Microstructure and mechanical properties of Al2O3/Er3Al5O12/ZrO2 prepared by a high-frequency zone melting method

Oxide directionally solidified eutectic ceramics (DSECs) have excellent mechanical properties, oxidation resistance, and ablation resistance in an ultra-high temperature environment above 1600 °C. In this study, Al₂O₃/Er₃Al₅O₁₂/ZrO₂ ternary DSECs were prepared by high-frequency induction zone melting. Their diameters were considerably greater than those of samples prepared with other processing techniques under the conditions where the microstructures were uniform. The component, microstructure, and mechanical properties in these samples were investigated. The results indicate that these DSECs were composed of only Al₂O₃, Er₃Al₅O₁₂, and ZrO₂ phases. As the solidification rate increased, both the eutectic phase size and eutectic spacing decreased continuously, and the microstructure was refined. The relationship between the eutectic spacing and solidification rate satisfied the formula λ²ν ≈ 33.8 ± 0.49. A polygonal colony structure appeared at a growth rate of 6.7 μm/s, which was associated with the uneven distribution of the temperature field. The hardness and indentation fracture resistance increased marginally with an increase in solidification rate, achieving 17.6 ± 0.8 GPa and 5.0 ± 0.5 MPa·m^1/2, respectively. The hardness of the Al₂O₃/Er₃Al₅O₁₂/ZrO₂ ternary DSEC was 18.3% less than that of the Al₂O₃/Er₃Al₅O₁₂ binary DSEC owing to the reduced hardness of the ZrO₂ phase added in the eutectic composition. The ternary DSEC's indentation fracture resistance was 88.4% greater than that of the binary eutectic ceramic owing to the phase transformation toughening of the ZrO₂ phase.     

激光悬浮区熔定向凝固Al2O3/YAG/ZrO2三元过共晶合金的微观组织

利用自行研制的激光悬浮区熔设备制备了Al₂O₃/YAG/ZrO₂三元过共晶自生复合材料.在过共晶成分下获得了不含初生相的全共晶层片状组织.详细分析了固/液界面形貌形成原因,并由界面形貌出发阐述了Al₂O₃/YAG/ZrO₂三元过共晶组织织构化趋势.结果表明,低凝固速率下,三元过共晶成分下层片间距大于三元共晶成分下层片间距,而在高凝固速率下则相反,这主要是由于ZrO₂的加入影响了体系的传热及传质条件,通过经典非规则共晶模型综合分析了传输条件对层片间距的影响.过共晶平均层片间距(λ_av)与凝固速率（V）满足λ_avV^0.5=14.7μm^1.5·s^-0.5,符合JH模型.对于激光加工中经常出现的带状组织形成机理也进行了讨论.     

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.     

The effect of the microstructure on mechanical properties of directionally solidified Al2O3/ZrO2(Y2O3) eutectic

The eutectic architecture of a continuous reinforcing phase within a higher volume fraction phase or matrix, can be described as a naturally occurring in-situ composite. Here we report the results of experiments aimed at identifying the sources of high temperature creep resistance and high levels of strength in a two phase Al₂O₃/ZrO₂(Y₂O₃) system. The mechanical properties of two phase Al₂O₃/ZrO₂(Y₂O₃) eutectic are superior to that of either constituent alone due to strong constraining effects provided by the coherent interfaces and micrsostructure. The Al₂O₃/ZrO₂(Y₂O₃) eutectic maintains a low energy interface resulting from directional solidification and can produce strong and stable reinforcing phase/matrix bonding. The phases comprising a eutectic are thermodynamically compatible at higher homologous temperatures than man-made composites and as such offer the potential for superior high temperature properties.     

Microstructure and physical properties of some oxide eutectic composites processed by directional solidification

Eutectic composites of lamellar ZrO₂–CaO and ZrO₂–NiO and fibrous Al₂O₃–ZrO₂, Al₂O₃–ZrO₂(Y₂O₃), ZrO₂–MgO and CaF₂–MgO wide gap materials have been grown from the melt by unidirectional solidification using laser floating zone and Bridgman techniques. The unique microstructure and interface morphology of these composites led to some remarkable mechanical (strength and toughness), optical (light guiding) and transport (ionic conduction) properties. The underlying relationships between microstructure and properties were briefly discussed in each case in the light of some possible applications of these eutectics.     

