国外多孔基体氧化铝/氧化铝复合材料工程应用进展

氧化铝/氧化铝复合材料(Al2O3/Al2O3)是20世纪90年代兴起的一类连续陶瓷纤维增强陶瓷基复合材料,已经发展为与SiC/SiC、C/SiC等非氧化物陶瓷基复合材料并列的一类陶瓷基复合材料。与非氧化物陶瓷基复合材料相比,Al2O3/Al2O3具有长时抗氧化、高温耐腐蚀、低成本等独特优势,已经在航空发动机、地面燃气轮机等军民两用热结构材料领域展现出广阔的应用前景。本文从材料应用的角度出发,系统分析阐述了目前在Al2O3/Al2O3占主导地位的多孔基体Al2O3/Al2O3(P-Al2O3/Al2O3)的增韧机制、成型工艺和性能特点,重点归纳了国外近年来P-Al2O3/Al2O3的工程化应用进展及前景,最后指出了P-Al2O3/Al2O3存在的局限性并展望了未来发展方向,旨在为国内Al2O3/Al2O3体系发展提供借鉴和参考。     

Microstructure and mechanical properties of Al2O3-Cr2O3 composite coatings produced by atmospheric plasma spraying

Al₂O₃, Al₂O₃-Cr₂O₃ and Cr₂O₃ coatings were deposited by atmospheric plasma spraying. Phase composition of powders and as-sprayed coatings was determined by X-ray diffraction. Electron probe microanalyzer was employed to investigate the polished and fractured surface morphologies of the coatings. Mechanical properties including microhardness, fracture toughness and bending strength were evaluated. The results indicate that the addition of Cr₂O₃ is conducive to the stabilization of α-Al₂O₃. Compared with the pure Al₂O₃ and Cr₂O₃ coatings, Al₂O₃-Cr₂O₃ composite coatings show lower porosities and denser structures. Heterogeneous nucleation of α-Al₂O₃ occurs over the isostructural Cr₂O₃ lamellae and partial solid solution of Al₂O₃ and Cr₂O₃ might be occurring as well. Furthermore, grain refining and solid solution strengthening facilitate the mechanical property enhancement of Al₂O₃-Cr₂O₃ composite coatings.     

Investigation on the corrosion and oxidation resistance of Ni-Al2O3 nano-composite coatings prepared by sediment co-deposition

Ni-Al₂O₃ composite coatings were prepared by using sediment co-deposition (SCD) technique from a Watt's type electrolyte containing nano-Al₂O₃ particles. The corrosion resistance and high temperature oxidation resistance of resulting composite coatings were investigated. It was found that the incorporation of nano-Al₂O₃ particles in Ni matrix refined the Ni crystal and changed the preferential orientation of composite coatings. Meanwhile, the corrosion and oxidation resistance were improved after the incorporation of nano-Al₂O₃ particles into Ni matrix. The nano-Al₂O₃ content in deposits plays an important role for improving the corrosion and oxidation protection. The corrosion and oxidation resistance of Ni-Al₂O₃ nano-composite coatings produced via SCD technique are superior to that of CEP technique. Compared to pure Ni and Ni-Al₂O₃ composite coatings fabricated using CEP technique, the Ni-7.58 wt.% Al₂O₃ composite coating obtained by SCD technique exhibits better corrosion resistance and enhanced high temperature oxidation resistance. Moreover, the mechanism of corrosion and high temperature oxidation resistance of Ni-Al₂O₃ nano-composite coatings are discussed.     

Mechanical and tribological performance of Al2O3-TiO2 coatings elaborated by flame and plasma spraying

Mechanical properties and wear rates of Al₂O₃-13 wt.% TiO₂ (AT-13) and Al₂O₃-43 wt.% TiO₂ (AT-43) coatings obtained by flame and atmospheric plasma spraying were studied. The feed stock was either ceramic cords or powders. Results show that the wear resistance of AT-13 coatings is higher than that of AT-43 and it seems that the effect of hardness on wear resistance is more important than that of toughness. Additionally, it was established that, according to conditions used to elaborate coatings and the sliding tribological test chosen, spray processes do not seem to have an important effect on the wear resistance of these coatings.     

