WC-Co硬质合金基体上高附着力金刚石薄膜的制备

采用微波等离子体化学气相沉积(CVD)法在WC-Co硬质合金基体上制备金刚石膜, 研究了TiN_x中间层的引入对金刚石薄膜质量及其附着性能的影响. 结果表明, 在酸浸蚀脱钴处理的基础上, 通过预沉积氮含量呈梯度变化的TiN_x中间过渡层, 可在硬质合金基体上制备出高质量的金刚石薄膜; 压痕法测试其临界载荷达1000N.     

电镀铬-金刚石复合过渡层提高金刚石膜/基结合力

在铜基体上沉积铬-金刚石复合过渡层, 用热丝CVD系统在复合过渡层上沉积连续的金刚石涂层. 用扫描电镜(SEM)、X射线(XRD)、拉曼光谱及压痕试验对所沉积的镶嵌结构界面金刚石膜的相结构及膜/基结合性能进行了研究. 结果表明, 非晶态的电镀Cr在CVD过程中转变成Cr₃C₂, 由于金刚石颗粒与Cr₃C₂的相互咬合作用, 金刚石膜/基结合力高; 在294 N载荷压痕试验时, 压痕外围不产生大块涂层崩落和径向裂纹, 只形成环状裂纹.     

用压痕试验法研究CVD金刚石膜的粘附性能

在观察与分析压入过程中CVD金刚石膜开裂方式的基础上,初步探讨了用压痕试验法评定CVD金刚石膜粘附性能的可行性．采用反映膜／基粘附性能的临界开裂或剥落载荷P_er和抗裂性参数dP／dX两指标评定了硬质合金基体表面经不同预处理方法和沉积工艺参数合成的金刚石膜的粘附性能;研究了粘附性能指标与沉积工艺参数（如甲烷浓度、沉积气压、沉积功率）之间的关系．适当的表面预处理、适中的甲烷浓度、较低的沉积气压、较高的沉积功率均有利于改善金刚石膜的粘附性能．     

Chemically vapour deposited diamond coatings on cemented tungsten carbides: Substrate pretreatments, adhesion and cutting performance

Chemical vapour deposition (CVD) of diamond films onto Co-cemented tungsten carbide (WC-Co) tools and wear parts presents several problems due to interfacial graphitization induced by the binder phase and thermal expansion mismatch of diamond and WC-Co. Methods used to improve diamond film adhesion include substrate-modification processes that create a three-dimensional compositionally graded interface. This paper reviews substrate pretreatments and adhesion issues of chemically vapour deposited diamond films on WC-Co. The combined effect of pretreatments and substrate microstructure on the adhesive toughness and wear rate of CVD diamond in dry machining of highly abrasive materials was analyzed. The role of diamond film surface morphology on chip evacuation in dry milling of ceramics was also investigated by comparing feed forces of coated and uncoated mills. The overall tribological performance of diamond coated mills depended on coating microstructure and smoothness. The use of smother films did allow to reduce cutting forces by facilitating chip evacuation.     

Raman spectroscopy characterization of diamond films on steel substrates with titanium carbide arc-plated interlayer

Diamond chemical vapour deposition (CVD) on steel represents a difficult task. The major problem is represented by large diffusion of carbon into steel at CVD temperatures. This leads to very low diamond nucleation and degradation of steel microstructure and properties. Recent work [R. Polini, F. Pighetti Mantini, M. Braic, M. Amar, W. Ahmed, H. Taylor, Thin Solid Films 494 (2006) 116] demonstrated that well-adherent diamond films can be grown on high-speed steels by using a TiC interlayer deposited by the PVD-arc technique. The resulting multilayer (TiC/diamond) coating had a rough surface morphology due to the presence of droplets formed at the substrate surface during the reactive evaporation of TiC. In this work, we first present an extensive Raman investigation of 2 μm, 4 μm and 6 μm thick diamond films deposited by hot filament CVD on TiC interlayers obtained by the PVD-arc technique. The stress state of the diamond was dependent on both the films thickness and the spatial position of the coating on the substrate. In fact, on the top of TiC droplets, the stress state of the diamond was much lower than that of diamond in flatter substrate areas. These results showed that diamond films deposited on rough TiC interlayers exhibited a wide distribution of stress values and that very large compressive stress exists in the diamond film grown on flat regions of steel substrates with a TiC interlayer. Diamond films could accommodate stresses as large as 10 GPa without delamination.     