以超重力熔铸新技术快速制备Al2O3/YAG/YSZ三元共晶陶瓷

研究一种大块致密Al2O3/YAG/YSZ三元共晶陶瓷的快速制备新技术,以Al/Fe2O3/Y2O3/ZrO2为反应剂,通过诱发各组元间的燃烧合成反应,首先获得陶瓷(Al2O3/YAG/YSZ)和金属(Fe)的混合熔体;随后利用两种熔体的密度差异,在超重力场中实现陶瓷熔体和金属熔体的彻底分离和凝固.在超重力场作用下,先凝固的陶瓷相局部沉陷到金属熔体中,并受到金属熔体对之施加的接近2 MPa的瞬态等静压力,因此得以实现完全致密化.微观结构分析表明,所获得的三元共晶陶瓷的相组成和晶粒形貌沿超重力方向呈现明显的梯度渐变特征.     

TC4/ZrO2复合材料激光近净成形微观组织分析

采用激光近净成形系统成形了不同ZrO_2掺入量的TC4/ZrO_2薄壁,研究了扫描速率对金属基陶瓷材料成形热应力的影响,利用X射线衍射仪(XRD)、扫描电镜(SEM)、X射线能量色散谱仪(EDS)对薄壁样件进行相组成分析、微观组织观察以及元素分布检测。研究表明,相对较低的扫描速度可以减小薄壁件的残余应力,抑制样件的宏观裂纹;XRD结果显示当ZrO_2含量达到30%以上时,生成了TiO.325的Ti的非化学计量氧化物;TC4基体的微观组织随着ZrO_2掺入量的增多晶粒逐渐从针状过渡到板条状、块状;EDS结果显示当Ti晶粒为板条状,晶界间有ZrO_2富集;随着ZrO_2含量增多,Ti固溶体中固溶的Zr增多。本研究为最终成形TC4/ZrO_2梯度材料提供了可靠的技术支持。     

Microstructure Characterization of the FeAl<Subscript>2</Subscript>O<Subscript>4</Subscript>-Based Nanostructured Composite Coating Synthesized by Plasma Spraying Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/Al Powders

The microstructure of the coating prepared by reactive plasma spraying Fe₂O₃/Al composite powders was characterized by x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The results indicated that the coating exhibited nanostructured microstructure which consisted of FeAl₂O₄, Fe or Fe solid solution, Al₂O₃ and a little FeAl. In the composite coating, spherical Fe particles (tens of nanometers to hundreds of nanometers) were distributed uniformly within the equiaxed and columnar nanograins FeAl₂O₄ matrix. There were two kinds of Al₂O₃ phases present in the composite coating. One kind was nano-sized Al₂O₃ particles uniformly dispersed within the matrix, forming eutectic structure of (FeAl₂O₄ + γ-Al₂O₃); the other was 1-1.5 μm Al₂O₃ particles embedded individually within the matrix. The composite coating had higher toughness than the conventional microstructured Al₂O₃ coating.     

Laser surface cladding of MRI 153M magnesium alloy with (Al+Al2O3)

Laser surface cladding was carried out on a creep-resistant MRI 153M magnesium alloy with a mixture of Al and Al₂O₃ powders using a pulsed Nd:YAG laser at scan speeds of 21, 42, 63 and 84 mm/s. The Al₂O₃ particles partially or completely melted during laser irradiation and re-solidified with irregular shapes in the size range of 5-60 µm along with a few islands as large as 500 µm, within the grain-refined Mg-rich dendritic matrix. More than an order of magnitude improvement in wear resistance after cladding was attributed to the presence of ultra-hard Al₂O₃ particles, increased solid solubility of Al and other alloying elements, and a very fine dendritic microstructure as a result of rapid solidification in the cladded layer. However, corrosion resistance of the laser cladded alloy was reduced by almost an order of magnitude compared to that of the as-cast alloy mainly due to the presence of cracks and pores in the cladded layer.     

