面向铝熔体测氢的双层复合质子导体材料的基础研究

Hydrogen is a harmful element in aluminum. Its mechanical performance and reliability are reduced by hydrogen induced defeats. Measuring of hydrogen content of aluminum melts in the production and dehydrogenation in time can be treated as effective methods to avoid hydrogen induced defeats. The hydrogen sensor in aluminum melts biased on high temperature proton conductors has a good development prospect. The oxygen vacancy conducting will be produced by the existing proton conductor in aluminum melts, even failure.in order to solve this key problem, blocking oxygen vacancy conducting by coating will be put forward in this project. Bilayer proton conductors with long-term proton conduction in aluminum melts will be prepared. The main contents include: the multi-doping proton conductors will be prepared, and its preparation process will be explored. The influence of conductivity with crystal structure, oxygen vacancy concentration will be analyzed. The higher conductivity and the proton transfer number material will be developed. In order to further block of oxygen vacancy conduction, coating will be used. The microstructure, corrosion resistance, electrical conductivity and the proton transfer number of bilayer material will be analyzed. The influence of preparation technology, the thickness of coating, oxygen vacancy concentration for the bilayer material will be researched. Bilayer proton conductor materials which can be used in high temperature aluminum melts will be developed. Under the condition of little oxygen and water, carriers transfer mechanism in bilayer materials will be revealed. It also provides a basement for the application of proton conductors in the aluminum melts.

氢为铝材的有害元素，氢致缺陷严重降低其力学性能及可靠性。在生产中快速、在线监测氢含量，从而及时脱氢，是避免氢致缺陷的有效手段。高温质子导体传感法测氢拥有测试速度快、结果准确可靠等优势，具有良好的应用前景。但现有质子导体在铝熔体中易产生氧空位导电，导致其失效。针对这一关键问题，项目提出研制双层复合质子导体，利用涂层阻塞氧空位导电，研制出在铝熔体中呈现高质子迁移数的材料。主要内容包括：研制多元掺杂的质子导体，探索其制备工艺，分析晶体结构、氧空位浓度等因素对其导电性的影响规律，制备质子迁移数较高的材料；通过双层复合，采用涂层进一步阻塞氧空位，分析双层材料的微观组织、耐蚀性、电导率及质子迁移数，研究涂层制备工艺、涂层厚度、氧空位浓度对双层材料的性能影响。研制出可以用于铝熔体的双层质子导体材料，揭示低氧、低水条件下双层材料中各载流子导电机理，丰富固态离子理论，为质子导体在铝熔体测氢中的应用奠定基础。

在铝冶炼及加工过程中，监测铝熔体氢含量，及时脱氢，可避免氢致缺陷。测氢传感器的氢敏感材料在铝熔体中失效的难题，研究了铝熔体中长效工作的质子导体氢敏感材料及传感器。项目研制了CaZr0.9-xMxSc0.1O3-α（M=Sn、Pr）、CaHf1-xScxO3-α、Ba3Ca1+xNb2-xO9-δ、Ba3Sr1+xTa2−xO9−δ、Ba3Ca1+xNb2-xO9-δ-BaZr0.9In0.1O3-δ、CaZr0.9M0.1O3-α-CaZrO3（M=In、Sc）等多种新型质子导体氢敏感材料，分析了材料的晶体结构、微观组织、各载流子电导率、迁移率及迁移数。研制的在双层质子导体在500~750℃时，质子迁移均接近于1。采用自行研制的质子导体研制的氢传感器，在铝熔体中测氢结果稳定，测量值与闭路循环法测量结果一致，项目研制的双层质子导体有效的解决了材料在铝熔体中失效的难题。.项目研制了复合质子导体，防止材料中晶格氧的丢失，避免质子导体失效，为质子导体的研究及应用提供一个新的思路，研发的铝熔体测氢传感器可测试铝熔体中涉氢热力学及动力学基础数据，因此，本项目的研究成果在冶金物理化学、固体离子学领域具有重要的科学意义。.本项目研究的复合质子导体解决了氢敏感材料在铝熔体中失效的难题，研发的铝熔体测氢传感器可连续监测生产过程中铝熔体氢含量，反馈数据，可用于控制铝熔体净化设备进行及时、高效、合适脱氢处理，提高铝产品的质量稳定性及可靠性，为我国企业智能化改造提供硬件及技术基础。因此，本项目研发的复合质子导体及氢传感器具有良好的应用前景。.在研究的基础上，发表文章14篇，其中SCI收录12篇，EI收录12篇。申请国家发明11项，授权4项，授权美国、日本、欧洲等国际专利3项，合作培养毕业博士研究生1人，硕士研究生3人，培养毕业本科生3人。超额完成了项目的预期研究目标。