Thermal conductivity and thermal cycle life of La2O3 and HfO2 doped ZrO2-Y2O3 coatings produced by EB-PVD

The effects of La₂O₃ and HfO₂ addition on thermal conductivity and thermal cycle life of EB-PVD YSZ coatings were investigated. La₂O₃ and HfO₂ were selected as additives, because they significantly suppress the sintering of YSZ. The developed coating showed low thermal conductivity as well as high resistance to sintering. Burner rig tests confirmed that the developed coating have a superior thermal insulating effect and have a longer life than that of a coating with conventional composition.     

Effects of particle size of 8 mol% Y2O3 stabilized ZrO2 (YSZ) and additive Ta2O5 on the phase composition and the microstructure of sintered YSZ electrolyte

The chemical stability and sinterability of nano- and micro-sized yttria stabilized zirconia (YSZ) powders were investigated, and the effect of Ta₂O₅ additive on the sinterability of YSZ electrolyte was also studied. Addition of Ta₂O₅ easily causes phase transformation of YSZ from cubic to monoclinic, and thus unfavorable for the improvement of ionic conductivity of YSZ electrolyte. Nano-sized YSZ easily causes abnormal grain growth and hence readily results in inhomogeneous microstructure of YSZ matrix, while micro-sized YSZ displays relatively low sinterability. Comparatively, mixture with 50 wt.% nano-sized and 50 wt.% micro-sized YSZ powders exhibits high sinterability and could be sintered to homogeneous microstructure, which can be used as starting materials to prepare dense YSZ electrolyte at low temperatures.     

Thermal conductivity of nanoporous ZrO2-4 mol% Y2O3 multilayer coatings fabricated by EB-PVD

The effect of multilayer configurations on the thermal conductivity of 4 mol% Y₂O₃⁻ stabilized ZrO₂ coatings fabricated by EB-PVD has been investigated. The deposited coating layers consist of columnar grains containing nano-sized pores. Multilayer specimens are found to contain many pores at the interfaces between layers. The density and thermal conductivity of the multilayer coatings decreases with increasing number of coating layers for one to six layers. The thermal conductivities of coatings deposited onto rotating substrates are lower than those of coatings deposited on stationary substrates. The decreased thermal conductivity of multilayer coatings is ascribed to the increased total porosity resulting from an increase in the number of interface pores concomitant with the formation of non-uniform interfaces between layers, which causes increased phonon scattering.     

Miniaturized bend tests on partially stabilized EB-PVD ZrO2 thermal barrier coatings

The elastic properties of thermal barrier coatings (TBCs) are important for modelling the lifetime of these coatings. A new test setup has been developed to measure the system modulus of electron-beam enhanced physical vapour deposited (EB-PVD) TBC coatings by miniaturized bend tests.Due to the brittleness, low stiffness and small thickness of the top coat and its complex microstructure, it is difficult to measure its Young's modulus by standard mechanical testing. For this reason, a special sample material has been prepared which consists of a 1 mm thick layer of EB-PVD TBC. This material was isothermally heat treated for different times at 950 °C, 1100 °C and 1200 °C and then tested in a specially developed miniaturized bend test. The bend test setup permits mechanical tests with a high resolution in stress and strain, where the strain is measured by digital image correlation. So the stiffness of the free-standing TBC samples could be measured with a high accuracy and the sintering behaviour of the EB-PVD TBC and the consequent rise of Young's modulus could be determined. The results show a significant increase of the system modulus with heat treatment time and temperature caused by sintering of the coating. An activation energy of 220 kJ/mol for the process has been determined.In addition, the material was tested by nanoindentation in order to measure Young's modulus on a local scale, and the porosity of the samples was determined by quantitative image analysis.     

等离子喷涂La2(Zr0.7Ce0.3)2O7热障涂层的抗热震性能

采用等离子喷涂制备了La₂(Zr_0.7Ce_0.3)₂O₇（LZ7C3）热障涂层,并对涂层的微观组织、相结构、成分、相稳定性、涂层热导率以及抗热震性能进行了研究.结果表明,LZ7C3涂层由单相烧绿石结构物质组成,高温稳定性较好;涂层的热导率较块材下降约20%,这是由于涂层具有较高的孔隙率所致:涂层在不同温度范围的热震寿命和失效机制不同,在室温至约1000℃间的热震寿命为116 cyc,涂层失效方式以片状剥落为主:在室温至1100℃间的热震寿命为53 cyc,涂层失效方式为片状剥落和层状撕裂;在室温至1200℃间的热震寿命为3 cyc,涂层失效方式以层状撕裂为主.     