Phase and Microstructure Evolution and Toughening Mechanism of a Hierarchical Architectured Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Y<Subscript>2</Subscript>O<Subscript>3</Subscript> Coating under High Temperature

In recent years, numerous techniques have been developed to mimic nacre-like hierarchical architectures in order to improve the damage tolerance of materials. We present herein a simple strategy to fabricate such a hierarchical architectured Al₂O₃–Y₂O₃ composite coating via atmospheric plasma spraying. The evolution of the phase and microstructure of the Al₂O₃–Y₂O₃ composite coating were characterized under conditions of high-temperature exposure in air at 800-1350 °C. The hardness and porosity of several typical coatings were determined. In situ formation of dense hierarchical architectured Al₂O₃–YAG composite coating with improved hardness was achieved after heat treatment at 1350 °C. Compared with Al₂O₃ coating, elevated toughness was found for the hierarchical architectured Al₂O₃–YAG composite coating, which can be ascribed to the distribution of YAG phase that contributed to crack termination and deflection, and microbridging. After thermal aging treatment at 1350 °C, the hierarchical architectured Al₂O₃–YAG composite coating was quite stable after 100 h of thermal exposure. Furthermore, the Al₂O₃–Y₂O₃ composite coating exhibited superior sintering resistance compared with the Al₂O₃ coating.     

Cyclic oxidation behavior and thermal barrier effect of YSZ-(Al2O3/YAG) double-layer TBCs prepared by the composite sol-gel method

Novel YSZ (6 wt.% yttria partially stabilized zirconia)-(Al₂O₃/YAG) (alumina-yttrium aluminum garnet, Y₃Al₅O₁₂) double-layer ceramic coatings were fabricated using the composite sol-gel and pressure filtration microwave sintering (PFMS) technologies. The thin Al₂O₃/YAG layer had good adherence with substrate and thick YSZ top layer, which presented the structure of micro-sized YAG particles embedded in nano-sized α-Al₂O₃ film. Cyclic oxidation tests at 1000 °C indicated that they possessed superior properties to resist oxidation of alloy and improve the spallation resistance. The thermal insulation capability tests at 1000 °C and 1100 °C indicate that the 250 μm coating had better thermal barrier effect than that of the 150 μm coating at different cooling gas rates. These beneficial effects should be mainly attributed to that, the oxidation rate of thermal grown oxides (TGO) scale is decreased by the “sealing effect” of α-Al₂O₃, the “reactive element effect”, and the reduced thermal stresses by means of nano/micro composite structure. This double-layer coating can be considered as a promising TBC.     

CVD deposition and characterization of coloured Al2O3/ZrO2 multilayers

Coloured Al₂O₃/ZrO₂ multilayers have been deposited onto WC-Co based inserts by a CVD process. Through physical as well as optical analysis of such multilayers, colour is believed to originate from interference. The coatings are obtained with good process reproducibility. It was found that the ZrO₂ process used in the multilayer, with ZrCl₄ as the only metal chloride precursor, results in a mixture of tetragonal and monoclinic ZrO₂ phases. However by adding a relatively small amount of AlCl₃ during such a process results in ZrO₂ layers being composed of predominantly tetragonal ZrO₂ phase. Corresponding multilayers seem to have a more fine grained and smoother morphology whereas multilayers containing monoclinic ZrO₂ phase seem to be less perfect with existence of larger grains of ZrO₂ which are believed to scatter light and alter the reflectance of such a multilayer. In addition to this, such multilayers were found to be free of or with greatly reduced amount of thermal cracks, normally present in pure CVD grown Al₂O₃ layers.It is believed that, in the studied Al₂O₃/ZrO₂ multilayers, the observed tetragonal ZrO₂ phase is the result of a size effect, where small enough ZrO₂ crystallites energetically favor the tetragonal phase. However as the ZrO₂ crystallite size distribution is shifted to larger sizes it is believed that a mixture of crystallites with both stable and metastable tetragonal phases as well as a stable monoclinic phase is obtained. The proposed metastable tetragonal ZrO₂ phase may in fact explain the absence of thermal cracks in such multilayers through a transformation toughening mechanism, well known in ZrO₂ based ceramics.     

