A2Zr2O7型稀土锆酸盐热障涂层研究进展

综述了国内外稀土锆酸盐热障涂层在制备技术,纳米涂层,涂层结构及涂层的热物理性能、力学性能及热腐蚀性能等方面的研究成果,讨论了稀土锆酸盐热障涂层在每个方面研究存在的不足。指出未来应该进一步改善稀土锆酸盐涂层的制备工艺及后处理工艺,提高涂层的结合强度,延长涂层的服役寿命,改善涂层耐腐蚀、抗烧结等性能;开发新的涂层制备工艺,重点研究各类纳米稀土锆酸盐涂层的性能;进一步提高涂层的隔热效果、服役温度及工作寿命。     

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.     

表面陶瓷层厚度对Sm2Zr2O7/8YSZ热障涂层热冲击性能的影响

稀土锆酸盐与8YSZ所组成的双陶瓷层涂层是目前热障涂层领域研究的热点,而陶瓷层厚度对其热冲击性能有着显著影响。采用有限元软件ANSYS研究了表层厚度对Sm2Zr2O7/8YSZ热障涂层淬冲击热应力的影响,并与单一Sm2Zr2O7涂层进行了比较。结果表明,在Sm2Zr2O7/8YSZ涂层的表面处具有最大的径向热冲击应力,最大轴向应力则存在于陶瓷层/金属粘结层界面处,涂层各处剪应力基本相当。涂层表面及两陶瓷层界面处的径向热应力随表层厚度的增加而减小,陶瓷层/粘结层界面处径向应力则随表层厚度增加而增大。每个界面处的轴向应力随表层厚度增加而降低,而剪应力绝对值则随表层厚度增加而增大。与单一Sm2Zr2O7涂层相比,Sm2Zr2O7/8YSZ涂层的热应力明显偏小,说明增加涂层的层数有利益改善涂层的抗热冲击性能。     

沉积气氛对电火花沉积Mo2FeB2基金属陶瓷涂层组织与性能的影响

采用电火花沉积分别在空气和氩气中制备了Mo_2FeB_2基金属陶瓷涂层,通过扫描电镜(SEM)、X射线衍射(XRD)、显微硬度计和摩擦磨损试验机研究了沉积气氛对涂层形貌、相组成、硬度和摩擦磨损性能的影响。结果表明,2种气氛中沉积所得涂层的组织结构都致密,涂层与基体间无分层,呈冶金结合的特征,但空气中沉积涂层的表面较粗糙,并发生了严重的氧化,涂层均匀性也较差。它们都主要由非晶相和马氏体相组成,但氩气中沉积的涂层含有更多的非晶相。氩气和空气中沉积涂层的最大显微硬度(HV_(0.05))分别为12 862和10 129 MPa,相差2733 MPa,前者涂层2 h的磨损量几乎仅为后者涂层的1/7,表现出更好的耐磨性。2种涂层的主要磨损机制都是疲劳磨损和磨粒磨损,但氩气中沉积涂层以疲劳磨损为主,空气中沉积涂层则以磨粒磨损为主。     

La2O3-modified YSZ coatings: High-temperature stability and improved thermal barrier properties

Lanthana precursor was coated on yttria-stabilized-zirconia (YSZ) powders by wet chemical infiltration, and was introduced to the crystalline structure and grain boundaries of YSZ after plasma spraying of thermal barrier coatings (TBCs). The microstructural stability and thermal barrier properties of this new kind of TBCs were studied under different annealing conditions. It demonstrates that the La₂O₃ surface coating restrains grain growth of YSZ during both deposition and post-annealing processes, compared to a TBC obtained from commercially available unmodified YSZ powders. According to the composition analysis, lanthana partially dissolved in the zirconia matrix after heat treatment. The thermal diffusivity of YSZ coating significantly decreased after lanthana modification, typically from 0.354 mm² s^− 1 for an unmodified sample to 0.243 mm² s^− 1, reflecting a decrease of 31%. Even after annealed at 1200 °C for 50 h, the thermal diffusivity of modified coatings still shows a reduction of 25% than unmodified samples.     

Production of LaPO4 coatings using a novel ultrasonically-assisted plating technique

Dense LaPO₄ and LaPO₄-Al₂O₃ coating films were produced on the surface of stainless steel substrates at room temperature and ambient pressure with the aid of a novel ultrasonic-based mechanical coating method, which we call UMCA. The main emphasis was on examining the conditions necessary for the successful coating operation and characterizing the as-deposited coatings for the thickness, uniformity and surface morphology. The experimental results suggested that hardness and thermal conductivity of balls and substrate are key parameters influencing the coating efficiency. The coated samples showed an improved hot corrosion resistant in Na₂SO₄-NaCl molten salts at 950 °C.     