Preparation, microstructure and properties of molybdenum alloys reinforced by in-situ Al2O3 particles

The conventional molybdenum alloys, lacking of hard particles enhancing wear property, have relative poor wear resistance though they are widely used in wear parts. To resolve the above question, Mo alloys reinforced by in-situ Al₂O₃ particles are developed using powder metallurgy method. The in-situ α-Al₂O₃ particles in molybdenum matrix are obtained by the decomposition of aluminum nitrate after liquid-solid incorporation of MoO₂ and Al(NO₃)₃ aqueous solution. The α-Al₂O₃ particles well bonded with molybdenum distribute evenly in matrix of Mo alloys, which refine grains of alloys and increase hardness of alloys. The absolute density of alloy increases firstly and then decreases with the increase of Al₂O₃ content, while the relative density rises continuously. The friction coefficient of alloy, fluctuating around 0.5, is slightly influenced by Al₂O₃. However, the wear resistance of alloy obviously affected by the Al₂O₃ particles rises remarkably with the increasing of Al₂O₃ content. The Al₂O₃ particles can efficiently resist micro-cutting to protect molybdenum matrix, and therefore enhances the wear resistance of Mo alloy.     

Electrodeposition of sol-enhanced nanostructured Ni-TiO2 composite coatings

A novel electroplating method has been developed to produce nanocrystalline metal-matrix nano-structured composite coatings. A small amount of transparent TiO₂ sol was added into the traditional electroplating Ni solution, leading to the formation of nanocrystalline Ni-TiO₂ composite coatings. These coatings have a smooth surface. The Ni nodules changed from traditional pyramid-like shape to spherical shape. The grain size of Ni was also significantly reduced to the level of 50 nm. It was found that the amorphous anatase TiO₂ nano-particles (∼ 10 nm) were highly dispersed in the coating matrix. The microhardness was significantly increased from 320 HV₁₀₀ of the traditional Ni coating to 430 HV₁₀₀ of the novel composite coating with 3.26 wt.% TiO₂. Correspondingly, the wear resistance of the composite coating was improved by ∼ 50%.     

Al2O3-nanodiamond composite coatings with high durability and hydrophobicity prepared by aerosol deposition

We attempted the room-temperature fabrication of Al₂O₃-based nanodiamond (ND) composite coating films on glass substrates by an aerosol deposition (AD) process to improve the anti-scratch and anti-smudge properties of the films. Submicron Al₂O₃ powder capable of fabricating transparent hard coating films was used as a base material for the starting powders, and ND treated by 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFOTES) was added to the Al₂O₃ to increase the hydrophobicity and anti-wear properties. The ND powder treated by PFOTES was mixed with the Al₂O₃ powder by ball milling to ratios of 0.01 wt.%, 0.03 wt.%, and 0.05 wt.% ND. The water contact angle (CA) of the Al₂O₃-ND composite coating films was increased as the ND ratio increased, and the maximum water CA among all the films was 110°. In contrast to the water CA, the Al₂O₃-ND composite coating films showed low transmittance values of below 50% at a wavelength of 550 nm due to the strong agglomeration of ND. To prevent the agglomeration of ND, the starting powders were mixed by attrition milling. As a result, Al₂O₃-ND composite coating films were produced that showed high transmittance values of close to 80%, even though the starting powder included 1.0 wt.% ND. In addition, the Al₂O₃-ND composite coating films had a high water CA of 109° and superior anti-wear properties compared to those of glass substrates.     

Preparation and characterization of nano TiO2/micron Cr2O3 composite particles

Nano-TiO₂/micro-size Cr₂O₃ composite particles were first prepared by hydrolysis of Ti(OBu)₄ in an abundant acidic aqueous solution without calcinations at room temperature. XPS analysis shows that the element C, O, Ti and Sn existed on the surfaces of the composite particles. Observation by field emission scanning electronic microscope shows TiO₂ particles of 10-15 nm covers on Cr₂O₃ powder surfaces to form nanometer/micron composite particles. UV-vis spectra show a red shift of the absorption edge and a significant increase of absorption intensity in the visible region. These results confirm that TiO₂ of anatase type can be synthesized on the surface of Cr₂O₃.     

