Characterization of zirconia- and niobia-silica mixture coatings produced by ion-beam sputtering

ZrO2-SiO2 and Nb2O5-SiO2 mixture coatings as well as those of pure zirconia (ZrO2), niobia (Nb2O5), and silica (SiO2) deposited by ion-beam sputtering were investigated. Refractive-index dispersions, bandgaps, and volumetric fractions of materials in mixed coatings were analyzed from spectrophotometric data. Optical scattering, surface roughness, nanostructure, and optical resistance were also studied. Zirconia-silica mixtures experience the transition from crystalline to amorphous phase by increasing the content of SiO2. This also results in reduced surface roughness. All niobia and silica coatings and their mixtures were amorphous. The obtained laser-induced damage thresholds in the subpicosecond range also correlates with respect to the silica content in both zirconia- and niobia-silica mixtures.     

单分散SiO_2/TiO_2/SiO_2多层复合微球的制备

采用一种以醇盐水解法为基础的生长硅溶胶的方法,制备了粒径为２００ｎｍ的单分散二氧化硅球形颗粒,并将其作为核心,利用常温连续进料的钛酸丁酯水解的多步法,在二氧化硅核心外经多次包覆形成厚层二氧化钛;在正硅酸乙酯的水解和陈化环境下,将上述ＴｉＯ２／ＳｉＯ２复合颗粒外再包覆一薄层二氧化硅,形成一种高折射率,可用于组装光子晶体的ＳｉＯ２／ＴｉＯ２／ＳｉＯ２多层复合微球．对该复合微球用重力沉降法、透射电镜法（ＴＥＭ）、Ｘ射线能谱分析法（ＥＤＳ）进行了表征．其中,重力沉降法是一种将Ｓｔｏｋｅｓ公式为基础推导的复合颗粒的粒径与沉降速度关系式所得的一系列数据进行拟合外延,来测定复合颗粒的粒径及包覆厚度的方法．     

Roughness and Light Scattering of Ion-Beam-Sputtered Fluoride Coatings for 193 nm

Scattering characteristics of multilayer fluoride coatings for 193 nm deposited by ion beam sputtering and the related interfacial roughnesses are investigated. Quarter- and half-wave stacks of MgF(2) and LaF(3) with increasing thickness are deposited onto CaF(2) and fused silica and are systematically characterized. Roughness measurements carried out by atomic force microscopy reveal the evolution of the power spectral densities of the interfaces with coating thickness. Backward-scattering measurements are presented, and the results are compared with theoretical predictions that use different models for the statistical correlation of interfacial roughnesses.     

Layer-by-layer self-assembly of multilayer zirconia nanoparticles on silica spheres for HPLC packings

A novel zirconia-based HPLC packing material, ZrO2/SiO2, which consists of micrometer-sized silica spheres as core and nanometer-sized zirconia particles as surface coating, was prepared by a layer-by-layer self-assembly technique. The material exhibits favorable characteristics for HPLC applications, including high surface area and pore volume, good pore structure, narrow particle size, and pore size distribution. Not only the support ZrO2/SiO2 but also the stationary-phase C18 bonded ZrO2/SiO2 exhibits excellent chemical stability. In addition, good permeability was observed for both of them. High specific area surface and good permeability of ZrO2/SiO2 permit a high loading amount of chiral polymer on it and greatly improved the enantioselectivity and resolution for some chiral separations.     

SiO2—TiO2—ZrO2系涂层的制备及其特性

用溶胶－凝胶法（sol-gel method）在不锈钢表面制备了SiO2-TiO2-ZrO2系无机氧化膜（STZ）。用DTA／TG、IR、XRD和SEM等手段研究了涂层制备时由凝胶向玻璃态的转变以及涂层薄膜的显微结构特点，考察了涂层对基体的保护效果。试验结果表明，在溶胶至凝胶最终转变为无机氧化物的过程中形成了无机网络，Si^4 和Zr^4 充当了网络骨架的形成离子。涂层为无定型玻璃态，其间混有石英、锐钛矿或金红石等微晶。     

Effect of substrate rotation on structure, hardness and adhesion of magnetron sputtered TiB2 coating on high speed steel

