of pressure.Absorbing Hydrogen in the same condition,the maximum Hydrogen desorption of Li allay is more than Titanium、Zirconium and Vanadium.
(2) The XRD analyse reveals that the structure of Titanium before hydrogen-absorption is close-packed hexagonal,the TiH_2 that formed via hydrogen-absorption is body-centered tetragonal,and the TiH that formed due to hydrogen-desertion of TiH_2 is cubic.The phase-structure of pure Vanadium is body centered cubic.It turns into face centured cubic after absorbing Hydrogen. It's body centered tetragonal and face centured cubic coexist after dcsorbing Hydrogen.After absorbing and desorbing Hydrogen,their lattice parameters increas,and the lattice volumes also increas.The peak of Lithium and LiH appear in the picture of XRD,which is proved that Lithium diffusing successfully.
(3) By SEM analyse,it's compact and flawless for Vanadium before absorbing Hydrogen.There are many flaws after absorbing and desorbing Hydrogen.It's observed that the flaw pulverize badly by high degree miscoscope.It can be concluded that the shape of sample pulverize badly and appear some passages for Hydrogen after absorbing and desorbing Hydrogen.
(4) By SIMS analyse,the depth of Hydrogen in Titanium、Zirconium and Vanadium is more than 1.2μm、2.8μm and 2.7μm,it meets the need of Tritium target's depth,so they can be used for Tritium target.
引文
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