生长温度对CVD金刚石薄膜的影响

系统研究了ＣＶＤ金刚石薄膜成膜过程中生长温度对薄膜质量、生长率和力学性能的影响。研究结果表明：在典型沉积条件下，生长温度愈高、薄膜的晶体质量愈好；但薄膜的应力状况和附着性能变坏；在８００℃时，金刚石薄膜的生长速率最大。讨论了ＣＶＤ金刚石薄膜作为机械工具涂层的最佳生长温度。     

Mechanical properties of diamond thin films

Abstract

The mechanical properties of diamond films deposited via hot filament chemical vapour deposition have been determined using a range of techniques, and related to the composition and morphology of the diamond films as determined by laser Raman spectroscopy. As the quality of the film increases, its hardness (as determined by the volume law of mixtures hardness model) also increases until it is larger than values often reported for polycrystalline bulk material, a consequence of the very small grain size in the films. Coating adhesion, as determined from indentation adhesion tests, also appears to improve with coating quality. Variations in the behaviour of the friction coefficient between diamond films and diamond and steel counterfaces are less well defined, but it appears that the surface morphology of the film is important in dictating the behaviour rather than the quality of the diamond. These results are discussed in the context of the potential use of diamond coatings in tribological applications.

MST/1695     

Effects of Ti- and Zr-based interlayer coatings on the hot filament chemical vapour deposition of diamond on high speed steel

The prospect of obtaining good adhesion of diamond films onto steel substrates is highly exciting because the achievement of this objective will open up applications in the cutting and drilling industry. However, a major problem with depositing diamond onto steel is high diffusion of carbon into steel at chemical vapour deposition (CVD) temperatures leading to very low nucleation density and cementite (Fe₃C) formation. Therefore, the study of the nucleation and growth processes is timely and will yield data that can be utilised to get a better understanding of how adhesion can be improved. This work focuses on investigating the adhesion of thin diamond films on high speed steel previously coated with various interlayers such as ZrN, ZrC, TiC and TiC/Ti(C,N)/TiN. The role of seeding on nucleation density and the effect of diamond film thickness on stress development and adhesion has been investigated using SEM, XRD and Raman spectroscopy.The main emphasis in this study is the TiC interlayer which for the first time proved to be a suitable layer for diamond CVD on high speed steel (HSS). In contrast from other interlayer materials investigated here, no delamination was observed even after 3 h of CVD at 650 °C only when TiC was employed. Nevertheless, the increase of diamond film thickness on TiC coated HSS substrates led to the delamination of small areas in various regions of the substrate. This occurrence suggests that there was a distribution of adhesive toughness values at the diamond/TiC interface with stress development being dependent on film thickness.     

Nanoindentation and nanoscratch behaviour of reactive sputtered deposited W–S–C film

Transition metal dichalcogenides having layered structure are promising self lubricating film and can be considered as substitute for carbon based films in several varieties of environmental conditions. The macrotribological properties of these films are studied extensively and are fairly well understood. However, mechanical and tribological behaviour of these films in millinewton load range have hardly been reported. Study of mechanical and tribological properties at applied load in the millinewton range is useful for possible application related to microelectro mechanical systems or micromechanical assemblies. In view of the above, the present work is undertaken to understand the indentation behaviour and scratch behaviour under constant and low applied load of reactive sputtered deposited W–S–C thin films. Towards that purpose, W–S films containing various amount of C are deposited on 100Cr6 steel using a radio frequency magnetron sputtering unit. The load vs. displacement curves of all these films are generated for four different loads to assess the load effect, substrate effect and size effect on the hardness and the load displacement curves of these films. Curves showing the variation of load as a function of the square of displacement are also evaluated in order to understand deformation and fracture mechanisms of these films and the interface between various microstructures of these films. The scratch behaviour of these films under constant load is determined to examine the friction and wear performance. The results show that the film containing 54 at.% carbon has the maximum hardness and the minimum scratch depth. In contrast, the minimum friction coefficient is exhibited by the film containing the maximum carbon.     

硫化锌窗口上CVD法制备金刚石膜的研究进展

金刚石具有优异的红外透过性能,可作为硫化锌红外窗口的保护膜。但由于CVD金刚石的沉积过程会刻蚀硫化锌衬底,导致在窗口表面直接生长金刚石膜比较困难。本文主要综述了近年来通过添加过渡层沉积金刚石薄膜的方法和光学焊接金刚石厚膜的方法来增强硫化锌窗口的性能,并介绍了CVD金刚石膜的光学应用及其目前所存在的问题,最后对未来CVD金刚石膜发展的方向作出了展望。     

