Ba(Mg1/3Ta2/3)O3热障涂层的制备及抗热震性能研究

本文以BaCO₃、MgO、Ta₂O₅为原料,采用固相反应法合成了Ba(Mg_1/3Ta_2/3)O₃(简称BMT)陶瓷粉末,利用大气等离子喷涂技术制备了BMT/YSZ双层陶瓷涂层。利用XRD、SEM和金相显微镜检测了BMT粉体及涂层的物相组成和显微结构。采用水淬法考核了涂层的抗热震性能。结果表明：1450℃下煅烧4h可合成出具有复合钙钛矿结构的BMT粉末,粉末具有良好的高温相结构稳定性。等离子喷涂制备的BMT/YSZ涂层组织致密,涂层系统中各界面结合紧密。涂层在室温至1150℃间热震9次后发生片状剥落,剥落位置位于BMT层间,BMT材料低的断裂韧性和第二相Ba₃Ta₅O₁₅的存在是导致涂层失效的主要原因。     

La2(Zr0.7Ce0.3)2O7固相合成行为及热物理性能

采用固相合成制备了热障涂层陶瓷材料La2(Zr0.7Ce0.3)2O7(LZ7C3)。通过差热分析、X射线衍射等分析方法对固相合成行为影响因素进行研究,并用激光脉冲法和高温膨胀仪测试了LZ7C3粉末的热扩散系数和热膨胀系数。结果表明:完全合成LZ7C3的温度至少1400℃,煅烧时间至少5 h,反应粉末的粒度为0.82μm时,合成的LZ7C3粉末X射线衍射图谱没有La2 O3残留峰,其La∶Zr∶Ce为50.09∶35.12∶14.79,非常接近理论原子比例10∶7∶3;LZ7C3的热导率在1200℃时为0.79 W.m-1.K-1,热膨胀系数在1200℃时为11.6×10-6K-1,从室温到1200℃的加热过程中没有失重和相变发生,具有较高的相稳定性。     

Ba(Mg_(1/3)Ta_(2/3))O_3热障涂层的制备及抗热震性能

以Ba CO_3、Mg O、Ta_2O_5为原料,采用固相反应法合成了Ba(Mg_(1/3)Ta_(2/3))O_3(BMT)陶瓷粉末,利用大气等离子喷涂技术制备了BMT/YSZ(氧化钇部分稳定氧化锆)双层陶瓷涂层。利用XRD、SEM和金相显微镜检测了BMT粉体及涂层的物相组成和显微结构。采用水淬法考核了涂层的抗热震性能。结果表明:1450℃下煅烧4 h可合成出具有复合钙钛矿结构的BMT粉末,粉末具有良好的高温相结构稳定性。等离子喷涂制备的BMT/YSZ涂层组织致密,涂层系统中各界面结合紧密。涂层在室温至1150℃间热震9次后发生片状剥落,剥落位置位于BMT层内。BMT材料低的断裂韧性和第二相Ba_3Ta_5O_(15)的存在是导致涂层失效的主要原因。     

GYSZ-NiCr2O4复相陶瓷材料的高温稳定性及隔热能力研究

针对目前热障涂层光子导热较高的问题，设计了Gd掺杂YSZ-NiCr₂O₄复相陶瓷材料(GYSZ-NCO)，并对其烧结参数、热稳定性及热导率进行了分析。结果表明，在烧结温度为1600℃时可获得四方相GYSZ材料，且GYSZ-NCO系列材料在1500℃下具有较高的热稳定性，保温300 h无相变发生，加入NiCr₂O₄后，GYSZ材料热导率在高温下无明显回升，表现出了优良的抗光子导热能力，GYSZ-5%NCO材料热导率最低，在1200℃时仅为2.23 W/(m·K)。     

等离子喷涂(La0.4Sm0.5Yb0.1)2Zr2O7涂层的热性能研究

本文采用大气等离子喷涂制备了(La0.4Sm0.5Yb0.1)2Zr2O7涂层,并在相同的条件下制备了Sm2Zr2O7涂层作为对比。分别用扫描电子显微镜和X射线衍射仪分析 LSYZO涂层的微观形貌和相结构,并对两种涂层的热导率进行测定。结果表明,等离子喷涂后LSYZO涂层的相结构未发生变化。LSYZO涂层的结合强度为22 MPa,与SZO涂层相当。LSYZO涂层热震40次后发生失效,其热导率明显低于SZO涂层,这主要与LSYZO陶瓷自身的复杂结构有关。     

