Uniform coating of CVD diamond on metallic wire substrates

Diamond was coated onto wire substrates of various transition metals (Mo, W or Ti) of 0.5 mm diameter by the microwave plasma CVD method from a gas mixture of the CO–H₂ system. The CVD conditions for a uniform diamond coating were microwave power, 750–1100 W; total pressure, 2000 Pa; total flow rate, 200 ml min-1; CO concentration, 5 vol%; treatment time, 5 h. The wire substrates were mounted vertically or horizontally on a pyrophyllite susceptor, which was placed parallel to the irradiation direction of microwave power. Homogeneous and fine-grained diamond film was prepared on the whole surface of horizontal W wire substrate with a wire height of 2 mm from the susceptor. To obtain a dense diamond coating, the height has to be as low as possible in the plasma region, where the plasma density is higher at lower substrate temperature. Low pressure and high microwave power were suited for fine-grained coating. Diamond deposition rate was found to be more dependent on pressure than substrate temperature. As the pressure increased, a glassy carbon film was formed instead of diamond. This revised version was published online in November 2006 with corrections to the Cover Date.     

DEPOSITION OF DIAMOND FOR CUTTING TOOL APPLICATIONS

The poor adhesion of diamond film to substrates is one of the major problems for practical use in a cutting tool (1-4). in this study, sintered tungsten carbide (WC) body without Co metal, not cemented carbide, was used as the substrate (5), and the effects of surface decarburization of the substrate for improvement in the adhesion of diamond films were investigated. The surface decarburization and diamond coating were carried out in a microwave plasma CVD system. From the results of several adhesion tests, including the cutting tests, it is concluded that the good adhesion is obtained by surface decarburization of the substrate before diamond coating. The reasons for improvement in adhesion are considered by observing the interface structure between the film and the substrate. The damage mechanism of diamond coating on cutting an AI-18%Si alloy with increasing cutting speed is also discussed.     

Nucleation control of diamond synthesized by microwave plasma CVD on cemented carbide substrate

Diamond was coated on to cemented carbide substrate by microwave plasma CVD, in which nucleation control of diamond crystals was investigated under constant deposition conditions; total pressure 30 torr, CH₄ flow rate 1 ml min^–1, H₂ flow rate 199 ml min^–1 and microwave power 550 W. Nucleation tends to occur selectively on the edge part of WC grains of the cemented carbide substrate with coarse WC grain size of about 1 m, where the nucleation density was 9×10⁶ cm^–2. The density increased to about 5×10⁷ cm^–2 when using a finegrained substrate (WC grain size 0.5 m). A considerably enhanced nucleation was observed by introducing a number of fine microflaws on to the substrate surface. Microflawing treatment with diamond fine powder (grain size 0–1/4 m) suspended in an ultrasonic cleaner bath was effective for increasing the diamond nucleation density up to 5×10⁸ cm^–2. The grain size of grown diamond crystals decreased with increasing microflawing time.     

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.     

Effect of methane concentration on physical properties of diamond-coated cemented carbide tool inserts obtained by hot-filament chemical vapour deposition

Diamond-coated tools can greatly improve the productivity of machining highly abrasive materials such as high silicon–aluminium alloys used in the automotive industry. Cemented-carbide diamond-coated tool inserts have not become an off-the-shelf product owing to several difficulties including insufficient adhesion of diamond to the substrate and questionable reproducibilty in their machining performance in the manufacturing. In order to overcome these difficulties, a better understanding of the effects of the chemical vapour deposition (CVD) conditions such as methane concentration, reactor pressure and substrate temperature is important. In this work, cemented tungsten carbide tool inserts with 6 wt% Co (WC–Co) were coated with diamond films deposited at five different methane concentrations (1–9 vol%). Here we present preliminary results of the effect of methane concentration variation on the following physical properties of the diamond coating: surface morphology; crystal structure; chemical quality; surface roughness; residual stress. The results indicate that the best physical properties of diamond-coated tool inserts using hot-filament CVD are achieved with diamond coatings deposited at methane concentrations ranging from 1 to 3%.     