La2O3对EXD602-WC烧结涂层组织与性能的影响

采用热压烧结技术在45钢基片表面制备50EXD602-50WC复合涂层,利用光学显微镜(OM)、扫描电子显微镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)进行组织观察、成分以及物相分析,研究了La2O3对涂层组织、表面磨损形貌和耐磨性能的影响。结果表明:涂层中主要含有WC、CuSn相和富Fe相,未添加La2O3的涂层组织中存在较多缺陷,表面磨损严重。随着La2O3的加入,涂层组织和耐磨性能得到不同程度的改善。La2O3质量分数为1.0%时,涂层孔隙率最低仅为0.84%,硬度为54.8HRC,相对耐磨系数9.76。表面磨损形貌平整且无剥落坑,划痕较浅,涂层与母材结合紧密,表现出最佳的耐磨性能。     

柠檬酸法制备热障涂层用La2Ce2O7粉体

以ZrO(NO3)2·2H2O、Ce(NO3)·6H2O和La2O3为原料,采用柠檬酸法制备了La2Ce2O7粉体,研究了pH值、乙二醇及柠檬酸用量、煅烧温度等工艺参数对La2Ce2O7粉体的影响。结果表明,采用该方法能够制备纯净的La2Ce2O7粉体,最佳实验条件是pH值为5,乙二醇、柠檬酸与金属离子的摩尔比分别是1.8和2,煅烧温度为400℃。     

Effect of La2O3 on resistance to high-temperature oxidation of laser clad ferrite-based alloy coatings

Ferrite-based alloy powders with different contents of La₂O₃ were laser-clad on AISI 1115 steel substrates. The oxidation kinetic of the coatings was studied by testing the weight gain. Cyclic oxidation tests were performed to determine the eventual weight loss due to spallation. The morphologies and phase structures of the coatings were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The experimental results showed that Cr₂O₃ was formed on all coatings after oxidation. The coatings with La₂O₃ exhibited excellent high-temperature oxidation behavior including low oxidation rates and high resistance to spallation. In addition, the effect of La₂O₃ was discussed. This included the change of transport mechanism in the oxide scales, the increase in the nucleation rate of the oxide, the release of stresses in the oxide scales by refining the oxide grains and the improvement of the adhesion of the oxide scales to the coatings by changing the scale growth mechanisms.     

La2O3掺杂AgSnO2电接触材料的制备及性能研究

以Ag、Sn、La₂O₃粉为原料,采用机械合金法制备复合粉体。结合氧化法与粉末冶金工艺,对复合粉体进行氧化、压制、烧结。采用扫描电镜(SEM)和能谱仪、硬度计、金相显微镜、金属电导率测量仪等对复合粉体氧化前后的形貌以及电接触材料烧结前后的性能进行表征。结果表明：烧结后,电接触材料硬度较于烧结前明显下降。同时电接触材料随Sn含量增大,电阻率升高,密度反而下降。在一定的La₂O₃(0wt.%、0.75wt.%、1.5wt.%、2.25wt.%、3wt.%)含量范围内,La₂O₃掺杂量越高,密度越低。同时电接触材料经烧结后,随La₂O₃含量增加,其电阻率先降后升,在La₂O₃含量为0.75wt.%时,电接触材料的电阻率最低。     

烧结助剂Y2O3和Pr6O11对Al2O3陶瓷相对密度和热导率的影响

采用高分子网络法制备混合纳米粉体,研究稀土氧化物Y2O3和Pr6O11加入量对Al2O3陶瓷相对密度和热导率的影响。采用阿基米德方法测定样品的体积密度,利用激光脉冲法测量试样的热扩散率并计算得出热导率。结果表明:两种添加剂都可以降低Al2O3陶瓷的烧结温度,提高Al2O3陶瓷的热导率,其中Y2O3的促进作用较强;当保温时间相同、烧结温度为1 500~1 650℃时,Al2O3陶瓷的相对密度和热导率都随烧结温度的升高而增大;当烧结温度相同、保温时间为30~120 min时,Al2O3陶瓷的相对密度和热导率也随保温时间的延长而增大。     

Properties of ZrO2–Al2O3 composite as a function of isothermal holding time

Zirconia and alumina based ceramics present interesting properties for their application as implants, such as biocompatibility, good fracture resistance, as well as high fracture toughness and hardness. In this work the influence of sintering time on the properties of a ZrO₂–Al₂O₃ composite material, containing 20 wt% of Al₂O₃, has been investigated. The ceramic composites were obtained by sintering, in air, at 1600 °C for sintering times between 0 and 1440 min. Sintered samples were characterized by microstructure and crystalline phases, as well as by mechanical properties. The grain growth exponents, n, for the ZrO₂ and Al₂O₃ were 2.8 and 4.1, respectively, indicating that different mechanisms are responsible for grain growth of each phase. After sintering at 1600 °C, the material exhibited a dependency of hardness as function of sintering time, with hardness values between 1500 HV (120 min) and 1310 HV (1440 min) and a fracture toughness of 8 MPa m^1/2, which makes it suitable for bioapplications, such as dental implants.     

