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.     

Adhesion Enhancement of Diamond Films on Various Substrates by Carbide Interlayer

Diamond films were prepared on various substrates by a combustion flame technique using an oxyacetylene torch. During the deposition, a carbide interlayer was formed between the surface of the substrate and deposited diamond. The hard interlayers were seen on the molybdenum, tungsten as well as silicon substrates. The adhesion of diamond on the molybdenum substrate was improved with increase in the hardness of the carbide layer. This result strongly supports the premise that the carbide interlayer and/or carbon diffused layer enhances the adhesion of diamond to substrates.     

Diamond deposition on Mo with thermal stress buffer layer coated mild steel substrate by combustion flame CVD

In order to develop wear resistance diamond/molybdenum (Mo) hybrid coating process can be conducted in open air. Diamond deposition on the molybdenum with thermal stress buffer layer coated mild steel substrate by the combustion flame chemical vapor deposition (CFCVD) was carried out. As the thermal stress buffer layer, atmospheric plasma sprayed Mo/Fe mixture coating was deposited between Mo top coat and mild steel substrate. Consequently, crack generation and peeling off of the coating occurred due to thermal influences on the condition of Mo coated mild steel substrate in our previous study, diamond particles could be created on the Mo coating without fracture and peeling off. Besides, an additional Mo coating after diamond deposition increases the adhesion force between the diamond coating and the initial Mo coating. This encapsulation of the diamond particles between two Mo layers dramatically improves the resistance of the global coating making it strong enough to resist to the wearing test. These results demonstrate the high potential of thermal sprayed coating for the wear resistance improvement.     

Advanced deposition characteristics of kinetic sprayed bronze/diamond composite by tailoring feedstock properties

In this study, the effect of protective nickel film on diamond particles was studied with the goal of preventing fracture and obtaining a uniform diamond distribution in a bronze/diamond composite coating during kinetic spraying. Two types of bronze/diamond composite were deposited on aluminum substrate. For comparison with experimental results, the impact behavior between diamonds in the gas flow field was simulated by finite element analysis (using ABAQUS/Explicit 6.7-2). Size distribution and deposition efficiency of the diamond particles in the composite coatings were analyzed through scanning electron microscopy and image analysis methods. Diamond fracturing was avoided because the impact energy was mostly absorbed by the outer protective nickel film on the diamond particle during impact. The uniform distribution and deposition efficiency of diamond particles in the coating layer could also be achieved by tailoring the physical properties (density, size, etc.) of the feedstock.     

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.     

Corrosion behaviour of TiN films obtained by plasma-assisted chemical vapour deposition

Titanium nitride (TiN) coatings with a dense structure were prepared on high-speed steel by plasma-assisted chemical vapour deposition (PACVD). The electrochemical polarization measurement of TiN coating was compared with that of the uncoated substrate. It was found that the TiN coating had a higher corrosion potential, and a lower corrosion rate (current density), about three orders of magnitude less than for the steel substrate. The major corrosion mechanism of TiN was pitting corrosion through surface defects and/or open pores. The number and size of pits decreased with the chlorine content of the film. The TiN coating deposited by PACVD, regardless of the amount of residual chlorine, proved to be a good anti-corrosion coating on a steel substrate.     

HF-CVD of diamond coatings onto Fluidized Bed (FB) treated CrN interlayers

In the present investigation, Fluidized Bed (FB) treatment is applied to pre-treat CrN interlayers onto WC-Co substrates to promote the growth on them of highly adherent diamond coatings. During FB treatment, the CrN interlayers are submitted to high speed impacts of loose abrasives. The action of their cutting edges is able to deeply change the starting morphology of the as-deposited Physical Vapour Deposition (PVD) CrN interlayers, thus promoting the establishment of a highly corrugated surface on which to grow Hot Filament-Chemical Vapour Deposition (HF-CVD) diamond coatings.Growth, morphology, adhesion and wear resistance of the CVD deposited diamond coatings onto the FB treated and just seeded CrN interlayers were looked into and compared to diamond coated WC-Co substrates with the untreated CrN interlayers or pre-treated with a two-step chemical etching (Murakami's reagent and Caro's acid, MC-treatment) or with FB.FB treatment proved to be an effective technique to tailor the surface morphology and roughness of CrN films deposited by PVD-arc technique, and was found to be very useful in improving the adhesion and wear resistance of CVD diamond onto the CrN interlayers.     

