YSZ热障涂层的层状组织调控及其对热导率和寿命的影响研究
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摘要
近年来,热障涂层(Thermal Barrier Coatings,TBCs)在服役环境极端恶劣的燃气涡轮发动机热端部件上获得了越来越多的应用。当前的TBCs陶瓷层材料主要选择6-8wt%氧化钇稳定的氧化锆。TBCs勺组织、结构和性能依赖于其制备方法。喷涂制备的TBCs呈层状结构,结合性能一般,但热导率较低；EB-PVD TBCs则为柱状晶结构,具有优异的结合性能和良好的应变容限,但热导率偏高。如何有效降低EB-PVD TBCs的热导率一直是相关研究的热点。借鉴喷涂TBCs中的层片状组织结构有利于减少向涂层内部的热传导这一特点,尝试实现EB-PVD TBCs的多层化是其中新兴的一个研究方向。本文设计并采用离子束辅助沉积、低转速、以及沉积温度的高低交错等方法成功制备了多层陶瓷层和微叠层分层陶瓷层两种层状结构TBCs,对陶瓷层引入层状结构后的组织形貌及其对热导率和寿命等的影响进行了研究。
在对离子源的工作特性进行研究的基础上,采用束流密度约为0-0.094mA/cm2的脉冲Ti离子辅助可获得微叠层分层陶瓷层TBCs;其他方法可获得横跨截面的多层陶瓷层TBCs,形成大量扁平带状的孔隙。微叠层结构TBCs伴随着大量的分层界面和相邻分层间的密度调制变化,同时柱状晶晶粒得到细化。离子辅助效应导致的微叠层分层和晶粒细化特征随着离子轰击水平的提升而进一步明显,但基体温度在原子迁移扩散和表面形貌控制上仍是更为重要的因素。离子辅助对成分影响较小,实际引入的Ti含量极低,且不会引起TBCs的致密化。
两种层状结构TBCs仍呈现不可转变的四方相(t’)结构特征。离子辅助带来的额外能量可诱发占优取向从(100)逐渐变化到(111),]BCs内部织构变为{100}型和{111}型织构共存。引入离子与蒸气粒子以及蒸气粒子之间的碰撞导致了晶格重构和溅射,而占优取向的变化机制源于离子束导致的晶粒净生长速率和生长方向的调整以及表面粗糙度引起的生长不稳定性的共同作用。
相对于常规TBCs,两种层状结构TBCs在相应温度下的热扩散系数和热导率都有所降低,其中离子辅助微叠层分层结构导致的热导率降低效果更为明显,室温热导率最高可降低约35%,其机制在于引入的分层界面垂直于热传导方向,带来大量界面热阻,同时,细化的晶粒和由此而来的更多的晶界以及相邻分层间的密度调制共同作用进一步降低了声子传热。
两种层状结构形成的分层界面均有助于降低粘结层的氧化速率。依据这两种分层结构本身的差异及其位置的不同,低转速分层试样粘结层的抗氧化性能更好,但涂层寿命较差；而离子辅助试样粘结层的抗氧化性能稍优于常规TBCs(?),但涂层寿命较优,其机制在于两种分层界面在阻挡传热、增强抗氧化性能的同时,是否降低了YSZ柱晶的应变容限。总体而言,离子束辅助EB-PVD可作为TBCs的新型制备方法。
During the past decades, TBCs had got more than ever employed in the hot section of gas turbine engines for protection against extreme service conditions. The current state-of-art material for TBCs was6-8wt%YSZ and it was well-established the microstructure and properties of TBCs could vary enormously depending on their manufacturing method. TBCs prepared by plasma spray took on a layered structure with general adhesion but very low thermal conductivity. TBCs produced by EB-PVD presented columnar microstructure with superior adhesion and excellent strain tolerance which qualified its application on high-stress hot section such as the turbine blades, however, the thermal conductivity is high. How to effectively reduce the thermal conductivity of the EB-PVD TBCs has been focus within related research. Recently, considering the lamilar structure within sprayed TBCs can favour reduction of the heat transfer into the coatings for reference, layering of the EB-PVD TBCs is an emerging direction. In the present strudy, the two kinds of layered TBCs were designed within the top coat and successfully prepared using ion beam assisted deposition, low substrate rotation speed as well as the high-low deposition temperature staggered, etc. Then, microstructure and performance was investigated after the introduction of layered structure.