Titanium diboride (TiB₂) coatings have been deposited on stationary and rotating high speed steel substrates by magnetron sputtering of a TiB₂ target. The structure and hardness of the coatings and the coating–substrate adhesion have been investigated by X-ray diffraction, field emission scanning electron microscopy, nanoindentation and microscratch tests. The results show that substrate rotation has a significant effect on these structural and properties features. It was found that, with substrate rotation, the TiB₂ coating exhibits a columnar structure with random orientation and relatively low hardness and coating–substrate adhesion. On the other hand, without substrate rotation, the TiB₂ coating shows a strong (001) texture with dense, equiaxed grain structure. The hardness and coating–substrate adhesion of the coatings deposited on stationary substrates are much higher than those deposited on rotating substrates. The observed phenomena are discussed in terms of the energy of the sputtered flux, which varies with the substrate–target distance during deposition.     

Deposition and spectral performance of an inhomogeneous broadband wide-angular antireflective coating

Gradient index coatings and optical filters are a challenge for fabrication. In a round-robin experiment, basically the same hybrid antireflection coating for the visible spectral region, combining homogeneous refractive index layers of pure materials and linear gradient refractive index layers of material mixtures, has been deposited. The experiment involved three different deposition techniques: electron-beam evaporation, ion-beam sputtering, and radio frequency magnetron sputtering. The material combinations used by these techniques were Nb(2)O(5)/SiO(2), TiO(2)/SiO(2), and Ta(2)O(5)/SiO(2), respectively. The spectral performances of samples coated on one side and on both sides have been compared to the corresponding theoretical spectra of the designed profile. Also, the reproducibility of results for each process is verified. Finally, it is shown that ion-beam sputtering gave the best results in terms of deviation from the theoretical performance and reproducibility.     

Mechanical stress and thermal-elastic properties of oxide coatings for use in the deep-ultraviolet spectral region

Mechanical stress and the structures of SiO2, Al2O3, and HfO2 single oxide layers and of high-reflection multilayer coatings deposited by reactive evaporation, plasma ion-assisted deposition, and ion-beam sputtering have been studied. The stress was related to the microstructure and to the incorporation of water by means of infrared spectroscopy. From the slopes of measured stress-temperature curves of these coatings deposited onto two substrate materials (silicon and fused silica), the biaxial moduli and the thermal expansion coefficients of the films were estimated.     

纳米ZrO2等离子涂层的结构,性能和工艺特点

采用大气等离子喷涂技术(APS)，制备了常规氧化锆和纳米结构氧化锆两种涂层．利用扫描电镜(SEM)对涂层的显微结构进行了观察．对两种涂层的沉积效率、表面粗糙度和显微硬度作了对比研究．结果表明，粉末原料的显微结构、粒度、形态、喷涂工艺参数(喷涂功率和距离)对涂层的显微结构有较大的影响．等离子喷涂造粒纳米氧化锆粉制备的涂层沉积效率高而稳定，其显微结构与喷涂功率和距离密切相关．与常规氧化锆涂层相比，纳米结构氧化锆涂层具有较高的显微硬度和较低的表面粗糙度．     

Preparation of silica thin films by novel wet process and study of their optical properties

Silicon dioxide (SiO2) thin films have gained considerable attention because of their various industrial applications. For example, SiO2 thin films are used in superhydrophilic self-cleaning surface glass, UV protection films, anti-reflection coatings, and insulating materials. Recently, many processes such as vacuum evaporation, sputtering, chemical vapor deposition, and spin coating have been widely applied to prepare thin films of functionally graded materials. However, these processes suffer from several engineering problems. For example, a special apparatus is required for the deposition of films, and conventional wet processes are not suitable for coating the surfaces of substrates with a large surface area and complex morphology. In this study, we investigated the film morphology and optical properties of SiO2 films prepared by a novel technique, namely, liquid phase deposition (LPD). Images of the SiO2 films were obtained by scanning electron microscopy (SEM) and atomic force microscopy (AFM) in order to study the surface morphology of these films: these images indicate that films deposited with different reaction times were uniform and dense and were composed of pure silica. Optical properties such as refractive index and transmittance were estimated by UV-vis spectroscopy and ellipsometry. SiO2 films with porous structures at the nanometer scale (100-250 nm) were successfully produced by LPD. The deposited film had excellent transmittance in the visible wavelength region.     