金刚石表面Cr金属化的界面扩散反应研究

利用直流磁控溅射法在金钢石颗粒表面沉积了厚度为１５０ｎｍ的金属Ｃｒ薄膜。ＳＥＭ研究表明在金刚石表面形成的Ｃｒ膜基本均匀,但有小的金属聚集体存在。俄歇深度剖析研究发现,在镀膜过程中Ｃｒ膜和金刚石基底间发生了显著的界面扩工用作用。相应的俄歇线形分析表明,沉积过程中在界面上发生化学反应形成了部分Ｃｒ２Ｃ３物种。溅射沉积功率对金刚石颗粒与金属Ｃｒ膜的界面反应有较大的影响,提高溅射功率可大大促进Ｃｒ元素的扩     

Effect of Plasma Power on the Deposition of Diamond Coatings on Pure Titanium

Diamond coatings appear to be a promising solution for the improvement of tribological behavior of titanium alloys. By means of microwave plasma assisted chemical vapor deposition (MW-PACVD), diamond coating was deposited on pure titanium using CH₄/H₂ gas mixtures under different plasma powers. Surface and interface characterization of the deposited coating under different plasma powers was carried out using SEM, grazing incidence x-ray diffraction (GIXD) and Raman spectroscopy. Adhesion of diamond coating with substrate was evaluated using an indentation tester. Results showed that adhesion of diamond coatings was not good under high plasma power, whereas the crystallinity of diamond coating was not good under low plasma power. The higher the plasma power, the larger the diamond crystal size, the less content of non-diamond carbon and the poorer the adhesion strength. During the diamond deposition, growth of TiC competed with diamond formation for the available carbon content. Relatively low plasma power inhibited TiC formation more than diamond formation. Under a high plasma power, the formation of a thick and porous TiC layer appeared to promote interfacial debonding and spallation of the diamond coating.     

Interfacial structure, residual stress and adhesion of diamond coatings deposited on titanium

The interfacial structures of diamond coatings deposited on pure titanium substrate were analyzed using scanning electron microscopy and grazing incidence X-ray diffraction. Results showed that beneath the diamond coating, there was one titanium carbide and hydride interlayer, followed by a heat-affected and carbon/hydrogen diffused Ti layer. Residual stress in the diamond coating and TiC interlayer under different process parameters were measured using Raman and X-ray diffraction (XRD) methods. Diamond coatings showed large compressive stress on the order of a few giga Pascal. XRD analysis also showed the presence of compressive stress in the TiC interlayer and tensile stress in the Ti substrate. With increasing deposition duration, or decreasing plasma power and concentration of CH₄ in gas mixture, the compressive residual stress in the diamond coating decreased. The large residual stress in the diamond coating resulted in poor adhesion of the coatings to substrate, but adhesion was also related to other factors, such as the thickness and nature of the TiC interlayer, etc. A graded interlayer design was proposed to lower the thermal stress, modify the interfacial structure and improve the adhesion strength.     

