Mass Transport and Thermodynamics at the Interface in the High-Temperature Metal/Ceramics Composites

高温金属/陶瓷复合材料界面的传质和热力学

• 批准号: 09450267
• 负责人: MARUYAMA Toshio
• 金额: $ 8.51万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09450267/
• 关键词: Metal; Ceramics interface; Oxygen potential; High temperature oxidation; Scale; Diffusion coefficient; Standard Gibbs energy change; NdCrOィイD23ィエD2; BaTiOィイD23ィエD2; セラミックス複合材料; ギブスエネルギ; 活量依存性; LaCrO_3; 固体間反応; Ni-Cr合金

Metals/ceramics composites are the promising materials for structure application at high temperatures. Typical materials are superalloys with ceramic coatings, metallic particles dispersion ceramic matrix composites, and functionally gradual materials comprised of ceramics and metals. The interface between ceramics and metals has chemically and mechanically different feature from each bulk material.The objective of the present research is that the interface between ceramics and metals is generalized as a basis of the thermodynamics and transport phenomena to discuss the chemical stability of the interface. Two different topics are carried out to generalize the interfacial phenomena. One is the measurements of thermodynamic properties and diffusion coefficient of the complex oxides which are the products at the interface. Another is high temperature oxidation at the interface between oxide ceramics and metals.(1) Thermodynamic properties and diffusion coefficient of the complex oxidesPe … More rovskite type chromites (ABOィイD23ィエD2) are focused in the present work. They have important role at the interface between CrィイD22ィエD2OィイD23ィエD2 scale and alloy to improve the scale adhesion. With respect to the thermodynamic properties, the standard Gibbs energy change of formation, ΔG°, on NdCrOィイD23ィエD2 was determined by measuring the electroconductivities of the different two-phase samples, NdCrOィイD23ィエD2 with CrィイD22ィエD2OィイD22ィエD2 and NdィイD22ィエD2OィイD23ィエD2. As compared with the reported ones of YCrOィイD23ィエD2 and LaCrOィイD23ィエD2, the value of ΔG°is consistent in the relationship between ΔG°and ionic radius of A ion.Diffusion coefficients of A ions in LaCrOィイD23ィエD2 and NdCrOィイD23ィエD2 was determined by the solid state reaction technique. Discussed their diffusion coefficients with the reported value of Y ion in YCrOィイD23ィエD2, the absolute values can be explained with the concentration of A site vacancy. The activation energy depends on the ionic radius of A ions.In order to compare with their chromites, diffusion coefficient of Ba ion in BaTiOィイD23ィエD2 is also measured by the same method. The values of BaTiOィイD23ィエD2 is very similar to their chromites. Diffusion coefficient of A ion in the perovskite oxides has little dependence of the valances of A and B ions.(2) High temperature oxidation at the interface between oxide ceramics and metalsOxidation of Ni covered by YィイD22ィエD2OィイD23ィエD2-stabilized ZrOィイD22ィエD2 (YSZ) is investigated in this work. The one dimensional model of the oxidation kinetics is established to assume that flux of OィイD12-ィエD1 in YSZ is equal to one of NiィイD12+ィエD1 in the NiO scale. In order to verify the kinetic model, the oxidation rate and oxygen partial pressure at the interface were investigated on the close cell with YSZ thin plate including Ni in the inside. The experimental results are in agreement with the kinetic model. The life design of the interface of the ceramic coating on the metals and metal particle dispersion ceramics matrix composite can be enable as a basis of the kinetic model. Less

