ZrV系合金吸气特性和应用研究

发布时间：2018-04-23 05:17

本文选题：吸气剂 + ZrV系　；参考：《北京有色金属研究总院》2015年博士论文

【摘要】：吸气材料是电真空器件内部真空环境长效无源维持的有效解决方案之一。随着电真空器件向小型化、集成化趋势的快速发展,传统吸气材料的高温激活过程会增加微型化的电真空器件中热敏感组件的损伤概率,对器件的可靠性产生不利影响。同时,随着电真空器件服役时间的日益延长,对吸气材料的吸气(H2、CO)能力、激活效率以及重复激活性能也提出了更高的要求。因此,研发具备更低的激活温度、更高的吸气能力和激活效率、更佳的重复激活特性等综合性能的新型吸气材料已成为学术和工程领域迫切需要解决的热点问题。本论文针对上述问题开展了系统的研究工作,旨在探索吸气材料微观结构与吸气和激活特性之间的联系,开发一种满足工程应用要求的新型吸气材料。通过对现有主流低温激活吸气材料ZrVFe合金相组成、吸气动力学、激活效率和重复激活性能的研究,探讨了合金相组成对吸气特性的影响规律,从而通过元素替代和稀土添加等手段对ZrV系吸气材料的激活和吸气特性进行了改进,并对综合性能相对更好的新型ZrVMnCe吸气材料进行了工程应用方面的初步探索。课题的主要研究内容如下：(1)基于ZrV_2-ZrFe_2-Zr三元合金相图,对合金中Zr、V、Fe三组元的配比进行了设计,制备了不同成分的Zr56.97xV35.85yFe7.18z(x=1,y=1,Z=1; X=1.2,y=1,Z=1; x=0.8,y=1,z=1; x=1,y=1.4,z=1; x=1,y=0.6,z=1; x=l,y=1,z=1.5; x=1,y=1,z=0.5)合金。研究成分变化对合金相组成、吸气性能、吸气动力学、激活效率和重复激活性能的影响。XRD全谱分析发现,当z=0.5和z=1时,合金由a-Zr相和C15 Laves目组成,且吸气性能随着C15 Laves相含量的增加呈现出上升趋势。当z=1.5时,合金由a-Zr相、C15 Laves相和C14 Laves相三相组成。C14 Laves相的出现对合金的吸气性能有着显著的提高作用,特征吸H2速率和吸CO速率分别达到2137.9cm3/s·g和1300.6cm3/sˉg,相比传统配比的Zr56.97V35.85Fe7.18合金分别提高了71.9%和59.3%。通过对合金吸气激活能的计算,发现C14 Laves相的出现改善了合金的吸气动力学性能。当z=1.5时,吸气(H2、CO)扩散激活能Ed分别降低为1.95 kcal/mol和5.22 kcal/mol。同时,研究结果表明,Fe含量的增加和V含量的减少不利于合金激活效率和重复激活性能的提高。(2)运用元素替换的方式制备了Zr56.97V35.85X7.18 (X=Cr、Mn、Fe、Co、Ni)合金,以期进一步提高合金中的C14 Laves相含量,改善合金的吸气动力学性能。通过XRD全谱分析发现,Cr、Mn、Co、Ni的替换有利于提高合金中C14 Laves相的含量,从而改善了ZrV系合金的室温吸气(H2、CO)性能。其中,Mn的替换改善效果最为明显。Zr56.97V35.85Mn7.18合金的特征吸气(H2、CO)速率分别达到2295.7cm3/s·g和1349.0cm3/s·g,比Zr56.97V35.85Fe7.18合金高出84.6%和65.2%。Zr56.97V35.85Mn7.18合金的吸气扩散激活能Ed降低为1.57kcal/mol和5.00kcal/mol.(3)研究了稀土元素La、Ce、Pr、Nd的添加对ZrV系合金相组成、吸气和激活特性的影响。通过XRD全谱分析发现,La、Ce、Pr、Nd的添加都导致合金中出现新的稀土氧化物RE203相。La、Ce、Pr、Nd的添加均提高了ZrV系合金的室温吸气(H2、CO)性能。其中,Ce的添加改善效果最为明显。Zr56.97V35.85Mn7.18Ce2.65合金的特征吸气(H2、CO)速率分别达到2479.7cm3/s·g和1494.2cm3/s·g,比Zr56.97V35.85Mn7.18合金高出8.01%和10.8%。La、Ce、Pr、Nd的添加明显改善了ZrV系合金吸气动力学性能。Zr56.97V35.85Mn7.18Ce2.65合金的吸气扩散激活能Ed分别降低为1.35kcal/mol和4.24kcal/mol。La、Ce、Pr、Nd的添加明显提高了ZrV系合金的激活效率,对合金重复激活性能亦有一定的改善。(4)探索了Zr56.97V35.85Mn7.18Ce2.65合金在工程应用中的可行性。采用注塑成型和真空烧结工艺制备了Zr56.97V35.85Mn7.18Ce2.6560%-Zr40%烧结多孔型吸气元件。通过对材料的孔隙率、比表面积、碳含量和吸气性能的研究,初步确定了优选制备工艺条件。所制备的Zr56.97V35.85Mn7.18Ce2.6560%-Zr40%吸气材料的特征吸气(H2、CO)速率分别达到1454.2 ml/s·g和901.9 ml/s·g,比传统商用的Zr56.97V35.85Fe7.1860%-Zr40%吸气材料分别提高了19.4%和9.6%。同时,在450℃激活温度下,Zr56.97V35.85Mn7.18Ce2.6560%-Zr40%吸气材料也表现出了相对更高的激活效率和更优的低温激活性能。
[Abstract]:The suction material is one of the effective solutions for the passive maintenance of the vacuum environment in the vacuum environment. As the electric vacuum device is miniaturized and the integration trend is fast developing, the high temperature activation process of the traditional suction material will increase the damage probability of the thermosensitive components in the miniature electric vacuum device, and the reliability of the device is not produced. At the same time, with the increasing service time of electric vacuum devices, higher requirements for the absorption (H2, CO) capacity, activation efficiency and reactivation performance of the aspirated materials are also raised. Therefore, a new type of new type of comprehensive performance, such as lower activation temperature, higher inhalation and activation efficiency, and better repetitive activation properties, is developed. The suction material has become a hot issue in the academic and engineering fields. This paper has carried out a systematic research on the above problems in order to explore the relationship between the microstructure of the suction material and the characteristics of suction and activation, and to develop a new type of suction material to meet the requirements of the engineering application. The phase composition, inspiratory dynamics, activation efficiency and reactivation properties of ZrVFe alloy were studied. The influence of phase composition on the absorption characteristics of the alloy was discussed, and the activation and suction characteristics of ZrV gas absorbing materials were