钛合金表面等离子喷涂Y2O3稳定的ZrO2涂层的 扫描热显微镜分析

以纳米结构Y2O3稳定的ZrO2热喷涂粉末为原料,采用等离子喷涂法在Ti-6Al-4V合金上制备了纳米结构的热障涂层。利用扫描电镜(SEM)及扫描热显微镜(SThM)对涂层的微观组织及热性能进行了分析。在实验基础上建立了理论模型,并对涂层及基体的热导率进行了估算。结果表明:采用SThM分析方法估算的涂层厚度及涂层上的缺陷尺寸与采用其它分析方法测得的结果一致;虽然热导率的估算结果与采用其它方法得出的结果差异较大,但显示出扫描热显微镜分析是估算材料热导率潜在的方法。     

Electroless ternary Ni-W-P alloys containing micron size Al2O3 particles

In the present investigation electroless ternary NiWP-Al₂O₃ composite coatings were prepared using an electroless nickel bath. Second phase alumina particles (1 µm) were used to codeposit in the NiWP matrix. Nanocrystalline ternary NiWP alloys and composite coatings were obtained using an alkaline citrate based bath which was operated at pH 9 and temperature at 88 ± 2 °C. Mild steel was used as a substrate material and deposition was carried out for about 4 h to get a coating thickness of 25 ± 3 µm. Metallographic cross-sections were prepared to find out the coating thickness and also the uniform distribution of the aluminum oxide particles in NiWP matrix. Surface analysis carried out on both the coatings using scanning electron microscope (SEM) showed that particle incorporation in ternary NiWP matrix has increased the nodularity of composite coatings compared to fine nodular NiWP deposits. Elemental analysis of energy dispersive X-ray (EDX) results showed that codeposited P and W elements in plain NiWP deposit were 13 and 1.2 wt.%, respectively. There was a decrease in P content from 13 to 10 wt.% with a marginal variation in the incorporated W (1.01 wt.%) due to the codeposition of aluminum oxide particles in NiWP matrix. X-ray diffraction (XRD) studies carried out on as-plated deposits showed that both the deposits are X-ray amorphous with a grain size of around 3 nm. Phase transformation studies carried out on both the coatings showed that composite coatings exhibited better thermal stability compared to plain NiWP deposits. From the XRD studies it was found that metastable phases such as NiP and Ni₅P₂ present in the composite coatings heat treated at major exothermic peak temperature. Annealed composite coatings at various temperatures revealed higher microhardness values compared to plain NiWP deposits.     

Stress analysis of high temperature ZrO2 insulation coatings on Ag using finite element method

The aim of this study is to investigate residual stresses occurred during cooling procedure of ZrO₂ insulation coating on Ag substrate for magnet technologies. ZrO₂ coatings were produced on Ag tape substrate by using a reel-to-reel sol–gel technique. SEM inspection showed that ZrO₂ coatings had mosaic structures. ANSYS finite element software was used to calculate the temperature and stress distribution of the ZrO₂/Ag structure. The effect of coating thickness on residual stresses was also examined. The results obtained showed that thermal stresses in ZrO₂ coating and Ag substrate were considerably affected by the cooling time and coating thickness. It is concluded the thermal stresses increase with increase of film thickness.     

Microstructure and oxidation of multi-layer MoSi2-CrSi2-Si coatings for SiC coated carbon/carbon composites

Multi-layer MoSi₂-CrSi₂-Si anti-oxidation coatings with different compositional ratios were prepared on the surface of SiC coated carbon/carbon (C/C) composites by a two-step pack cementation method. The microstructure and anti-oxidation performance of the coating were studied. The results show that the multi-layered coatings could protect the C/C composites from oxidation in air at 1773 K for 1000 h or 1873 K for 750 h, respectively. The anti-oxidation performance of the multi-layer MoSi₂-CrSi₂-Si coating is mainly attributed to their dense and microcrack-free structure, appropriate thermal expansion coefficient and the well dispersed MoSi₂ and CrSi₂ in the coating.     

