本文選題：吸氣劑 + ZrV系　； 參考：《北京有色金屬研究總院》2015年博士論文

【摘要】：吸氣材料是電真空器件內(nèi)部真空環(huán)境長效無源維持的有效解決方案之一。隨著電真空器件向小型化、集成化趨勢的快速發(fā)展,傳統(tǒng)吸氣材料的高溫激活過程會增加微型化的電真空器件中熱敏感組件的損傷概率,對器件的可靠性產(chǎn)生不利影響。同時,隨著電真空器件服役時間的日益延長,對吸氣材料的吸氣(H2、CO)能力、激活效率以及重復(fù)激活性能也提出了更高的要求。因此,研發(fā)具備更低的激活溫度、更高的吸氣能力和激活效率、更佳的重復(fù)激活特性等綜合性能的新型吸氣材料已成為學(xué)術(shù)和工程領(lǐng)域迫切需要解決的熱點問題。本論文針對上述問題開展了系統(tǒng)的研究工作,旨在探索吸氣材料微觀結(jié)構(gòu)與吸氣和激活特性之間的聯(lián)系,開發(fā)一種滿足工程應(yīng)用要求的新型吸氣材料。通過對現(xiàn)有主流低溫激活吸氣材料ZrVFe合金相組成、吸氣動力學(xué)、激活效率和重復(fù)激活性能的研究,探討了合金相組成對吸氣特性的影響規(guī)律,從而通過元素替代和稀土添加等手段對ZrV系吸氣材料的激活和吸氣特性進行了改進,并對綜合性能相對更好的新型ZrVMnCe吸氣材料進行了工程應(yīng)用方面的初步探索。課題的主要研究內(nèi)容如下：(1)基于ZrV_2-ZrFe_2-Zr三元合金相圖,對合金中Zr、V、Fe三組元的配比進行了設(shè)計,制備了不同成分的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。研究成分變化對合金相組成、吸氣性能、吸氣動力學(xué)、激活效率和重復(fù)激活性能的影響。XRD全譜分析發(fā)現(xiàn),當(dāng)z=0.5和z=1時,合金由a-Zr相和C15 Laves目組成,且吸氣性能隨著C15 Laves相含量的增加呈現(xiàn)出上升趨勢。當(dāng)z=1.5時,合金由a-Zr相、C15 Laves相和C14 Laves相三相組成。C14 Laves相的出現(xiàn)對合金的吸氣性能有著顯著的提高作用,特征吸H2速率和吸CO速率分別達到2137.9cm3/s·g和1300.6cm3/sˉg,相比傳統(tǒng)配比的Zr56.97V35.85Fe7.18合金分別提高了71.9%和59.3%。通過對合金吸氣激活能的計算,發(fā)現(xiàn)C14 Laves相的出現(xiàn)改善了合金的吸氣動力學(xué)性能。當(dāng)z=1.5時,吸氣(H2、CO)擴散激活能Ed分別降低為1.95 kcal/mol和5.22 kcal/mol。同時,研究結(jié)果表明,Fe含量的增加和V含量的減少不利于合金激活效率和重復(fù)激活性能的提高。(2)運用元素替換的方式制備了Zr56.97V35.85X7.18 (X=Cr、Mn、Fe、Co、Ni)合金,以期進一步提高合金中的C14 Laves相含量,改善合金的吸氣動力學(xué)性能。通過XRD全譜分析發(fā)現(xiàn),Cr、Mn、Co、Ni的替換有利于提高合金中C14 Laves相的含量,從而改善了ZrV系合金的室溫吸氣(H2、CO)性能。其中,Mn的替換改善效果最為明顯。Zr56.97V35.85Mn7.18合金的特征吸氣(H2、CO)速率分別達到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合金的吸氣擴散激活能Ed降低為1.57kcal/mol和5.00kcal/mol.(3)研究了稀土元素La、Ce、Pr、Nd的添加對ZrV系合金相組成、吸氣和激活特性的影響。通過XRD全譜分析發(fā)現(xiàn),La、Ce、Pr、Nd的添加都導(dǎo)致合金中出現(xiàn)新的稀土氧化物RE203相。La、Ce、Pr、Nd的添加均提高了ZrV系合金的室溫吸氣(H2、CO)性能。其中,Ce的添加改善效果最為明顯。Zr56.97V35.85Mn7.18Ce2.65合金的特征吸氣(H2、CO)速率分別達到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的添加明顯改善了ZrV系合金吸氣動力學(xué)性能。Zr56.97V35.85Mn7.18Ce2.65合金的吸氣擴散激活能Ed分別降低為1.35kcal/mol和4.24kcal/mol。La、Ce、Pr、Nd的添加明顯提高了ZrV系合金的激活效率,對合金重復(fù)激活性能亦有一定的改善。(4)探索了Zr56.97V35.85Mn7.18Ce2.65合金在工程應(yīng)用中的可行性。采用注塑成型和真空燒結(jié)工藝制備了Zr56.97V35.85Mn7.18Ce2.6560%-Zr40%燒結(jié)多孔型吸氣元件。通過對材料的孔隙率、比表面積、碳含量和吸氣性能的研究,初步確定了優(yōu)選制備工藝條件。所制備的Zr56.97V35.85Mn7.18Ce2.6560%-Zr40%吸氣材料的特征吸氣(H2、CO)速率分別達到1454.2 ml/s·g和901.9 ml/s·g,比傳統(tǒng)商用的Zr56.97V35.85Fe7.1860%-Zr40%吸氣材料分別提高了19.4%和9.6%。同時,在450℃激活溫度下,Zr56.97V35.85Mn7.18Ce2.6560%-Zr40%吸氣材料也表現(xiàn)出了相對更高的激活效率和更優(yōu)的低溫激活性能。
[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.

【學(xué)位授予單位】：北京有色金屬研究總院
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TG146.414

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本文編號：1790612