Solidification microstructure of laser remelted Al2O3ZrO2 eutectic

Surface resolidification experiments using a high power CO₂-laser have been performed on an Al₂O₃ZrO₂ containing 36.8 at.% ZrO₂ eutectic alloy at beam velocities between 0.3 and 8 mm·s⁻¹. The local growth rate has been measured by observation of the orientation of the microstructure using scanning electron microscopy. In the whole range of velocities, the structure is essentially a regular lamellar eutectic and the value of the growth productλ²V was found to be ≈ 9.6·10⁻¹⁷ m³·s⁻¹. The measured eutectic spacings were compared with Jackson and Hunt model. Using thermophysical properties from the literature, the measured spacings were more than four times larger than the calculated ones. Assuming all parameters of the growth relationship except the diffusion coefficient to be of the right order of magnitude or to have a negligible influence, agreement is found when using a larger liquid diffusion coefficient,D_L≈5·10⁻¹⁰m²·s⁻¹.     

ZrCr梯度界面层对Zr/Al2O3涂层体系抗热震性能影响及机理研究

采用中频磁控溅射和超音速等离子喷涂依次在锆合金(Zr-4)基体表面制备了Zr(84.61 at.%)Cr/Zr(17.39 at.%)Cr/Al₂O₃(ZrCr梯度界面层)和Al₂O₃ (无ZrCr梯度界面层)涂层。利用XRD、SEM和HRTEM等重点分析了ZrCr梯度界面层对Zr-4/Al₂O₃涂层界面微观结构、结合强度和抗热震性能的影响。研究结果表明：通过增设ZrCr梯度界面层,能显著提升Zr-4/ZrCr/Al₂O₃体系结合强度至50.3±2.52 MPa,较Zr-4/Al₂O₃体系结合强度值提升约46%;循环热震条件下,Zr-4/ZrCr/Al₂O₃体系膜基界面完整,与ZrCr梯度界面层能显著提升界面结合强度且喷涂及热震实验过程中ZrCr梯度界面层Cr原子优先形成较致密的Cr₂O₃能进一步有效抑制氧扩散至Zr-4有关;Zr-4/Al₂O₃膜基界面则出现明显开裂甚至剥离行为,其主因是Zr-4/Al₂O₃两者界面热应力集中而导致Zr-4/Al₂O₃界面开裂;HRTEM和EDS线扫描结果证实在Zr-4/Al₂O₃界面开裂处形成的疏松ZrO₂氧化物是后续热震循环中进一步加剧涂层大面积剥落失效的根本原因。     

Fabrication of A356 composite reinforced with micro and nano Al2O3 particles by a developed compocasting method and study of its properties

Aluminum/alumina composites are used in automotive and aerospace industries due to their low density and good mechanical strength. In this study, compocasting was used to fabricate aluminum-matrix composite reinforced with micro and nano-alumina particles. Different weight fractions of micro (3, 5 and 7.5 wt.%) and nano (1, 2, 3 and 4 wt.%) alumina particles were injected by argon gas into the semi-solid state A356 aluminum alloy and stirred by a mechanical stirrer with different speeds of 200, 300 and 450 rpm. The microstructure of the composite samples was investigated by Optical and Scanning Electron Microscopy. Also, density and hardness variation of micro and nano composites were measured. The microstructure study results revealed that application of compocasting process led to a transformation of a dendritic to a nondendritic structure of the matrix alloy. The SEM micrographs revealed that Al₂O₃ nano particles were surrounded by silicon eutectic and inclined to move toward inter-dendritic regions. They were dispersed uniformly in the matrix when 1, 2 and 3 wt.% nano Al₂O₃ or 3 and 5 wt.% micro Al₂O₃ was added, while, further increase in Al₂O₃ (4 wt.% nano Al₂O₃ and 7.5 wt.% micro Al₂O₃) led to agglomeration. The density measurements showed that the amount of porosity in the composites increased with increasing weight fraction and speed of stirring and decreasing particle size. The hardness results indicated that the hardness of the composites increased with decreasing size and increasing weight fraction of particles.     