La2O3含量对Al2O3/Cu基复合材料组织与性能的影响

以La₂O₃粉、Al粉、CuO粉为反应物原料、纯铜为基体,采用原位合成技术和近熔点铸造法制备颗粒增强Cu基复合材料,研究La₂O₃对Al-CuO体系制备的Cu基复合材料组织及性能的影响。结果表明：添加La₂O₃可获得纳米Al₂O₃颗粒,且弥散分布于Cu基体中,制备的材料组织更加细小、均匀,其材料的电导率及摩擦磨损性能明显提高。当添加0.6%wtLa₂O₃,复合材料的电导率达到90.2%IACS,磨损量达到最小,相比未添加La₂O₃,其导电率提高10.1%,磨损量减小36.6%。     

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.     

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.     

Al_2O_3/MoS_2复合涂层的制备及摩擦磨损性能

以大气等离子喷涂工艺制备的Al_2O_3陶瓷涂层为模板,利用陶瓷涂层中存在的孔隙和微裂纹,采用水热反应在其内部原位合成具有润滑特性的MoS_2,制备出Al_2O_3/MoS_2的复合涂层。结果表明,通过水热反应在陶瓷涂层原有的微观缺陷中成功合成了MoS_2,合成的MoS_2固体粉末呈类球形状,并且这球状的粉末是由纳米片层状的MoS_2搭建组成的。摩擦试验结果表明,与纯Al_2O_3涂层相比,复合涂层中由于MoS_2润滑膜的形成,其摩擦因数和磨损率都显著降低,且载荷越大,复合涂层的摩擦性能越好。     

Fe3O4/SiO2/Bi2WO6磁性复合光催化剂的制备及其光催化性能

钨酸铋(Bi₂WO₆),结构最简单的Aurivillius相化合物,是近期受到研究者关注的新型光催化材料。然而,光催化剂粉末在反应介质中难被回收,工业化应用成本较高。本文用三步方法合成了可回收的Fe₃O₄/SiO₂/Bi₂WO₆磁性复合光催化剂,通过溶剂热法合成具有磁性的Fe₃O₄,用溶胶凝胶法在Fe₃O₄表面覆盖SiO₂层,后将磁性颗粒与Bi₂WO₆纳米片相结合。光催化剂的形貌结构及性能通过XRD、SEM、PL、UV-vis进行表征测试。结果表明,直径约500 nm的Fe₃O₄微球附着在边长约500 nm的Bi₂WO₆纳米片的表面,SiO₂在两者之间起到了粘连作用。光催化剂Fe₃O₄/SiO₂/Bi₂WO₆对于罗丹明B的光降解活性较好,且有一定磁性,可以通过外加磁场将其从溶液中分离,有较大的应用潜力。     

Thermal shock fatigue behavior of TiC/Al2O3 composite ceramics

The thermal shock fatigue behaviors of pure hot-pressed alumina and 30 wt.% TiC/Al₂O₃ composites were studied. The effect of TiC and Al₂O₃ starting particle size on the mechanical properties of the composites was discussed. Indentation-quench test was conducted to evaluate the effect of thermal fatigue temperature difference (ΔT) and number of thermal cycles (N) on fatigue crack growth (Δa). The mechanical properties and thermal fatigue resistance of TiC/Al₂O₃ composites are remarkably improved by the addition of TiC. The thermal shock fatigue of monolithic alumina and TiC/Al₂O₃ composites is due to a “true” cycling effect (thermal fatigue). Crack deflection and bridging are the predominant reasons for the improvement of thermal shock fatigue resistance of the composites.     