热震对包覆ZrB2-SiC-La2O3/SiC涂层渗硅石墨力学性能的影响

采用涂刷法和包埋法在渗硅石墨基体表面制备了双层结构的ZrB₂-SiC-La₂O₃/SiC防护涂层,与表面无包覆涂层的渗硅石墨作对比,采用三点弯曲实验方法研究了热震对其力学性能的影响。结果表明,1500℃到室温之间循环热震10次后,表面无包覆涂层的样品单位面积氧化失重为52.1 mg/cm²,弯曲强度保持率仅为52.0%;而包覆涂层样品单位面积氧化增重为5.6 mg/cm²,弯曲强度保持率达78.5%,包覆ZrB2-SiC-La2O3/SiC涂层的样品热震后能保持良好的力学性能。在热震过程中ZrB₂-SiC-La₂O₃/SiC涂层氧化生成的氧化层可有效地保护石墨基体不被氧化,避免了样品内部各种缺陷的产生,从而提高了其弯曲强度。     

温度对铜表面喷涂层冷热疲劳性的影响及失效机理

文中用等离子喷涂在CuCo2Be表面制备了Cr3C2-NiCr涂层,并分别在500,550,600,650℃进行热震试验,研究温度对其疲劳寿命的影响;选用XRD,SEM,EDS等研究了涂层及化合物相的形成、不同温度热震后涂层内、外表面的微观形貌、氧化产物等.结果表明,涂层呈现层状,化合物为角状Cr3C2-NiCr,涂层与界面的结合以机械结合为主;XRD分析发现涂层中形成了一定非晶相,热震后涂层中存在铜、镍氧化物.分析其热震失效机制为:500℃时主要是热膨胀系数突变引起的应力与氧化共同作用;随热震温度升高,涂层与基体结合处应力增大,涂层失效机制逐步转变为应力主导失效.     

钼合金MoSi2涂层高温热震行为与裂纹扩展

采用料浆烧结法在钼合金表面制备了MoSi₂涂层,利用内热法测试了涂层室温～1600℃抗热震性能,通过扫描电镜(SEM)、电子探针(EPMA)、波谱分析(WDS)和X射线衍射(XRD)等测试手段分析了不同热震次数的涂层微观形貌、组织结构以及裂纹萌生扩展。结果表明：涂层可承受室温～1600℃热震400次,热震过程中涂层由原始的MoSi₂-Mo₅Si₃双层结构演变为SiO₂-MoSi₂-Mo₅Si₃多层结构,涂层热震初期形成纵向裂纹并不断向基体扩展,热震后期裂纹贯穿涂层到达基体,MoO₃挥发使涂层/基体界面应力增大产生横向裂纹,导致涂层剥落失效。     

孔隙率对水热合成Bi2Te3热电性能的影响

用水热法制备了晶粒尺寸为几十纳米到几百纳米的Bi₂Te₃粉末,再通过压片法制得不同孔隙率的Bi₂Te₃薄片材料,研究了孔隙率对Bi₂Te₃热电性能的影响。通过对热电性能的测试,研究发现压片法制得的Bi₂Te₃样品具有较高的孔隙率,且样品的热传导符合多孔材料的热传导规律。当Bi₂Te₃样品孔隙率较大时具有较低的热导率,在室温下测得孔隙率为43%的Bi₂Te₃薄片热导率为0.282W·m^-1·K^-1。材料热导率、电导率和ZT值均随孔隙率的增加而减小。     

超声冲击处理提高超音速等离子喷涂Cr3C2-NiCr涂层性能

Cr₃C₂-NiCr涂层是中高温下理想的耐磨、抗氧化、耐蚀涂层,常用于高温下的燃气冲蚀磨损、磨粒磨损、微动磨损、硬表面磨损等场合.文中采用超音速等离子喷涂的方法在CuCrZr合金表面制备Cr₃C₂-NiCr涂层,并采用超声冲击的方法对涂层进行后处理.结果表明,经超声冲击处理后,涂层孔隙率由2.34%降低至1.83%;涂层的平均显微硬度由8.9 GPa提高至9.6 GPa,且硬度分布更均匀;在650℃下进行热震试验,涂层的热震寿命显著提高,热震裂纹的扩展路径也发生了变化.     

Thermal cycle behavior of plasma sprayed La2O3, Y2O3 stabilized ZrO2 coatings

The effects of La₂O₃ addition on thermal conductivity, phase stability and thermal cycle life of Y₂O₃ stabilized ZrO₂ plasma sprayed coatings were investigated. Although low thermal conductivity as well as high resistance to sintering was achieved by La₂O₃ addition, it tended to also result in lower phase stability and thermal cycle life of the coatings. Optimization of the composition and structure of the coatings improved these properties, and the optimized coatings showed prolonged thermal cycle life.     