氧化锆纳米等离子涂层的结构与热震性能研究

利用大气等离子喷涂技术, 制备了氧化锆纳米结构和常规结构涂层, 并对涂层的显微结构进行了探查. 结果表明: 纳米结构涂层是由直径为100nm左右的柱状晶粒组成的层状结构; 涂层中存在大量的微裂纹和分布均匀的细小圆气孔. 纳米结构的涂层具有比常规涂层更好的抗热震性能, 其热震行为与常规涂层不同.     

有序蘑菇状负载型纳米TiO_2光催化剂制备

为了解决TiO2光催化剂分散性差、难回收、难固定等问题,提出一种利用有序纳米结构作为载体的负载型催化剂制备技术,来制备三维纳米TiO2光催化剂.利用SiO2和SiNx材料具有不同刻蚀选择比的特点,首先将SiO2纳米球(直径60～90 nm)作为掩模刻蚀衬底上的SiNx薄膜.然后将刻蚀形成的结构作为载体,利用磁控溅射技术在其上制备TiO2薄膜.实验结果表明,样品经刻蚀后形成由SiNx纳米柱和SiO2纳米扁球组成的三维纳米载体,所制备的TiO2分散地负载在该纳米载体上,形成一种由TiO2、SiO2和SiNx构成的蘑菇状三维纳米复合体系.这种通过纳米球刻蚀结合镀膜的方法是制备纳米载体及三维纳米负载型催化剂的技术之一,利用该技术制备的负载型催化剂分散性好、易于回收和重复利用.     

透明陶瓷保护膜的研究

对黄铜基材装饰件表面先采用高能级磁控溅射离子镀(专利号:85102600.1)技术镀不锈钢代替电镀钯-镍合金,再采用等离子体型阴极弧源-磁控溅射镀(专利号:ZL98236950.6)技术在不锈钢镀膜表面上镀制TiN/Au/透明陶瓷保护膜SiO2、TiO2.对其硬度、耐蚀性及耐磨性进行分析.     

Characterisation of TiN and TiAlN thin films deposited on ground surfaces using focused ion beam milling

TiN and TiAlN/TiN PVD coatings deposited onto as-ground surfaces have been characterised via direct cross-sectional imaging and transmission electron microscopy with the aid of a focused ion beam system. Cross-sections showed that the coatings exhibit consistent coverage, even in sheltered areas such as at the base of grooves resulting from prior grinding. A columnar grain structure was observed in all coatings. A number of defects were observed such as seams and voids resulting from coating onto the as-ground surface and macroparticles which were shown to be deposited during the metal ion etching stage. Cross-sections through nanoindents revealed that the coatings deform by through-thickness shear cracking.The combination of the excellent coverage provided by PVD and the deformation mechanisms, which are related to the microstructure, contribute to the excellent performance of these coatings that has lead to their widespread application.     

镁合金表面微弧氧化-SiO2复合膜层的微观结构和耐蚀性

采用有机醇盐水解法制备SiO2溶胶,用浸溃-提拉制膜技术在AZ31B镁合金微弧氧化陶瓷层表面制备SiO2膜层,研究了镁合金表面微弧氧化-SiO2复合膜层的微观结构和耐蚀性.结果表明:SiO2溶胶进入微弧氧化陶瓷层表面的微孔并形成了SiO2膜层;由微弧氧化陶瓷层和SiO2膜层组成的复合膜层的腐蚀电位比单一陶瓷层明显提高,...     

SiO2/TiO2复合气凝胶的孔道结构研究

为了在常压干燥下制备高比表面积且具有多级孔道结构的SiO2/TiO2复合气凝胶,以正硅酸乙酯、钛酸丁酯为原料,利用低聚体聚合将分相平行引入到溶胶凝胶过程中,获得SiO2/TiO2醇凝胶,并通过溶剂替换技术实现气凝胶的常压干燥制备.不同硅钛比气凝胶的内部结构研究表明:合成的气凝胶是由纳米SiO2和TiO2颗粒分散复合而成的介孔块体,其中Ti—O—Ti、Si—O—Si和Ti—O—Si键相互交织.气凝胶的结构变化是分相与溶胶凝胶过程相互竞争的结果.Si含量能显著改善气凝胶的结构,当n(Ti)∶n(Si)为3∶1时,比表面积高达712.2 m2/g,平均孔径为3.36 nm;当n(Ti)∶n(Si)为1.5∶1时,复合气凝胶具有明显双连续孔道,比表面积高,同时孔状结构清晰.     