Fracture toughness of sintered Mo–La2O3 alloy and the toughening mechanism

The K_IC of sintered Mo–La₂O₃ alloy and pure molybdenum was tested and the micro-structure was investigated by SEM, TEM and AES. The results show that the K_IC of Mo–La₂O₃ alloy reaches 24.76 MPa m^1/2, which is 2.5 times as much as that of pure Mo. The sintered Mo–La₂O₃ alloy and pure molybdenum have similar equiaxed grain structure. The AES analysis revealed that the same content of interstitial impurities exist on grain boundaries of Mo–La₂O₃ alloy and pure molybdenum. A toughening mechanism was proposed to be that large number of dislocations were pinned around La₂O₃ particles, shortening the efficient slip length and decreasing the dislocation pile-up on grain boundaries of Mo. The improvement of toughness of Mo–La₂O₃ alloy was attributed to the relief of stress concentration at the grain boundaries of Mo–La₂O₃ alloy and the weaker tendency to intergranular fracture on grain boundaries.     

Thermal conductivity of EB-PVD ZrO2-4 mol% Y2O3 films using the laser flash method

The variation in thermal conductivity and thermal diffusivity of ZrO₂-4 mol% Y₂O₃ coatings deposited onto Inconel substrates by EB-PVD is examined as a function of coating thickness using the laser flash method. The coatings are found to consist of columnar grains with a feather-like microstructure. The thermal conductivities of the coatings are calculated using two methods: the first involves separating the coating from the substrate and measuring the thermal diffusivity directly; the second uses thermal diffusion results from coatings still attached to the substrate and is based on the response function method. The results of both methods are in excellent agreement, and show that the thermal conductivities of the coatings increase with increasing coating thickness. The results also confirm that the double layer method can be used successfully to calculate the thermal conductivities of thin film coatings.     

La2O3与Sb2O3掺杂钛酸锶钡陶瓷的介电性能及相变（英文）

采用固相法制备La2O3与Sb2O3掺杂的钛酸锶钡陶瓷,研究其介电性能及相变特性。通过X射线衍射法分析体系微观结构并利用扫描电镜观察其表面微观形貌。(La,Sb)共掺杂的钛酸锶钡陶瓷具有典型的钙钛矿结构,且随着Sb2O3掺杂量的增多其平均粒径显著减小。La3+离子以及Sb3+离子均占据钙钛矿晶格的A位。La2O3与Sb2O3添加量的改变显著影响钛酸锶钡基陶瓷的介电常数以及介电损耗。La2O3改性的钛酸锶钡陶瓷其四方?立方相变为二级相变,且居里温度随着La2O3掺杂量的增多向低温方向移动。(La,Sb)共掺杂的钛酸锶钡陶瓷则体现为弥散相变,随着Sb2O3含量的增大而偏离居里-外斯定律越显著。由于Sb3+离子对晶格原位离子的取代使得(La,Sb)共掺杂的钛酸锶钡陶瓷的介电常数最大值下的温度亦随着Sb2O3含量的增大而降低。     

Development of moderate temperature CVD Al2O3 coatings

Chemically vapor deposited Al₂O₃ coatings, due to their high hardness and chemical inertness, are currently the state of art in the cutting tool industry. The conventional high deposition temperature of about 1050 °C for Al₂O₃ coatings, based on the water–gas shift process, has to a great extend restricted the development of several hybrid coatings, such as TiC/TiN/TiCN/Al₂O₃. To overcome this limitation, alternate systems to deposit Al₂O₃ at moderate temperatures have been investigated. Systems using NO–H₂, H₂O₂, NO₂–H₂ and HCOOH were identified and thermodynamic calculations were performed to evaluate them as potential sources of oxygen donors to form Al₂O₃ in the moderate temperature range of 700–950 °C. Preliminary results have clearly demonstrated that it is possible to grow moderate temperature alumina (using such alternate sources) on the TiC/TiN coated cemented carbide substrates.     