Phase relations of La2O3---CaO---CuO ternary system and Ca substitution for La in La2CuO4

The subsolidus phase relations of the system La₂O₃-CaO-CuO sintered at 980 °C in air have been investigated by X-ray powder diffraction (XRD). The system can be divided into seven three-phase regions and two extended two-phase regions. In this system there exist two binary compounds La₂CuO₄ and Ca₂CuO₃, two ternary compounds La₂CaCu₂O₆ and LaCa₂Cu₅O_γ and one solid solution La_2-χCa_χCuO_4-δ. The effects of Ca²⁺ substitution for La³⁺ on the superconductivity and crystal structure of La₂CuO₄ have been investigated by XRD, differential thermal analysis, electrical and oxygen content measurements.     

双脉冲电沉积纳米晶Ni-CeO2复合镀层的微观结构及其高温抗氧化性能

在超声波振荡环境下,用双脉冲电源在Watt-Ni电解液体系中电沉积了纳米晶Ni CeO₂复合镀层,采用E-S:EM,TEM和XRD对镀层的形貌,微观结构及相组成进行分析;通过循环氧化增重曲线和DSC曲线,比较研究了纯Ni镀层和NiCeO₂复合镀层的高温抗氧化性能与热稳定性.结果表明,超声波振荡能有效抑制纳米颗粒在镀液中的团聚;添加20 g/L CeO₂,可使Ni晶粒细化;在873 K空气中退火处理2 h,复合镀层中的CeO₂沿裂纹扩展间隙处析出并形成含有稀土元素的弥散相,可起到钉扎晶界和阻止热裂纹萌生的作用.晶界作为Ni的快速扩散通道,促进稀土弥散相沿晶界析出并形成连续的致密氧化膜,能有效抑制O与Ni原子在氧化膜中互扩散,从而降低镀层的氧化速率.通过测定不同升温速率下镀层DSC曲线的吸热峰对应温度,由Kissinger方程求得Ni CeO₂复合镀层中Ni晶粒长大的表观活化能为243.3 kJ/mol,明显高于纯Ni的晶粒长大表观活化能（159.2 kJ/mol）,吸热峰对应温度也较纯Ni镀层提高约130 K,因此Ni-CeO₂复合镀层具有更高的热稳定性.     

NiCrAlY/Al-Al2O3/Ti2AlNb高温抗氧化和力学性能研究

采用电弧离子镀技水在NiCrAlY涂层与O相Ti₂AlNb合金之间沉积不同Al:Al₂O₃比例的Al-Al₂O₃薄膜作为扩散阻挡层.研究了900℃下恒温氧化500 h后NiCrAlY/Al-Al₂O₃/Ti₂AlNb体系中Al-Al₂O₃层阻挡合金元素互扩散的行为,以及对涂层氧化动力学曲线的影响.结果表明,没有添加扩散阻挡层的NiCrAlY/Ti₂AlNb体系,涂层和基体之间的元素互扩散十分严重,涂层丧失抗氧化能力;而添加扩散阻挡层的材料体系,涂层和基体之间的元素互扩散受到抑制,涂层的长期抗高温氧化性能得到提高.对于3Al-Al₂O₃,1Al-Al₂O₃和0Al-Al₂O₃ 3种扩散阻挡层,综合比较材料体系的抗氧化性能、阻挡层阻挡涂层和基体元素互扩散能力、以及涂层和基体之间结合力,当1Al-Al₂O₃薄膜作为扩散阻挡层时,材料性能最优异.同时,本文利用扩散阻挡系数简洁定量地表示出不同Al:Al₂O₃比例阻挡层的阻挡扩散能力.     

掺杂sc的CaZrO3的制备及电学性能

采用掺杂Sc₂O₃,通过固相反应法制备了CaZr_1-xSc_xO_3-α（x=0,0.1,0.15）材料.在610-850℃采用交流阻抗谱法测定了CaZr_1-xSc_xO_3-α的电导率及电导激活能,并对CaZrO₃掺Sc及掺In样品的电学性能进行了比较.结果表明:在610-850℃,CaZrO₃的电导率为4.3×10^-19-1.4×10^-6S/cm,CaZr_1-xSc_xO_3-α（x=0.1,0.15）的电导率为1.16×10^-4-1.4×10^-3S/cm,CaZr_1-xIn_xO_3-α（x=0.1,0.15）的电导率为0.34×10^-4-4.33×10^-4S/cm,且随着温度的升高而提高;掺杂能极大提高CaZrO₃的电导率,并随着掺杂量的增加,电导激活能降低,电导率增加;温度及掺杂量相同时,掺Sc材料电导率明显高于掺In材料,说明掺Sc对提高材料的电导率更有效.     