镁合金微弧氧化-溶胶凝胶复合膜层的耐蚀性

用微弧氧化和溶胶凝胶法在AZ91D镁合金表面制备复合膜层,用扫描电镜(SEM)、能谱分析(EDS)、X射线衍射(XRD)和电化学测试等分析手段表征其成分、相结构和截面形貌,研究了复合膜层的耐蚀性.结果表明,溶胶凝胶膜有效地封闭了镁合金表面微弧氧化膜的微孔,形成结合力好且较为致密的复合膜层.复合膜层的组成主要有MgO、M...     

Effect of substrate bias voltage on structural and mechanical properties of pulsed DC magnetron sputtered TiN-MoSx composite coatings

TiN-MoS_x composite coatings were deposited by pulsed DC closed-field unbalanced magnetron sputtering (CFUBMS) using separate Ti and MoS₂ targets in an Ar and N₂ gas environment. The effect of substrate bias voltage on the structure and mechanical properties of TiN-MoS_x composite coating has been studied. The structure and composition of the coating were evaluated using field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS) by X-ray and grazing incidence X-ray diffraction (GIXRD). Scratch adhesion tests, Vickers microhardness tests and ball-on-disc tests with a cemented carbide (WC-6%Co) ball were carried out to investigate mechanical properties of the coating. Application of substrate bias was found to transform the structure of TiN-MoS_x composite coating from open columnar to a dense columnar structure. The changes in grain size and texture coefficient appear to be associated with variation in substrate bias voltage. The mechanical properties of the coating such as adhesion and composite microhardness were also observed to be related to the change in bias voltage. A maximum hardness of 22 GPa was obtained for a coating deposited at substrate bias voltage of −40 V. The improved structural and mechanical properties of the coating deposited at −40 V were also reflected in its excellent wear resistance property.     

金属陶瓷涂层耐蚀性能研究

采用溶胶 凝胶浸渍提拉法在不锈钢、纯铜及铝合金基底上制作了连续的ＳｉＯ２ 、ＴｉＯ２ 、Ａｌ２Ｏ３ 及ＳｉＯ２ ＴｉＯ２ 陶瓷涂层。通过阳极极化曲线、循环动电位极化曲线、点蚀电位、三氯化铁腐蚀试验、５ ％ 硫酸腐蚀试验以及氧化试验检测了陶瓷涂层对金属的保护能力。分析试验结果表明,这些陶瓷涂层大幅度提高了基底金属在腐蚀介质及氧化环境中的寿命。     

Passivation of pigment-grade TiO(2) particles by nanothick atomic layer deposited SiO(2) films

Pigment-grade TiO(2) particles were passivated using nanothick insulating films fabricated by atomic layer deposition (ALD). Conformal SiO(2) and Al(2)O(3) layers were coated onto anatase and rutile powders in a fluidized bed reactor. SiO(2) films were deposited using tris-dimethylaminosilane (TDMAS) and H(2)O(2) at 500?°C. Trimethylaluminum and water were used as precursors for Al(2)O(3) ALD at 177?°C. The photocatalytic activity of anatase pigment-grade TiO(2) was decreased by 98% after the deposition of 2?nm SiO(2) films. H(2)SO(4) digest tests were performed to exhibit the pinhole-free nature of the coatings and the TiO(2) digest rate was 40 times faster for uncoated TiO(2) than SiO(2) coated over a 24?h period. Mass spectrometry was used to monitor reaction progress and allowed for dosing time optimization. These results demonstrate that the TDMAS-H(2)O(2) chemistry can deposit high quality, fully dense SiO(2) films on high radius of curvature substrates. Particle ALD is a viable passivation method for pigment-grade TiO(2) particles.