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用于海底高温高压环境下的YSZ氧传感器的研制
李娟
导师李和平
2014
学位授予单位中国科学院研究生院
学位授予地点北京
学位名称博士
学位专业地球化学
关键词氧传感器 氧逸度 Ysz陶瓷管 整体烧结 高温高压 水热体系
摘要海底黑烟囱、热液矿产及其周围共存的相关生物群落的发现,是近几十年海洋科学取得的最重要的科学成就之一。对于海底热液,其氧逸度的高低,携带了大量有关地球内部物质与作用过程的信息,海底高温高压水热体系中氧逸度的获得是人们研究各种洋中脊热液作用过程的必备前提。 近几年本课题组一直致力于高温高压水热体系相关方面的研究,已研制出具有很好Nernst响应特性的YSZ氧传感器,但早期研制的YSZ氧传感器存在内阻太高(适用于500 oC以上)和结构过于零散的问题。本论文针对该弊端对此传感器的结构和制备工艺进行了优化,优化后的传感器具有较低的内阻(适用于200 oC以上)、优良的抗热冲击性能、耐压性能、耐腐蚀性能和Nernst响应特性且传感器外形尺寸按美国Alvin号深潜器探头需求加工制作。论文具体工作内容包括: (1) 论文工作早期,以热等静压烧结+线切割得到的Cr/Cr2O3圆柱体为基体,采用涂覆、注浆或注浆+梯度材料法在其表面制备了薄厚不一的YSZ陶瓷膜层。但制备出的YSZ陶瓷膜层太薄不能保证传感器的机械强度,YSZ陶瓷膜层太厚则易因陶瓷和Cr/Cr2O3基体的性能和组织差异、热膨胀系数不匹配以及应力释放等原因导致陶瓷膜开裂,因此调整实验方案。 (2) 采用注浆法制备YSZ陶瓷管,然后将球磨混合均匀的Cr/Cr2O3固体氧参考缓冲剂粉末装入YSZ陶瓷管中,并以一定的工艺进行整体烧结。制备出了YSZ管表面无裂纹、Cr/Cr2O3固体氧参考缓冲剂粉末和YSZ陶瓷管之间无缝隙、Cr/Cr2O3固体氧参考缓冲剂粉末较致密且导电的具有较强机械强度的YSZ-Cr/Cr2O3复合陶瓷制品。 (3) 采用Pt浆法,以“涂覆+焙烧”工艺制备出了结构疏松、气孔发达、活性位点多且具有较高催化活性的传感器电极膜层。 (4) 在实验室对传感器进行了抗热冲击性能、耐压性能和电极膜层耐腐蚀性能的考察。结果表明自行研制的YSZ氧传感器具有较好的抗热冲击性,少量Al2O3的加入对YSZ陶瓷管的力学性能有一定的改善作用;具有较高的耐压性能;Pt电极膜层具有较强的耐腐蚀性。 (5) 将传感器与课题组高温高压水热体系测试平台对接,考察了传感器是否具有Nernst响应特性。结果表明通过向高压釜内投放足够多的Ni/NiO固体氧参考缓冲剂控制高温高压水热体系氧逸度后,传感器于450 oC测得的稳定电动势值与根据热力学数据手册计算出的理论电动势值较为接近,相对误差小于2.5%,说明本工作研制的YSZ氧传感器具有很好的Nernst响应特性。 (6) 利用研制出的传感器对初始浓度为3.5% NaCl溶液的高温高压水热体系氧逸度进行了测量。结果表明在同一次实验的反复升温和降温过程中,同一温度下的测量数据具有较好的重复性;使用输入阻抗高达1016 Ω的Keithley 6430表采集数据时,氧传感器最低使用温度可达240 oC左右。 总之,通过本论文的工作,已初步完成了用于海底高温高压环境下的YSZ氧传感器在实验室的可行性验证工作,结果比较满意。可以预见,未来通过对管式YSZ氧传感器的制备工艺做进一步的改进和完善,本文作者所在的课题组有望在国际上首次研制出一套拥有我国自主知识产权的海底热液氧逸度原位探测系统。
其他摘要The discovery of black chimney, hydrothermal ore deposits and the symbiotic related biotic community, is one of the most scientific achievements over the past few decades in the field of ocean science. To submarine hydrothermal, the value of oxygen fugacity carry lots of information about materials and mechanisms of the earth's interior, so, how to get the parameter of oxygen fugacity of hydrothermal systems under high temperature and high pressure (HTHP), has been a prerequisite for reveal their interaction mechanisms of the hydrothermal existing in the different mid-ocean ridges.   In recent years, our research group concentrated on the study of hydrothermal under HTHP, and had designed and manufactured a good Nernst response YSZ oxygen sensor, however, the YSZ oxygen sensor previously developed exist some defects, such as, higher inner resistance (when used above 500 oC) and fractional structure. To solve the above defects, we optimized the sensor structure and manufacture process, the improved sensor has the qualities of lower inner (can used above 200 oC), superior resistant to thermal-shock, pressure, corrosion and Nernst response, furthermore, its dimensions of outlines match the deep-diving vehicle probe of Alvin, American. Detailed contents of this thesis are shown as following:   (1) During the beginning stage of the thesis research, we