Machining of Hypereutectic Al-Si Alloy with CVD Diamond Coated Si4N4. Inserts

Due to its excellent mechanical properties, diamond can be used for many applications in mechanical engineering. With the help of the Chemical Vapor Deposition (CVD) method it is possible to deposit polycrystalline diamond films on different substrate materials of nearly any shape and surface. So diamond cutting tools with complex geometry are now possible. In this investigation diamond coatings deposited by microwave plasma CVD (MW-PACVD) on Si₃N₄ inserts were used for turning experiments. By means of changes in the CH₄/H₂ gas ratio two different types of film morphology were generated, one rather highly faceted and the other one fine-grained ballas-type surface microstructure. The cutting performance of the CVD diamond coated triangular silicon nitride inserts was analyzed for continuous dry turning of the hypereutectic AISi 17Cu4Mg alloy with different cutting speeds. During the experiments no wear of the diamond films could be detected; nevertheless, the adhesion to the Si₃N₄ substrate has still to be improved. The results of the cutting tests gave valuable information for favorable geometry and clamping devices of cutting tools coated with CVD diamond and for suitable machining parameters.     

Adhesion of Titanium Nitride Films Deposited on High Speed Steel Substrates by RF Plasma Assisted Chemical Vapor Deposition

Effects of growth condition of titanium interlayer and sputter-etching before its deposition on adhesion of titanium nitride films grown onto high speed steel substrates by RF (13.56 MHz) plasma-assisted chemical vapor deposition were investigated. Adhesion of TiN film increased with sputtering pressure for deposition of the interlayer. Preferred orientation (002) of the interlayer resulted in poor adhesion of TiN film. Proper sputter-preetching gave rise to adhesion up to 45 N and the film demonstrated a cohesive flaking mode during scratch test.     

金刚石薄膜用钢基表面过渡层研究进展

介绍了影响钢基表面金刚石薄膜沉积的不利因素,分析和综述了近10年来在提高金刚石薄膜质量以及薄膜粘结性等方面所采用的各种中间过渡层及其研究进展.过渡层可采用沉积法制备,也可采用表面改性法制备.过渡层可以制备成单层膜结构,也可制备成多层膜结构.对于不同的基底材料应选择不同的过渡层.     

金刚石膜在多孔硅发光中的应用

采用微波等离子体化学气相沉积（MPCVD）法成功地在多孔硅上沉积出均匀、致密的金刚石膜。光致发光测量表明,金刚石膜可以有效稳定多孔硅的发光波长和发光强度,具有明显的钝化效应。金刚石膜的这个特点再加上高硬度特性使金刚石膜成为多孔硅的一种潜在的钝化膜。     

Mechanical characteristics of optical coatings prepared by various techniques: a comparative study

Good performance of optical coatings depends on the appropriate combination of optical and mechanical properties. Therefore, successful applications require good understanding of the relationship between optical microstructural and mechanical characteristics and film stability. In addition, there is a lack of standard mechanical tests that allow one to compare film properties measured in different laboratories. We give an overview of the methodology of mechanical measurements suitable for optical coatings; this includes depth-sensing indentation, scratch resistance, friction, abrasion and wear testing, and stress and adhesion evaluation. We used the techniques mentioned above in the same laboratory to systematically compare the mechanical behavior of frequently used high- and low-index materials, namely, TiO2, Ta2O5, and SiO2, prepared by different complementary techniques. They include ion-beam-assisted deposition by electron-beam evaporation, magnetron sputtering, dual-ion-beam sputtering, plasma-enhanced chemical-vapor deposition, and filtered cathodic arc deposition. The mechanical properties are correlated with the film microstructure that is inherently related to energetic conditions during film growth.     

Micro-scratch analysis and mechanical properties of plasma-deposited silicon-based coatings on polymer substrates

Advanced optical applications require multifunctional coatings with specific mechanical properties, such as resistance to damage and good adhesion to different types of substrates, including polymers. In the present study we deposited amorphous hydrogenated silicon nitride (SiN_1.3) and oxide (SiO₂) films on polycarbonate and on silicon substrates by plasma enhanced chemical vapor deposition (PECVD), using a dual-mode microwave/radio frequency plasma system. The film adhesion was determined by the micro-scratch test. Depth-sensing indentation and substrate curvature measurements were used to evaluate the microhardness. Young's modulus and residual stresses of the films. The adhesion strength, represented by the critical load, L_c, when the film starts to delaminate, was determined as a function of the substrate material and the energy of bombarding ions. A direct correlation between the L_c values and the mechanical properties of the films was found. The formation of different crack patterns in the coatings during the scratch procedure is explained in terms of stress release mechanism depending on the mechanical properties of the film, the substrate and the interface region. In addition, different models applicable to the evaluation of the work of adhesion in the case of hard coatings on soft substrates are critically reviewed.     