improved by means of element substitution and rare earth addition, and a new type of Z with a better comprehensive performance was introduced. The main research contents of the rVMnCe suction material are as follows: (1) based on the ZrV_2-ZrFe_2-Zr three element alloy phase diagram, the ratio of Zr, V and Fe three components in the alloy is designed, and the Zr56.97xV35.85yFe7.18z (x =1, y=1, Z=1, X=1.2, y=1) is prepared. =1, y=0.6, z=1, x=l, y=1, z=1.5, x=1, y=1, z=0.5) alloys. The effects of component changes on the phase composition, inspiratory performance, inspiratory kinetics, activation efficiency and reactivation properties of the alloy were investigated by.XRD When z=1.5, the appearance of.C14 Laves phase composed of a-Zr phase, C15 Laves phase and C14 Laves phase of the alloy has a significant effect on the absorption performance of the alloy. The characteristics of the absorption H2 rate and the absorption CO rate are 2137.9cm3/s. G and Laves, respectively, by 71.9% and 59., respectively. By calculating the activation energy of the gas absorption of the alloy, 3%. found that the emergence of C14 Laves phase improved the dynamic performance of the alloy. When z=1.5, the absorption (H2, CO) diffusion activation energy of Ed decreased to 1.95 kcal/mol and 5.22 kcal/mol. respectively. The results showed that the increase of Fe content and the decrease of V content were not conducive to the activation efficiency and repeated excitation of the alloy. The improvement of active energy. (2) Zr56.97V35.85X7.18 (X=Cr, Mn, Fe, Co, Ni) alloys were prepared by means of element substitution. In order to further improve the content of C14 Laves phase in the alloy and improve the dynamic performance of the alloy, the replacement of Cr, Mn, Co, and Co is helpful to improve the content of the alloys by the XRD full spectrum analysis. The properties of room temperature absorption (H2, CO) of ZrV alloy are obtained. Among them, the improvement effect of Mn is most obvious, the characteristic absorption of.Zr56.97V35.85Mn7.18 alloy (H2, CO) is 2295.7cm3/s. G and 1349.0cm3/s. G, which is 84.6% and 65.2% higher than that of Zr56.97V35.85Fe7.18 alloy. L/mol and 5.00kcal/mol. (3) studied the effects of the addition of rare earth elements La, Ce, Pr, Nd on the phase composition, suction and activation of the ZrV alloy. Through XRD full spectrum analysis, the addition of La, Ce, Pr and Nd all resulted in the appearance of new rare earth oxides in the alloys. In the addition of Ce, the most obvious improvement effect of.Zr56.97V35.85Mn7.18Ce2.65 alloy is the characteristic inspiratory (H2, CO) rate of 2479.7cm3/s. G and 1494.2cm3/s. G, 8.01% higher than Zr56.97V35.85Mn7.18 alloy, 10.8%.La, Ce, and Pr. The activation energy of gas diffusion Ed was reduced to 1.35kcal/mol and 4.24kcal/mol.La respectively, Ce, Pr, Nd increased the activation efficiency of the ZrV alloy, and the reactivation properties of the alloy also improved. (4) the feasibility of Zr56.97V35.85Mn7.18Ce2.65 alloy in the engineering application was explored. Injection molding and vacuum sintering process were used to prepare Zr. Through the study of the porosity, specific surface area, carbon content and suction performance of the material, the optimum preparation conditions are preliminarily determined. The characteristic aspirating (H2, CO) rates of the prepared Zr56.97V35.85Mn7.18Ce2.6560%-Zr40% aspirating materials are 1454.2 ml/s. G and 901.9 ml/, respectively. S g, increased by 19.4% and 9.6%., respectively, compared with the traditional Zr56.97V35.85Fe7.1860%-Zr40% inhalation materials. At 450 C, the Zr56.97V35.85Mn7.18Ce2.6560%-Zr40% inhalation material also showed higher activation efficiency and better low temperature activation.

【学位授予单位】：北京有色金属研究总院
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TG146.414

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