金刚石纳米粉促进的CVD金刚石薄膜的生长行为研究

采用由普通炸药爆轰制备的金刚石纳米粉对光滑硅衬底进行了涂覆预处理,研究了金刚石薄膜经徐覆和研磨预处理的两种衬底上的生长行为及其演化过程．结果表明,纳米粉处理能在显著提高成核密度的同时,大大缩短长成连续膜所用的时间;薄膜的生长由前后相继的两个阶段所构成,即确定晶面形成前球状颗粒的成长与融合和晶面的逐渐显露与晶粒长大过程．经足够长的生长时间后,所得薄膜具有结构致密、晶面清晰、晶形完整和表面平整度高的特征,特别适合于高致密性自支持薄膜的生长．而研磨处理衬底上生长的薄膜一旦成核,便有确定晶面的显露,但却出现明显的二次成核和孪晶,所得薄膜的致密性与表面平整度均不及徐覆处理的好．文中还对结果进行了简要讨论．     

Synthesis of Diamond Thin Films on TC4 by Using a Scanning Linear Flame

A scanning linear flame is used to deposit diamond films over a large area, and with high quality and good continuity by employing appropriate cooling means for the substrate. It is found that the structure and morphology of the deposited films mainly depend on the substrate temperature, the ratio of 0₂ to C₂H₂ flow rate and the relative position of the substrate with respect to the flame. These factors affecting the structure and morphology of diamond films are interrelated. Moreover, the influences of surface pretreatments on nucleation and growth of diamond films are also studied. The experimental results show that the nucleation density of diamond films is enhanced by scratching the surface of the substrate with diamond grit and initially coating a mechanical pump oil layer. For the substrate surface etched with metallographic etching acid, the nucleation and growth of diamond films are very uniform. In addition, the adhesion between the film and substrate is enhanced. Nucleation is favored on the prominent features of the substrate, i.e. scratch and crystal boundary.     

Growth and corrosion of aluminum PVD-coating on AZ31 magnesium alloy

Magnetron sputtering was applied to prepare aluminum coating on a mechanically polished AZ31 magnesium alloy. A loose oxide film was spontaneously formed on the surface of AZ31 magnesium alloy during polishing process. The aluminum coating, which was subsequently deposited on this oxide layer, presented a developed columnar microstructure. Attributed to the barrier effect of Al coating, the Al coated AZ31 showed a higher corrosion resistance than bare AZ31 in corrosion tests. Generally, Al coating is cathodically protected by magnesium alloy substrate. But it is interesting in this study that Al coating still suffered from severe corrosion due to the occurrence of the alkalization effect.     

金刚石薄膜涂层硬质合金刀具的界面表征

采用SEM对金刚石薄膜涂层硬质合金刀具的金刚石薄膜表面、背面及金刚石薄膜剥落后的硬质合金刀片表面的典型形貌进行了观察,并采用TEM对金刚石薄膜／硬质合金刀片横截面的微观组织进行了研究,还采用FT—Raman光谱法对金刚石薄膜表面及金刚石薄膜剥落后的硬质合金刀片表面的微观结构进行了表征．结果表明：经适当的化学侵蚀脱钻和等离子体刻蚀脱碳预处理后,金刚石薄膜涂层硬质合金刀具的界面通常存在薄的（数十nm）石墨碳层;局部区域见到金刚石粒子直接生长在WC颗粒上,金刚石膜／基横截面的典型组织层次为：金刚石薄膜／薄的石墨碳层／细小的WC层／残留的脱碳层（η相＋W相）／原始的硬质合金基体．     

Properties of thin TiN films deposited onto stainless steel by an in-line dry coating process

A new coil-coating pilot plant, capable of utilizing ion plating, sputtering and plasma-assisted chemical vapor deposition (PACVD) processes, independently or in series, was developed and optimum conditions for TiN, TiC, Al_xO_y, SiO_x and Cr coating were established. This paper is mostly concerned with the results of characterization (conducted in parallel by the authors′ two institutions) of TiN films deposited by ion plating or sputtering onto type-304 stainless steel strips. In particular, the dependence of the basic properties such as chemical composition, structure, adhesion, and color on the coating process are discussed with respect to anti-corrosion, anti-wear, and decorative applications. TiN coatings with a very attractive gold coloration were obtained; they performed well in wear testing, but did not show satisfactory corrosion resistance. However, it was found that the latter can be improved significantly by depositing a SiO_x, top layer by PACVD above the TiN coating. Thus the in-line dry coating processes are capable of producing highly functional steel surfaces with decorative color and high corrosion resistance.     