used hot-isostatic press and wire-cutting to get the cylindrical Cr/Cr2O3 as the basal body, then, coating, slip casting, or slip casting combine gradient materials measures were used on the surface of Cr/Cr2O3 to get the different thickness YSZ ceramic membranes. But the membranes we got, either too thin cannot meet the needed mechanical strength of the sensor, or too thick resulting in ceramic membrane arise from YSZ membrane and Cr/Cr2O3 body has different properties and organizations, coefficient of thermal expansions and stress relief, and so on. So, we changed the experimental program.    (2) The YSZ ceramic tube was fabricated by plaster casting method, then poured into Cr/Cr2O3 power buffering agents, which were mixed well through ball milling, after these progress, the tube was firing as a whole. Depending on the above method, we got the composite ceramic YSZ-Cr/Cr2O3, which possess the characteristic of no crack on the YSZ tub surface, no seam between oxygen buffering power (Cr/Cr2O3) and YSZ ceramic tube.    (3) Depending on Pt slurry method and coating combined roasting progress, we prepared the electrode film for sensor, which has loose structure, plenty of blowholes, abundant of active sites, and high catalytic activity.     (4) Related to the sensor resistant to thermal-shock, compressive, and electrode tolerate corrosion experiments were carried in laboratory. Results show that the self-developed YSZ oxygen sensor had superior resistant to thermal-shock, mixed with a small amount of Al2O3 can improve the YSZ ceramic tube’s mechanical properties; the YSZ had high pressure resistance, and the electrode film had strong corrosion resistance.    (5) Depending on connected the sensor and HTHP hydrothermal systems test platform in our research group, we investigated the sensor to ensure whether it had Nernst respond. The results show, when enough Ni/NiO solid oxygen buffering power was putted into the autoclave to control the HTHP hydrothermal oxygen fugacity, the sensor measured electrodynamics’ potential value is close to the theoretical calculated results according to handbook of thermodynamic data at 450 oC, and the relative error is less than 2.5%. The results demonstrated the YSZ oxygen sensor developed in this work had perfect Nernst response.    (6) Depending on the developed sensor, we measured the HTHP hydrothermal oxygen fugacity of 3.5% NaCl solution. The results show, when repeated increased or increased the temperature in an experiment, the experimental data can well reappearance at the same temperature; moreover, when used Keithley 6430 (its biggest in
学科领域地球深部物质与流体作用地球化学
语种中文
文献类型学位论文
条目标识符http://ir.gyig.ac.cn/handle/352002/5922
专题研究生_研究生_学位论文
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李娟. 用于海底高温高压环境下的YSZ氧传感器的研制[D]. 北京. 中国科学院研究生院,2014.
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