Mechanical properties and scratch resistance of filtered-arc-deposited titanium oxide thin films on glass

The mechanical properties and the scratch resistance of titanium oxide (TiO₂) thin films on a glass substrate have been investigated. Three films, with crystalline (rutile and anatase) and amorphous structures, were deposited by the filtered cathodic vacuum arc deposition technique on glass, and characterized by means of nanoindentation and scratch tests. The different damage modes (arc-like, longitudinal and channel cracks in the crystalline films; Hertzian cracks in the amorphous film) were assessed by means of optical and focused ion beam microscopy. In all cases, the deposition of the TiO₂ film improved the contact-mechanical properties of uncoated glass. Crystalline films were found to possess a better combination of mechanical properties (i.e. elastic modulus up to 221 GPa, hardness up to 21 GPa, and fracture strength up to 3.6 GPa) than the amorphous film. However, under cyclic sliding contact above the critical fracture load, the amorphous film was found to withstand a higher number of cycles. The results are expected to provide useful insight for the design of optical coatings with improved contact-damage resistance.     

Study of adhesion of carbon nitride thin films on medical alloy substrates

The adhesion improvement of biocompatible thin films on medical metal alloy substrates commonly used for joint replacement implants is studied. Diamond-like carbon (DLC) and carbon nitride (CN) thin films are, because of their unique properties such as high hardness, wear resistance and low friction coefficient, candidates for coating of medical implants. However, poor adhesion on substrates with high thermal expansion coefficient limits their application. We deposited CN films by pulsed DC discharge vacuum sputtering of graphite target on CoCrMo and Ti6Al4V substrates. Surface nitridation of the substrate, changing the deposition parameters and use of interlayer led to improved adhesion properties of the films. Argon and nitrogen gas flow, thickness of the film and frequency of the deposition pulses had significant influence on the adhesion to the substrate. Properties of deposited films were analyzed using Scanning Electron Microscopy, Raman spectroscopy and tribology tests.     

The versatility of hot-filament activated chemical vapor deposition

In the field of activated chemical vapor deposition (CVD) of polycrystalline diamond films, hot-filament activation (HF-CVD) is widely used for applications where large deposition areas are needed or three-dimensional substrates have to be coated. We have developed processes for the deposition of conductive, boron-doped diamond films as well as for tribological crystalline diamond coatings on deposition areas up to 50 cm × 100 cm. Such multi-filament processes are used to produce diamond electrodes for advanced electrochemical processes or large batches of diamond-coated tools and parts, respectively. These processes demonstrate the high degree of uniformity and reproducibility of hot-filament CVD. The usability of hot-filament CVD for diamond deposition on three-dimensional substrates is well known for CVD diamond shaft tools. We also develop interior diamond coatings for drawing dies, nozzles, and thread guides.Hot-filament CVD also enables the deposition of diamond film modifications with tailored properties. In order to adjust the surface topography to specific applications, we apply processes for smooth, fine-grained or textured diamond films for cutting tools and tribological applications. Rough diamond is employed for grinding applications. Multilayers of fine-grained and coarse-grained diamond have been developed, showing increased shock resistance due to reduced crack propagation.Hot-filament CVD is also used for in situ deposition of carbide coatings and diamond-carbide composites, and the deposition of non-diamond, silicon-based films. These coatings are suitable as diffusion barriers and are also applied for adhesion and stress engineering and for semiconductor applications, respectively.     

In situ annealing of hydroxyapatite thin films

Hydroxyapatite is a bioactive ceramic that mimics the mineral composition of natural bone. Unfortunately, problems with adhesion, poor mechanical integrity, and incomplete bone ingrowth limit the use of many conventional hydroxyapatite surfaces. In this work, we have developed a novel technique to produce crystalline hydroxyapatite thin films involving pulsed laser deposition and postdeposition annealing. Hydroxyapatite films were deposited on Ti–6Al–4V alloy and Si (100) using pulsed laser deposition, and annealed within a high temperature X-ray diffraction system. The transformation from amorphous to crystalline hydroxyapatite was observed at 340 °C. Mechanical and adhesive properties were examined using nanoindentation and scratch adhesion testing, respectively. Nanohardness and Young's modulus values of 3.48 and 91.24 GPa were realized in unannealed hydroxyapatite films. Unannealed and 350 °C annealed hydroxyapatite films exhibited excellent adhesion to Ti–6Al–4V alloy substrates. We anticipate that the adhesion and biological properties of crystalline hydroxyapatite thin films may be enhanced by further consideration of deposition and annealing parameters.