Synthesis and characterization of doped LaCrO3 perovskite prepared by EDTA–citrate complexing method

The La_0.85Sr_0.15Cr_0.95Ni_0.02Co_0.02O₃ (LSC) interconnect materials for solid oxide fuel cells (SOFCs) were synthesized by EDTA–citrate complexing method. Thermal decomposition behavior of the gel, phase formation and morphology of LSC powders were characterized by thermogravimetry/differential thermal (DSC/TG) analysis, X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. It appeared that lower pH value (pH 4.9) of the precursor solution resulted in a transient liquid phase, SrCrO₄, in the calcined LSC powder. The sintering characteristics, electrical conductivity and thermal expansion properties of sintered bars were investigated. La_0.85Sr_0.15Cr_0.95Ni_0.02Co_0.02O₃ prepared in the condition of pH 4.9 showed an electrical conductivity of 15.6 S cm⁻¹ at 800 °C and a thermal expansion coefficient (TEC) of 10.8 × 10⁻⁶ K⁻¹ (20–900 °C), which is suitable for use as interconnect materials for SOFCs.     

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.     

Novel thermal barrier coatings based on La2(Zr0.7Ce0.3)2O7/8YSZ double-ceramic-layer systems deposited by electron beam physical vapor deposition

Double-ceramic-layer (DCL) thermal barrier coatings (TBCs) of La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) and yttria stabilized zirconia (YSZ) were deposited by electron beam-physical vapor deposition (EB-PVD). The thermal cycling test at 1373 K in an air furnace indicates the DCL coating has a much longer lifetime than the single layer LZ7C3 coating, and even longer than that of the single layer YSZ coating. The superior sintering-resistance of LZ7C3 coating, the similar thermal expansion behaviors of YSZ interlayer with LZ7C3 coating and thermally grown oxide (TGO) layer, and the unique growth modes of columns within DCL coating are all very helpful to the prolongation of thermal cycling life of DCL coating. The failure of DCL coating is mainly a result of the reduction-oxidation of cerium oxide, the crack initiation, propagation and extension, the abnormal oxidation of bond coat, the degradation of t′-phase in YSZ coating and the outward diffusion of Cr alloying element into LZ7C3 coating.     

Preparation and properties of a γ-Al2O3 washcoat deposited on a ceramic honeycomb

Washcoat deposited on ceramic honeycomb was prepared using pseudoboehmite, the CeO₂–ZrO₂–La₂O₃ solid solution, pore enlarger and other additives. The microstructures and surface performances of washcoat/honeycomb were investigated by SEM, BET surface area, XRD, ultrasonic vibration and hot shock simulation. The results show that the performance and loading of washcoat are affected obviously by the properties of slurry gel, such as the apparent viscosity, solid content, particle size and its distribution. When the apparent viscosity of slurry is lower, the gel with a narrow particle size distribution and finer particles can be obtained, with which the coating having an excellent performance can be prepared. Adding a small quantity of the CeO₂–ZrO₂–La₂O₃ solid solution can promote the thermal stability of washcoat, such as, after calcined at 1000 °C for 5 h the sample exhibits mainly the γ-Al₂O₃ phases and the θ-Al₂O₃ -Al₂O₃ and κ-Al₂O₃ phases have not been detected in the XRD spectra. It is found also that the washcoat prepared has excellent properties of the vibration-resistant, heat-resistant and its BET surface area reaches 50 m²/g.     

Ionic conductivity and Raman investigations on the phase transformations of Na4P2O7

The ionic conductivity and thermo-Raman spectra of anhydrous sodium pyrophosphate Na₄P₂O₇ were measured dynamically in the temperature range from 25 to 600 °C with a heating rate of 2 °C min⁻¹ to understand the structural evolution and phase transformation involved. The DSC thermogram was also measured in the same thermal process for the phase transformation investigation. The spectral variations observed in the thermo-Raman investigation indicated the transformation of Na₄P₂O₇ from low temperature phase () to high temperature phase () proceeded through pre-transitional region from 75 to 410 °C before the major orientational disorder at 420 °C and minor structural modifications at 511, 540 and 560 °C. The activation energies and enthalpies of the proposed phase transformations were determined. The possible mechanism for temperature dependent conductivity in Na₄P₂O₇ was discussed with the available data.