Thermal shock behavior of nanostructured and conventional Al2O3/13 wt%TiO2 coatings fabricated by plasma spraying

The thermal shock behavior of three kinds of Al₂O₃/13 wt%TiO₂ coatings fabricated by plasma spraying was studied in this paper. One kind of those coatings was derived from conventional fused and crushed feedstock powder available commercially; the other two kinds of coatings were derived from nanostructured agglomerated feedstock powders. These two nano coatings possess moderate pores and pre-existing microcracks, they were composed of fused structure and three-dimensional net or skeleton-like structure. For conventional coatings, the pores and pre-existing cracks were bigger, sharp-point and mostly distributed between splats. Thermal shock tests for the three coatings were performed by water quenching method. Testing result showed the two kinds of nano coatings had much higher thermal shock resistance than the conventional coatings. The improved thermal shock resistance for nano coatings could attribute to their improved microstructure and crack propagation mode. The damage evolution and failure mechanism of coatings was quite different at thermal shock temperature of 650 °C and 850 °C, which was explained by a simple model. Different crack propagating modes in nanostructured and conventional coatings during thermal shock tests were due to their different microstructures in these two kinds coatings. The stress state of coating surfaces during the thermal cycles was also discussed in this paper.     

Processing, microstructure, and properties of laser remelted Al2O3/Y3Al5O12（YAG） eutectic in situ composite

Laser remelting and rapid solidification were performed in preparing the high-performance Al2O3/Y3Al5O12（YAG） eutectic in situ composite. The microstructure characteristic and solidification behavior were studied using scanning electron microscopy（SEM）, energy dispersive spectroscopy（EDS）, X-ray diffractometry（XRD） and simultaneous thermal analysis（STA）. The hardness and fracture toughness were obtained using an indentation technique. The results show that the laser remelted Al2O3/YAG composite has a homogeneous eutectic microstructure without microcrack and pore. The component phases of Al2O3 and YAG are three-dimensionally and continuously reticular connected, and finely coupled without grain boundaries, colonies and amorphous phases between interfaces. The eutectic interspacing is greatly refined with increasing the scanning rate and average is only l μm. The synthetically thermal analysis indicates that the eutectic temperature of Al2O3-YAG is 1 824 ℃, well matching the phase diagram of Al2O3-Y2O3 system. The maximum hardness reaches 19.5 GPa and the room fracture toughness is 3.6 MPa.m^1/2.     

Preparation and thermal conductivities of Gd2Ce2O7 and (Gd0.9Ca0.1)2Ce2O6.9 ceramics for thermal barrier coatings

Two kinds of rare earth cerium oxides Gd₂Ce₂O₇ and (Gd_0.9Ca_0.1)₂Ce₂O_6.9 were prepared by solid state reaction method at 1600 °C for 10 h. The phase compositions, microstructures, and their thermal conductivities of these materials were investigated. XRD results revealed that single phase Gd₂Ce₂O₇ and (Gd_0.9Ca_0.1)₂Ce₂O_6.9 with fluorite structure were synthesized. Results of SEM and EDS showed that the microstructures of these materials were dense and no other phases existed among grains. Because of phonon scattering resulted by the oxygen vacancies and difference in atomic mass between substitutional atoms and host atoms, thermal conductivities of Gd₂Ce₂O₇ and (Gd_0.9Ca_0.1)₂Ce₂O_6.9 are lower than that of 8YSZ at 800 °C, and thermal conductivity of (Gd_0.9Ca_0.1)₂Ce₂O_6.9 is lower than that of Gd₂Ce₂O₇. These results imply the Gd₂Ce₂O₇ and (Gd_0.9Ca_0.1)₂Ce₂O_6.9 can be used as novel candidate materials for thermal barrier coatings in the future.     

Microstructural analysis of YSZ and YSZ/Al2O3 plasma sprayed thermal barrier coatings after high temperature oxidation

Air plasma sprayed TBCs usually include lamellar structure with high interconnected porosities which transfer oxygen from YSZ layer towards bond coat and cause TGO growth and internal oxidation of bond coat.The growth of thermally grown oxide (TGO) at the interface of bond coat and ceramic layer and internal oxidation of bond coat are considered as the main destructive factors in thermal barrier coatings.Oxidation phenomena of two types of plasma sprayed TBC were evaluated: (a) usual YSZ (yttria stabilized zirconia), (b) layer composite of (YSZ/Al₂O₃) which Al₂O₃ is as a top coat over YSZ coating. Oxidation tests were carried out on these coatings at 1100°C for 22, 42 and 100h. Microstructure studies by SEM demonstrated the growth of TGO underneath usual YSZ coating is higher than for YSZ/Al₂O₃ coating. Also cracking was observed in usual YSZ coating at the YSZ/bond coat interface. In addition severe internal oxidation of the bond coat occurred for usual YSZ coating and micro-XRD analysis revealed the formation of the oxides such as NiCr₂O₄, NiCrO₃ and NiCrO₄ which are accompanied with rapid volume increase, but internal oxidation of the bond coat for YSZ/Al₂O₃ coating was lower and the mentioned oxides were not detected.