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。     

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.     

HOPG上ALD沉积Al2O3介电薄膜的生长行为研究

本文采用原子层沉积(ALD)的方法,选择三甲基铝(TMA)和H₂O₂作为反应前驱体,在高定向热解石墨(HOPG)基体上沉积Al₂O₃。系统研究了反应温度和生长周次对Al₂O₃生长行为的影响。研究表明：受HOPG表面饱和成键的影响,Al₂O₃在衬底表面处形核困难,在生长初期主要表现为台阶处择优生长,其形态为线状结构。当沉积100周次Al₂O₃时,其中在沉积温度为50 °C、150 °C和200 °C时呈现为纳米线状结构,而在100 °C时呈现为非连续薄膜。随着生长周次的增加,不同温度下沉积态Al₂O₃都趋于形成连续薄膜,表明其生长行为发生了由三维岛状生长模式向二维平面生长模式的转变。分析认为,生长模式的转变是由纳米线状结构横向生长造成的;横向生长速率主要受生长温度影响。拉曼结果表明：沉积后的石墨烯层结构未受影响,可保留其原有的优越性能。     

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.     

Investigation of the defect density in ultra-thin Al2O3 films grown using atomic layer deposition

The film perfection in terms of pinhole defect densities of ultra-thin Al₂O₃ grown by atomic layer deposition (ALD) has been quantitatively characterized. A significant defect density reduction from ~ 1.2 × 10⁵/cm² to ~ 90/cm² was demonstrated for 2 nm-thick Al₂O₃ by using an ALD tungsten (W) buffer layer on the nickel (Ni) substrate. The reason for the defect reduction was attributed to efficient nucleation of ALD Al₂O₃ on ALD W. The effect of the buffer layer becomes less essential as the Al₂O₃ thickness increases, where the substrate surface physical conditions such as particle contamination become the main cause for defects.     

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.     

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.     

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%。     

Selective single pulse femtosecond laser removal of alumina (Al2O3) from a bilayered Al2O3/TiAlN/steel coating

We studied surface modification of a double layer protective coating on steel induced by single fs laser pulse irradiation in ambient air. The outer alumina (Al₂O₃) layer, which protects against aggressive environments, was 1.7 μm thick and the titanium aluminum nitride (TiAlN) layer in contact with the steel surface had a thickness of 1.9 μm. The pulses (λ = 775 nm, τ = 200 fs) were generated by a Ti:sapphire laser source. The pulse energy was varied from 0.32 μJ to 50 μJ, corresponding to an incident laser fluence of 0.11 J cm^− 2 to 16.47 J cm^− 2. The surface damage threshold was found to be 0.20 J cm^− 2 and the alumina layer removal was initiated at 0.56 J cm^− 2. This selective ablation of alumina was possible in a wide range of fluences, up to the maximum applied, without ablating the TiAlN layer beneath.     

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.     

Mechanochemical synthesis of Al2O3-TiB2 nanocomposite powder from Al-TiO2-H3BO3 mixture

Alumina-titanium diboride nanocomposite (Al₂O₃-TiB₂) was produced using mixtures of titanium dioxide, acid boric and pure aluminum as raw materials via mechanochemical process. The phase transformation and structural characterization during mechanochemical process were utilized by X-ray diffractometry (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analyses (TG-DTA) techniques. A thermodynamic appraisal showed that the reaction between TiO₂, B₂O₃ and Al is highly exothermic and should be self-sustaining. XRD analyses exhibited that the Al₂O₃-TiB₂ nanocomposite was formed after 1.5 h milling time. The results indicate that increasing milling time up to 40 h had no significant effect other than refining the crystallite size.     

原子层沉积Al2O3 保护层氢终端金刚石MISFETs的电学特性

研究了Zr-Si-N氢终端金刚石（H-diamond）绝缘栅场效应晶体管（MISFET）在有无Al₂O₃保护层情况下的电学特性。分别采用原子层沉积法（ALD）和射频溅射法（RF）制备了Al₂O₃保护层和Zr-Si-N栅介质层。MISFETs的转移特性曲线表明,其栅阈值电压在有无Al₂O₃保护的情况下从-2.5 V变化到3 V,表明器件从常关型转换为常开型。输出和转移特性曲线揭示了氧化铝的存在保护了氢终端,使其免受磁控溅射过程的损伤。     

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。     

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.     