等离子喷涂制备ZrB2/SiC/Ta2O5涂层抗烧蚀性能研究

为了提高C/C复合材料的抗烧蚀性能,通过等离子喷涂法在C/C表面制备了SiC/Al₂O₃内层和ZrB₂/SiC/Ta₂O₅外层的双层涂层,通过XRD,SEM和EDS分析了涂层烧蚀前后的物相组成、微观结构和成分分布。烧蚀前涂层表面没有裂纹并且内层与基体、内层与外层之间结合良好。元素Zr、Si、Ta在涂层表面的分布相近,涂层表面成分分布均匀性良好。通过氧乙炔火焰在1800 ℃下对涂层的抗烧蚀性能进行考核。烧蚀过程中形成的镶嵌结构有利于阻挡氧气的渗入,Ta-Si-O玻璃层的形成封填了涂层孔隙,对基体有良好的保护效果,涂层表现出了较好的抗烧蚀性能。     

Oxidation and interfacial fracture behaviour of NiCrAlY/Al2O3 coatings on an orthorhombic-Ti2AlNb alloy

Al₂O₃ diffusion barriers of various thicknesses have been fabricated by filtered arc ion plating between the NiCrAlY coating and the O-Ti₂AlNb alloy. Isothermal oxidation tests and three-point bend tests have been conducted to investigate the influence of the Al₂O₃ diffusion barriers on the oxidation and interfacial fracture behaviour of the coatings. The results indicate that the Al₂O₃ diffusion barrier defers interdiffusion and gives oxidation resistance of the NiCrAlY coatings. The thickness of the Al₂O₃ interlayer not only influences the oxidation behaviour but also affects the interfacial fracture properties. Additionally, thermal exposure affects the critical load in three-point bend tests.     

铝基板表面微弧氧化膜厚度对其导电导热性的影响

目的对LED封装用铝基板表面进行微弧氧化处理,用以调控其界面的导电导热行为,并构建微弧氧化膜的厚度与其导电性及导热性之间的关联性。方法采用XRD表征了不同厚度微弧氧化膜的相结构,借助SEM观察了不同厚度膜层的表面微观形貌,利用高阻计测试了不同外加电压下膜层的电阻率,采用闪光法测定了不同温度下膜层的热扩散系数。结果微弧氧化膜主要由γ-Al_2O_3相组成,随膜层厚度的增加,膜层的相结构无显著变化,但其表面多孔结构出现了明显变化。膜层电阻率随膜厚的增大而升高,在膜厚从10μm增至40μm的过程中,电阻率增大了4~8倍。膜层电阻率随测试电压的升高而降低,当测试电压从50 V升至100 V时,电阻率降幅达1~2个数量级。膜层的热扩散系数随膜厚的增大出现波动,当膜厚为10~40μm时,热扩散系数的变化量为21.6~24.8 m~2/s。膜层热扩散系数随测试温度的升高而降低,降幅最高可达8.9 m~2/s。结论厚度为40μm的微弧氧化膜既具有高的电阻率(7.1×1012?·cm),又具有高的热扩散系数(98.0 m~2/s),有望满足LED铝基板的界面绝缘与散热要求。     

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.     

The effect of pulsed magnetron sputtering on the structure and mechanical properties of CrB2 coatings

CrB₂ thin films possess desirable combinations of properties (high hardness, wear resistance, chemical inertness, high thermal and electrical conductivity), which are attractive for a wide range of potential applications. Pulsed magnetron sputtering (PMS) of loosely-packed blended powder targets has allowed the deposition of stoichiometric chromium diboride coatings. The structure and properties of these coatings were found to be strongly dependent on the deposition process parameters; therefore investigation of the coating structures could explain certain differences between them and provide important information about the characteristics of the deposition process. In this study, characterization of the CrB₂ films was performed by scanning and transmission electron microscopy (SEM and TEM) techniques. The microstructures and properties of coatings deposited with different parameters are compared and changes that resulted from the variation of these parameters (particularly the pulsing duty cycle and the substrate biasing conditions) are discussed. The results show that besides the pulsing frequency, the target pulsing duty cycle is an important parameter of the PMS process, which is able to affect such coating properties as hardness, thickness and stress. Coating thickness measurement results suggest more intense bombardment of a growing film by energetic ions at lower values of duty cycle. Structural TEM analysis revealed two extremely different types of coating microstructures, obtained at quite similar substrate biasing conditions, i.e. floating (∼ − 15 V) and negatively biased (− 30 V). It appears that the structures of the coatings deposited at the negatively biased substrate are significantly affected by high-energy ion bombardment, which is a peculiarity of PMS that can modify film growth conditions. These conditions are not present when the substrate is allowed to float.     