金属/陶瓷复合材料是一种很有前途的高温结构材料。典型的材料是具有陶瓷涂层的超合金、金属颗粒分散陶瓷基复合材料以及由陶瓷和金属组成的功能渐变材料。陶瓷与金属的界面具有不同于块体材料的化学和力学特性，本文的研究目的是将陶瓷与金属的界面作为热力学和输运现象的基础，讨论界面的化学稳定性。两个不同的主题进行了推广的界面现象。一是界面产物复合氧化物的热力学性质和扩散系数的测定。另一种是氧化物陶瓷与金属界面的高温氧化。(1)复合氧化物Pe的热力学性质和扩散系数 ...更多信息 本文重点研究了红柱石型铬铁矿（ABO型铬铁矿D23）。它们在Cr_（22）Cr_（23）Cr_（22）D_2O_（23）D_2氧化膜与合金的界面上起着重要的作用，提高了氧化膜的附着力。关于热力学性质，通过测量不同两相样品的电导率来确定NdCrO氧化物D23氧化物D2上的标准生成吉布斯能变化ΔG°，NdCrO氧化物D23氧化物D2与Cr氧化物D22氧化物D22氧化物D22氧化物D23氧化物D2。用固相反应法测定了A离子在LaCrO_（23）Nd_（23）D_2中的扩散系数。用文献报道的Y离子在YCrO单晶D23单晶D2中的扩散系数讨论了它们的扩散系数，其绝对值可用A位空位浓度来解释。为了与铬酸盐相比较，用同样的方法测定了Ba离子在BaTiO_2D_3D_2D_2中的扩散系数。BaTiO_2 O_（23）O_（24）A离子在钙钛矿氧化物中的扩散系数与A和B离子的价态关系不大。(2)本文研究了YSZ/D22/D2 O/D23/D2-ZrO/D22/D23/D2复合氧化物陶瓷表面Ni的高温氧化。建立了氧化动力学的一维模型，假定YSZ中O氧化物D_（12）-Ni氧化物D_（11）的通量等于NiO膜中Ni氧化物D_（12）+Ni氧化物D_（11）的通量。为了验证动力学模型，在内部含有Ni的YSZ薄板的封闭电池上研究了氧化速率和界面氧分压。实验结果与动力学模型一致。该动力学模型可作为金属-金属颗粒弥散陶瓷基复合材料陶瓷涂层界面寿命设计的基础。少

项目成果

Takashi Akaya et al.: "Solid-State Reaction Kinetics of LaCrOィイD23ィエD2 from the Oxides and Determination of LaィイD13+ィエD1 Diffusion Coefficient"J. Electrochemical Society. 145. 2090-2094 (1998)

Takashi Akaya 等人：“来自氧化物的 LaCrD23D2 的固态反应动力学和 LaCrD13+D1 扩散系数的测定”J. 电化学协会 145。2090-2094 (1998)

Akihiko Kitahara et al.: "Diffusion Coefficient of BaィイD12+ィエD1 Ion in BaTiOィイD23ィエD2, Proc. Electrochem. Soc."The Electrochemical Society, NJ. (in press). (2000)

Akihiko Kitahara 等人：“BaTiOiD12+IeD1 离子在 BaTiOiD23D2 中的扩散系数，Proc. Electrochem. Soc.”电化学协会，新泽西州（2000 年出版）。

Akihiko Kitahara: "Diffusion Coefficient of Ba^<2t> Ion in BaTiO_3"ECS Proc.. 99. (2000)

北原明彦：“BaTiO_3 中 Ba^<2t> 离子的扩散系数”ECS Proc.. 99. (2000)

Takaya Akashi et al.: "Diffusion Coefficient of LaィイD13+ィエD1 Ion in LaCrOィイD23ィエD2 Determined by Solid State Reaction"in Proc. of 5th Intl. Symp. SOFC (ECS Proc. 97-18), Ed. By U. Stimming, S. C. Singhal, H. Tagawa and W. Lehnert, The Electrochemical Soci

Takaya Akashi 等人：《LaCrOD23D2 中 LaD13+D1 离子的扩散系数通过固态反应测定》，第 5 版 SOFC 论文（ECS Proc. 97-18），作者：U. Stimming，S. C. Singhal。 ，H. Takawa 和 W. Lehnert，电化学学会。

Takaya Akashi: "Standard Gibbs Energy Change of A Reaction between Oxides determined by Electrical Cacluctivity" Electrochem.Soc.Proc.98・9. 550-557 (1998)

Takaya Akashi：“由电电容确定的氧化物之间反应的标准吉布斯能量变化”Electrochem.Soc.Proc.98・9（1998）。