BN/Al2O3 复合粉末及其聚合物基复合材料的制备与导热性能

采用固-液相共混法制备了多种BN/Al₂O₃复合粉末,通过冻融法和表面修饰法对BN进行了改性处理,改变表面修饰剂类型和摩尔比得到了前驱体和烧结态BN/Al₂O₃复合粉末,并利用机械混合法制备了聚合物基BN/Al₂O₃复合材料,并测试分析了其导热性能。结果表明,经冻融处理的BN分散性和界面相容性明显优于未经冻融处理的BN。多巴胺对BN的改性效果优于聚乙二醇。采用多巴胺作为表面修饰剂且BN与Al(NO₃)₃的摩尔比为1:1时,能够得到纳米Al₂O₃均匀包覆的微米BN粉末,即BN/Al₂O₃微纳复合粉末,其聚合物基复合材料的导热系数可达0.62 W·m^-1·K^-1,是纯聚合物导热系数的3倍,是采用纯微米BN粉末制备的聚合物基复合材料导热系数的1.5倍。在BN表面附着的Al₂O₃可以形成层状热传导通道,能够有效提高聚合物基BN/Al₂O₃复合材料的热导率。     

Preparation of Al2O3–ZrO2–SiO2 ceramic composites by high-gravity combustion synthesis

By a furnace-free technique of high-gravity combustion synthesis, Al₂O₃–ZrO₂–SiO₂ ceramic composites were prepared via melt solidification instead of conventional powder sintering. The solidification kinetics and microstructure evolution of the ceramic composites in high-gravity combustion synthesis were discussed. The phase assemblage of the ceramic composites depended on the chemical composition, where both (Al₂O₃ + ZrO₂) and (mullite + ZrO₂) composites were obtained. The ceramic composites consisted of ultrafine eutectics and sometimes also large primary crystals. In the (mullite + ZrO₂) composites, two different morphologies and orientations were observed for the primary mullite crystals, and the volume fraction of mullite increased with increasing SiO₂ content. The ceramic composites exhibited a hardness of 11.2–14.8 GPa, depending on the chemical composition and phase assemblage.     

High-temperature stability of nano-grained B2-structured RuAl-based intermetallics by mechanical alloying

A series of nano-grained B2-structured RuAl-based intermetallics and corresponding composites are synthesized by mechanical alloying. These RuAl-based materials include stoichiometric RuAl, B2-structured ternary (Ru,Ni)Al and (Ru,Ir)Al, eutectic RuAl–Ru and particle reinforced RuAl–ZrO₂ composite. The accumulation of impurities, mainly Fe, in grain boundaries and the structural evolution during grain growth are found to be the controlling factors for the grain growth stagnation in nano-grained B2-structured binary RuAl and ternary (Ru,Ni)Al and (Ru,Ir)Al intermetallics. Ternary alloying element forming iso-structured pseudo-binary compounds, eutectic in situ and ceramic particle reinforced composites are explored to be the effective routes to enhance the stability of single-phase RuAl. The thermal stability of microstructure in various RuAl-based materials are found to decrease in a sequence from pseudo-binary RuAl–IrAl, RuAl–NiAl, eutectic RuAl–Ru composites, ceramic particle reinforced RuAl–ZrO₂ composites to binary stoichiometric RuAl.     

Preparation of Al2O3–ZrO2–Y2O3 Composite Coatings by a Modified Sol–Gel Technique for Thermal Barrier Application

Spatial-network Al₂O₃–ZrO₂–Y₂O₃ composite coatings were prepared by a modified sol–gel technique, so-called thermal pressure and filtration of sol–gel paint. The composite coatings were derived from a composite paint of yttria partially stabilized zirconia (YSZ) particles, Al₂O₃ particles and Al₂O₃–Y₂O₃ sol. Their microstructure showed that YSZ particles were covered with spatial-network Al₂O₃–Y₂O₃ blanket. Cyclic oxidation at 1,050 °C in air for 200 h demonstrates that the oxygen diffusion rate in the coatings could be effectively inhibited. Meanwhile, suitable coefficients of thermal expansion (CTE) gave the composite coatings better spallation resistance than that of Al₂O₃–Y₂O₃ or ZrO₂–Y₂O₃ coatings. The positive results of cyclic oxidation indicated that the composite coating can be used as an interlayer between the bond coat and the top ceramic layer in traditional TBCs. Not only the depletion rate of aluminum-rich phase in MCrAlY alloy could be slowed down by spatial-network Al₂O₃–Y₂O₃, but also different thermal expansion between thermally grown oxides layer and top layer could be relieved by suitable CTE. In this paper, the mechanisms of the inhibition of oxygen diffusion and thermal match between ceramic coating and alloy are also discussed.