On the basis of research of assisted ion source, the microlaminar TBCs was fabricated by pulse ion beam bombardment with current density in the range0-0.094mA/cm2; while the other methods can develop the multilayered TBCs with the interfaces across the coating and resulted in a flat ribbon pores. The microlaminar TBCs were accompanied with greatdeal of interfaces and the density modulation variation between adjacent micro-laminates. The microlaminates and grain refinement can be more distinguished with increasing level of ion assistance, however, the substrate temperature is still dominant factor in the control of the atomic mobility and surface morphology. Ion assistance had little influence on the composition of layered TBCs, the introduced Ti content was very little and ignorable. In addition, there was no densification was presented.
The two kinds of layered TBCs were still showing the dominant non-transformation tetragonal (t') structural features. The dominant crystallographic orientation can be induced gradually from (100) to (111) by ion assistance, and then there was coexistence of{111} and {100} type texture. The mechanism resultd from the combined action between the adjustment of net growth and direction of columnar grains with orientations with respect to the ion beam and the growth instability induced by surface roughness.
Compared with the conventional TBCs, the thermal diffusivity and thermal conductivity of the two kinds of layered TBCs was both reduced at the same temperature, in which the microlaminar TBCs by ion assistance show a more significant reduction up to35%. The mechanism was attributed to a large interfacial thermal resistance after the introduction of interfaces which was perpendicular to the heat conduction gradient. In addition, refined grains and more boundaries and density modulation between adjacent micro-layer contributed together.
The oxidation rate of the bond coat was both reduced by the two kinds of layered structure. The low rotation specimens exhibited better performance of oxidation resistance, but worse coating life; the ion-assisted specimens shown slightly lower weight gain rate than that of the conventional TBCs, but better coatings duration lifetime. The mechanism lies in the difference of layered structure itself, the location of such two kinds of interface and whether these interfaces reduced the excellent strain tolerance of YSZ column when they restrain the heat transfer and improve the oxidation resistance within the coatings. Overall, ion beam assisted EB-PVD can be a novel method for the preparation of TBCs.
在对离子源的工作特性进行研究的基础上,采用束流密度约为0-0.094mA/cm2的脉冲Ti离子辅助可获得微叠层分层陶瓷层TBCs;其他方法可获得横跨截面的多层陶瓷层TBCs,形成大量扁平带状的孔隙。微叠层结构TBCs伴随着大量的分层界面和相邻分层间的密度调制变化,同时柱状晶晶粒得到细化。离子辅助效应导致的微叠层分层和晶粒细化特征随着离子轰击水平的提升而进一步明显,但基体温度在原子迁移扩散和表面形貌控制上仍是更为重要的因素。离子辅助对成分影响较小,实际引入的Ti含量极低,且不会引起TBCs的致密化。
两种层状结构TBCs仍呈现不可转变的四方相(t’)结构特征。离子辅助带来的额外能量可诱发占优取向从(100)逐渐变化到(111),]BCs内部织构变为{100}型和{111}型织构共存。引入离子与蒸气粒子以及蒸气粒子之间的碰撞导致了晶格重构和溅射,而占优取向的变化机制源于离子束导致的晶粒净生长速率和生长方向的调整以及表面粗糙度引起的生长不稳定性的共同作用。
相对于常规TBCs,两种层状结构TBCs在相应温度下的热扩散系数和热导率都有所降低,其中离子辅助微叠层分层结构导致的热导率降低效果更为明显,室温热导率最高可降低约35%,其机制在于引入的分层界面垂直于热传导方向,带来大量界面热阻,同时,细化的晶粒和由此而来的更多的晶界以及相邻分层间的密度调制共同作用进一步降低了声子传热。
两种层状结构形成的分层界面均有助于降低粘结层的氧化速率。依据这两种分层结构本身的差异及其位置的不同,低转速分层试样粘结层的抗氧化性能更好,但涂层寿命较差；而离子辅助试样粘结层的抗氧化性能稍优于常规TBCs(?),但涂层寿命较优,其机制在于两种分层界面在阻挡传热、增强抗氧化性能的同时,是否降低了YSZ柱晶的应变容限。总体而言,离子束辅助EB-PVD可作为TBCs的新型制备方法。