Al2O3陶瓷Ti+Nb/Mo金属化对其与Kovar合金钎焊连接的组织和力学性能的影响

采用磁控溅射在Al₂O₃陶瓷表面沉积了Ti+Nb/Mo金属层,实现了氧化铝陶瓷的金属化,并通过电镀镍提高了金属化效果.采用AgCu28钎料,实现了金属化Al₂O₃陶瓷与Kovar合金的可靠连接.通过扫描电子显微镜和能谱观察了钎缝的微观组织.结果表明,钎料与母材发生了明显的界面反应.Cu元素扩散进入Kovar合金,同时Ni元素扩散进入钎料的富铜区,从而促进AgCu/Kovar连接界面的形成;金属化层在Al₂O₃/AgCu钎料界面处,起到了关键作用,其中铌可以抑制脆性化合物形成,缓解残余应力.金属化层镀镍后,钎缝中AgCu共晶区明显,且钎缝较宽,对提高镀镍试样的钎焊接头强度有一定作用.     

The effect of plasma spray parameters on the cavitation erosion of Al2O3-TiO2 coatings

This paper reports a study of how the choice of plasma spray parameters, used during deposition of Al₂O₃-13%TiO₂ coatings on carbon steel, influences the cavitation erosion properties of such coatings. The parameters studied are the power feeding rate and hydrogen flow rate. The surface and cross section of coatings before and after cavitation were also observed by scanning electron microscopy (SEM). The phases present in the coatings were characterized by X-ray diffraction method (XRD). The microscopic observations were used to study the inter-lamellar connection, porosity, unmelted particles and so on inside the coating. We also measured the roughness, microhardness, adhesion strength and cavitation erosion of the coatings. The XRD results showed that the coating includes different allotropes of Al₂O₃ such as α and γ. The cavitation erosion studies of the coatings were conducted by ultrasonic cavitation testing on the basis of ASTM G32 standard. It was found that cavitation erosion is accelerated around the unmelted particles and porosities. The results reveal that the cavitation resistance of the coating is determined by its microstructure and that increasing discontinuities (inside the coating) reduce its cavitation resistance. We have found that the coating obtained at hydrogen gas flow rate of 16 L/min and powder feeding rate of 20 g/min has the best cavitation resistance.     

Al2O3包覆LiNi0.03Co0.05Mn1.92O4正极材料的制备及其电化学性能

以Al(NO3)3?9H2O为包覆原料,通过燃烧法制备得到LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料。通过X射线衍射(XRD),场发射扫描电子显微镜(FESEM)和透射电镜(TEM)等表征手段对材料的结构和形貌进行分析,并通过恒电流充放电、循环伏安(CV)、交流阻抗(EIS)等测试分析材料的电化学性能。结果表明,Al2O3包覆没有改变LiNi0.03Co0.05Mn1.92O4的尖晶石型结构,包覆层厚度约10.6nm。LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料电化学性能得到了明显改善,1 C和10 C倍率下初始放电比容量分别为119.9 mAh?g-1和106.3 mAh?g-1,充放电循环500次后容量保持率分别为88.4%和78.2%,而未包覆的LiNi0.03Co0.05Mn1.92O4在1 C和10 C倍率下初始放电比容量分别为121.2 mAh?g-1和104.0 mAh?g-1,500次循环后容量保持率分别为84.1%和67.6%。LiNi0.03Co0.05Mn1.92O4@Al2O3活化能为32.92 kJ?mol-1,而未包覆材料的活化能为36.24 kJ?mol-1,包覆有效降低了材料Li+扩散所需克服的能垒,提高了材料的电化学性能。     

采用Au基钎料真空钎焊Al2O3陶瓷

首先选用AgCuTi活性钎料在880℃/10 min参数下对A1₂O₃陶瓷表面进行金属化处理,之后尽量去除金属化层中的AgCu共晶组织,然后选用两种Au基高温钎料在980℃/10 min参数下对金属化后的A1₂O₃进行了钎焊连接.结果表明,在Al₂O₃/Au-Ni/Al₂O₃接头中靠近Al₂O₃母材的界面处生成一层薄薄的扩散反应层,该反应层主要由TiO₂和Al₂O₃组成;在Al₂O₃/Au-Cu/Al₂O₃接头中同样存在扩散反应层,与前者不同的是,接头中检测到Ti-Au相的存在.分别对Au-Ni和Au-Cu两种钎料获得的Al₂O₃接头进行了抗剪强度测试,前者对应接头强度为95.5 MPa,后者对应接头强度达到102.3 MPa.     

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.