热障涂层隔热性能测试方法分析

分别利用4种不同的隔热性能测试方法,对氧乙炔火焰喷涂工艺制备的ZrO2陶瓷热障涂层的隔热性能进行了测试,通过红外测温仪和热电偶连接温度记录仪两种不同方式,测试试样金属基体温度,获得4组不同涂层厚度试样金属基体的温度变化曲线,并结合陶瓷涂层的服役工况对测试结果进行了分析,结果表明,测试方法不同,隔热性能测试所得数据也有所差异,但这4种测试方法均可不同程度的反映热障涂层的隔热效果及变化趋势,在接近实际服役工况条件下,可定性评估涂层隔热性能。     

Microstructure and Thermal Characterization of Plasma-Sprayed Nanostructured La2Ce2O7-Doped YSZ Coatings

Nanostructured La₂Ce₂O₇-doped YSZ coatings were developed using atmospheric plasma-spraying technique by optimizing various process parameters. To ensure the retention of nanostructure, the molten state of nanoagglomerates was monitored using plasma and particle diagnostic tools. It was observed that the morphology of the coating exhibits a bimodal microstructure consisting of nanozones reinforced in a matrix of fully-molten particles. The thermal diffusivity of nano-LaCeYSZ coatings is lower than that of nano and bulk YSZ. The reason for this change in thermal diffusivity may be attributed to scattering of phonons at grain boundaries, point defect scattering and higher inter-splat porosity. Also, the thermal conductivity of the nanocomposite coatings was lower than those of nanostructured and bulk YSZ coatings. XRD results show cubic zirconia with a small amount of tetragonal zirconia. The average grain size of the as-sprayed La₂Ce₂O₇-YSZ nanocomposite coatings is ~150-200 nm. The improved thermal behavior is mainly due to a dense, packed, and more compact structure of the coatings.     

Synthesis and characterization of Y3Al5O12 and ZrO2-Y2O3 thermal barrier coatings by combustion spray pyrolysis

Y₃Al₅O₁₂ and ZrO₂-Y₂O₃ (8 mol% YSZ) coatings for potential application as thermal barrier coatings were prepared by combustion spray pyrolysis. Thermal cycling of as deposited coatings on stainless steel and FeCrAlY bond coat substrates was carried out at 1000 °C and 1200 °C to determine the thermal fatigue response. Structural and morphological studies on Y₃Al₅O₁₂ and 8 mol% YSZ coatings before and after thermal cycling have been carried out. It has been noted that the coatings on FeCrAlY substrates remain intact after 50 cycles between room temperature and 1200 °C, whereas the coatings on stainless steel show some minor damage such as peeling off near the periphery after 50 cycles at 1000 °C. Thermal diffusivity values of Y₃Al₅O₁₂ and 8 mol% YSZ films were measured by using photo thermal deflection spectroscopy and the values are lower than those of coatings produced by conventional techniques such as EBPVD and APS.     

An Investigation of the thermal degradation of the intumescent coating containing MoO3 and Fe2O3

An intumescent flame retardant coating was prepared using an ammonium polyphosphate (APP)-pentaerythritol (PER)-melamine (MEL) intumescent flame retardant (IFR) system. Molybdenum trioxide (MoO₃) and ferric oxide (Fe₂O₃) were used as modifiers to improve the thermal stability of the APP-PER-MEL coating. The effects of MoO₃ and Fe₂O₃ on the thermal stability of the residue chars were studied using thermogravimetric analysis (TGA), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) and scanning electric microscopy (SEM). The TGA results showed that adding MoO₃ and Fe₂O₃ increased the residue weights of the APP-PER-MEL coatings. XPS analysis demonstrated that the thermal stability of the coatings was improved. SEM images of chars illuminated that MoO₃ and Fe₂O₃ improved the outer and inner surface structure of the residue char layer. All the results indicated that MoO₃ and Fe₂O₃ were effective modifiers to improve the thermal stability of the APP-PER-MEL coating.     

等离子喷涂Gd2Zr2O7-SrZrO3复合陶瓷涂层的微观结构和性能

通过固相反应法合成了Gd2Zr2O7-SrZrO3 (GZSZ,Gd2Zr2O7:SrZrO3=7:3)复合陶瓷粉末,并采用喷雾造粒法和大气等离子喷涂法分别制备了适合等离子喷涂使用的相应喷涂粉末及涂层。使用X射线衍射、扫描电子显微镜对粉末和涂层的相组成、显微结构进行分析。借助激光热导仪、高温热膨胀仪对涂层的热扩散系数和热膨胀系数、烧结系数进行了表征。结果表明,制备的GZSZ复合陶瓷粉末和涂层都由Gd2Zr2O7和SrZrO3两相组成,粉末中的Gd2Zr2O7为烧绿石结构,而涂层中的Gd2Zr2O7为萤石结构,SrZrO3都为钙钛矿结构。制备态GZSZ涂层的孔隙率为~14%。GZSZ涂层1400℃热处理5 h后的热膨胀系数为(9.8~11.2)×10-6 K-1。制备态GZSZ涂层的热导率为~0.8 W·m-1·K-1,与制备态SrZrO3涂层的热导率~1.0 W·m-1·K-1相比降低~20%。1400℃热处理360 h后GZSZ涂层的热导率增加到~1.5 W·m-1.K-1。综上表明,GZSZ涂层是一种很有前景的复合陶瓷热障涂层材料。