During the past decades, TBCs had got more than ever employed in the hot section of gas turbine engines for protection against extreme service conditions. The current state-of-art material for TBCs was6-8wt%YSZ and it was well-established the microstructure and properties of TBCs could vary enormously depending on their manufacturing method. TBCs prepared by plasma spray took on a layered structure with general adhesion but very low thermal conductivity. TBCs produced by EB-PVD presented columnar microstructure with superior adhesion and excellent strain tolerance which qualified its application on high-stress hot section such as the turbine blades, however, the thermal conductivity is high. How to effectively reduce the thermal conductivity of the EB-PVD TBCs has been focus within related research. Recently, considering the lamilar structure within sprayed TBCs can favour reduction of the heat transfer into the coatings for reference, layering of the EB-PVD TBCs is an emerging direction. In the present strudy, the two kinds of layered TBCs were designed within the top coat and successfully prepared using ion beam assisted deposition, low substrate rotation speed as well as the high-low deposition temperature staggered, etc. Then, microstructure and performance was investigated after the introduction of layered structure.
On the basis of research of assisted ion source, the microlaminar TBCs was fabricated by pulse ion beam bombardment with current density in the range0-0.094mA/cm2; while the other methods can develop the multilayered TBCs with the interfaces across the coating and resulted in a flat ribbon pores. The microlaminar TBCs were accompanied with greatdeal of interfaces and the density modulation variation between adjacent micro-laminates. The microlaminates and grain refinement can be more distinguished with increasing level of ion assistance, however, the substrate temperature is still dominant factor in the control of the atomic mobility and surface morphology. Ion assistance had little influence on the composition of layered TBCs, the introduced Ti content was very little and ignorable. In addition, there was no densification was presented.
The two kinds of layered TBCs were still showing the dominant non-transformation tetragonal (t') structural features. The dominant crystallographic orientation can be induced gradually from (100) to (111) by ion assistance, and then there was coexistence of{111} and {100} type texture. The mechanism resultd from the combined action between the adjustment of net growth and direction of columnar grains with orientations with respect to the ion beam and the growth instability induced by surface roughness.
Compared with the conventional TBCs, the thermal diffusivity and thermal conductivity of the two kinds of layered TBCs was both reduced at the same temperature, in which the microlaminar TBCs by ion assistance show a more significant reduction up to35%. The mechanism was attributed to a large interfacial thermal resistance after the introduction of interfaces which was perpendicular to the heat conduction gradient. In addition, refined grains and more boundaries and density modulation between adjacent micro-layer contributed together.
The oxidation rate of the bond coat was both reduced by the two kinds of layered structure. The low rotation specimens exhibited better performance of oxidation resistance, but worse coating life; the ion-assisted specimens shown slightly lower weight gain rate than that of the conventional TBCs, but better coatings duration lifetime. The mechanism lies in the difference of layered structure itself, the location of such two kinds of interface and whether these interfaces reduced the excellent strain tolerance of YSZ column when they restrain the heat transfer and improve the oxidation resistance within the coatings. Overall, ion beam assisted EB-PVD can be a novel method for the preparation of TBCs.
引文
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