MPCVD法在氧化铝陶瓷上的金刚石膜沉积及其成核分析

用微波等离子体化学气相沉积（ＭＰＣＶＤ）法在氧化铝陶瓷基片上沉积了金刚石薄膜。实验表明，对基片进行适当的预处理，包括用金刚石研磨膏仔细研磨和沉积前原位沉积一层无定形碳层，可显著提高成核密度；对硅衬底和氧化铝基片上金刚石膜的成核过程进行了对比分析，并提出了提高氧化铝基片上沉积金刚石的成核的措施。     

Investigations on the Deposition and the Efficiency of a Multilayer High Temperature Coating System for Gas Turbine Blades

The content of this work is the development and investigation of a high temperature coating system for gas turbine blades. On a single crystal CMSX4 substrate a thin CVD layer of α‐alumina is deposited as diffusion barrier coating. As a protection against high‐temperature corrosion it is covered with a PVD NiCoCrAlY layer, which also performs as a bond‐coating for the following thermal barrier coating deposited by Atmospheric Plasma Spraying. The surface preparation techniques and coating parameters for the multilayer coating were optimized with respect to the bonding mechanisms of the different deposition techniques. The samples were annealed at 1100°C for 100 h under neutral atmosphere. Furthermore thermocycle experiments were carried out to investigate thermocycle behaviour. The coating system proved its efficiency: No cracks were observed except vertical segmentation cracks in the TBC, all layers showed good adhesion and the diffusion barrier remained intact suppressing any noticeable diffusion of Al, Cr, Ta, Re, W and Ti.     

Nanoporosity of Al2O3 coatings obtained by impulse plasma deposition

Investigations of the size distribution of nanopores were carried out for alumina coatings deposited by the impulse plasma method. The single-phase (metastable and stable correspondingly) alumina coatings were deposited under different conditions of impulse plasma processes. The investigation of nanopore distribution was carried out using small-angle X-ray scattering. Despite the different phase composition of the coatings obtained, the most probable value of nanopores for both alumina coating materials were practically the same and equal to 5 nm. It appears that a coating porosity of the order of nanometres is characteristic for all coatings deposited by the impulse plasma method, because previously similar dimensions of nanopores were found for diamond, TiN and BN. It seems that during the impulse plasma deposition the coating grows on the substrate surface by condensation of ultra-small particles nucleated in the impulse plasma.     

Microstructure and corrosion characteristics of CrN/NiP sputtering thin films

The CrN top layer and NiP interlayer were sequentially deposited to form a CrN/NiP composite coating through sputtering technique. The CrN/NiP coating systems deposited at 350 °C, 450 °C, and 550 °C, showed amorphous/nanocrystalline, nanocrystallize with precipitations, and fully crystallized microstructure respectively for the NiP interlayers. With the introduction of NiP interlayer, the coating assemblies exhibited superior corrosion characteristics than single CrN coatings. The amorphous NiP interlayer deposited at 350 °C revealed a lower corrosion current as compared to those with crystallized NiP layers owing to their structural defects in the alloy layer. With the combination of CrN and NiP layers the corrosion attach was retarded and a better corrosion resistance was found for the CrN/NiP composite coating.     

WS2软涂层刀具的材料优选及涂层制备

运用有限元软件分析了不同基体材料和过渡层的基体表面WS2软涂层的残余热应力。结果表明弹性模量和热膨胀系数等参数是影响涂层残余热应力大小的主要因素。采用中频磁控溅射、多弧离子镀外加离子束辅助沉积工艺制备了4种WS2软涂层刀具并对其性能进行了测试,分析结果符合有限元计算的结论,发现残余热应力对WS2软涂层刀具的性能产生很大的影响,并发现Zr过渡层能有效促进WS2Ⅱ型织构的生长。