Al2O3/TiB2/Al复合材料的微观结构和高温力学性能

以细雾化铝粉和TiB₂颗粒为原料,通过粉末冶金和热轧制制备微米TiB₂和纳米Al₂O₃颗粒增强铝基复合材料。室温时,由于TiB₂和Al₂O₃的综合强化作用,Al₂O₃/TiB₂/Al复合材料的屈服强度和抗拉强度分别为258.7 MPa和279.3 MPa,测试温度升至350℃时,TiB₂颗粒的增强效果显著减弱,原位纳米Al₂O₃颗粒与位错的交互作用使得复合材料的屈服强度和抗拉强度达到98.2MPa和122.5 MPa。经350℃退火1000 h后,由于纳米Al₂O₃对晶界的钉扎作用抑制晶粒长大,强度和硬度未发生显著的降低。     

Deposition, microstructure and properties of texture-controlled CVD α-Al2O3 coatings

The influence of nucleation on the microstructure and properties of CVD Al₂O₃ was investigated. The experimental α-Al₂O₃ layers were deposited (a) without nucleation control and (b) with nucleation steps resulting in pronounced , and growth textures. The experimental layers were characterised using X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Wear properties of the textured coatings were evaluated in turning. The chemistry of the nucleation surface appeared to be an important factor in pre-determining the phase content and growth textures of the Al₂O₃ layers. Optimised nucleation resulted in substantially improved wear properties and these kinds of α-Al₂O₃ layers were typically composed of relatively small, defect-free grains exhibiting no porosity. The textured α-Al₂O₃ layer showed the best wear resistance.     

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.     

In-situ TiB2 and Al2O3 formation by DC plasma spraying

In-situ plasma spraying (IPS) is a promising process to fabricate composite coatings with in-situ formed thermodynamically stable phases. In the present study, mechanically alloyed Al-12Si, B₂O₃ and TiO₂ powder was deposited onto an aluminum substrate using atmospheric plasma spraying (APS). It has been observed that, during the coating process, TiB₂ and Al₂O₃ are in-situ formed through the reaction between starting powders and finely dispersed in hypereutectic Al-Si matrix alloy. Also, obtained results demonstrate that in-situ reaction intensity strongly depends on spray conditions.     

Toughening and strengthening mechanism of plasma sprayed nanostructured Al2O3–13 wt.%TiO2 coatings

The starting materials of Al₂O₃, TiO₂, ZrO₂ and CeO₂ nanoparticles were agglomerated into sprayable feedstock powders and plasma sprayed to form nanostructured coatings. There were net structures and fused structures in plasma sprayed nanostructured Al₂O₃–13 wt.%TiO₂ coatings. The net structures were derived from partially melted feedstock powders and the fused structures were derived from fully melted feedstock powders. The nanostructured Al₂O₃–13 wt.%TiO₂ coatings possessed higher hardness, bonding strength and crack growth resistance than conventional Metco 130 coatings which were mainly composed of lamellar fused structures. The higher toughness and strength of nanostructured Al₂O₃–13 wt.%TiO₂ coatings were mainly related to the obtained net structures.     

Scratching of Al2O3 under pre-stressing

Pre-stressing scratching tests have been preformed on polished surfaces of Al₂O₃ ceramic under a Rockwell diamond indenter which moved with uniform speed and constant normal load to investigate how the pre-stress contributes to the material removal mechanism. With the measurement of acoustic emission signals as well as indenter tangential forces, surface damages and cross-section of grooves of Al₂O₃ ceramic were evaluated under the action of different values of pre-stress. It was found that the scratched groove width was increased with the increasing of pre-stress when same normal loads were applied. The existence of pre-stress tends to restrain the crack propagation along the direction of pre-stress, and obvious plastic deformation at the bottom of scratched groove has been observed. Moreover, the fluctuation of tangential force was obviously enhanced, and the magnitude of tangential force in the test of pre-stress was higher than that of without pre-stress. The acoustic emission signals showed that fewer damages were produced in the process of scratching with an appropriate pre-stress. However, the continuing increase of pre-stress would aggravate the machining process.