WC-Co硬质合金表面不同去钴预处理方法的比较研究

用微波等离子体化学气相沉积(MWPCVD)制备金刚石薄膜涂层之前,采用盐酸、硝酸化学腐蚀和氢-氧等离子体对WC-Co硬质合金(YG6)基体表面进行去钴预处理。扫描电子显微镜形貌观察和X射线衍射谱分析都表明,与化学腐蚀方法相比,氢-氧等离子体处理具有独特的表面去钴效果,沉积金刚石薄膜的喇曼谱分析更证实其对涂层质量的改善,且对MWPCVD过程而言有其技术上的一些优越性。     

微波等离子体刻蚀处理对金刚石薄膜涂层刀具附着力和切削性能的影响

用HFCVD法在硬质合金（YG6）刀具衬底上沉积金刚石薄膜,用氢微波等离子体刻蚀的方法对衬底进行表面预处理,研究了该预处理技术对WC硬质合金衬底表面成分的影响,进一步探讨了所沉积金刚石薄膜的表面形貌和附着力,并通过难加工材料实际切削试验。研究了所制备的金刚石薄膜涂层刀具的切削性能。试验结果表明,Ar-H2微波等离子体刻蚀脱碳处理是提高金刚石薄膜附着力和改善涂层刀具切削性能的有效预处理方法。     

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．     

Adhesion improvement of diamond films on cemented carbides with copper implant layer

The deposition of diamond films on cemented carbides is strongly influenced by the catalytic effect of cobalt under typical deposition conditions. Decreasing the content of Co on the surface of the cemented carbide is often used for the diamond film deposition. But the leaching of Co from the WC-Co substrate leads to a mechanical weak surface, often causing poor adhesion. In this paper we adopt a copper implant layer to improve the mechanical properties of the Co leached substrate. The copper implant layer is prepared with vaporization. The diamond films are grown by microwave plasma chemical vapor deposition from the CH₄/H₂ gas mixture. The morphology and the quality of the diamond films have been characterized by scanning electron microscopy and Raman spectroscopy. A Rockwell apparatus has evaluated the adhesion of the diamond on the substrate. The results indicate that the diamond films have good adhesion to the cemented carbide substrate due to the recovery of the mechanical properties of the Co depleted substrate after the copper implantation and less graphite formation between the substrate and the diamond film.     

Diamond deposition on copper: studies on nucleation, growth, and adhesion behaviours

This paper presents a systematic study on diamond growth on copper by microwave plasma chemical vapour deposition (MPCVD). It includes the following four main parts. 1. Effect of substrate pre-treatment on diamond nucleation. 2. Effect of deposition conditions on diamond nucleation and growth. 3.Preparation of free-standing diamond films using copper substrate. 4. Adherent diamond coating on copper using an interlayer. In the first part we show that diamond nucleation on copper is strongly affected by the substrate pre-treatment. The residues of abrasives left in the surface of the copper substrate play an important role in the diamond nucleation. In the second part we show that the diamond growth rate increases with microwave power and gas pressure. The effect of the microwave power is mainly an effect of substrate temperature. Increasing methane concentration results in a higher nucleation density and higher growth rate, but at the cost of a lower film quality. Gas flow rate has little influence on the diamond nucleation density and growth rate. In the third part we demonstrate the possibility of preparing large area free-standing diamond films using copper substrate, which has nearly no carbon affinity and usually leads to weak adhesion of the diamond films. The normally observed film cracking phenomenon is discussed and a two-step growth method is proposed for stress release. In the fourth part we show that adherent diamond coating on copper can be obtained using a titanium interlayer. Residual stress in the films is evaluated by Raman spectroscopy. It is found that with increase in the film thickness, the diamond Raman line shifts from higher wave numbers to lower, approaching 1332 cm–1. The stress variation along the depth of the film is also analysed using Airy stress theory.     

Wear behavior of carbide coated Co–Cr–Mo implant alloy

The wear behavior of a new type of metal carbide surface coating on Co–Cr–Mo implant alloy was studied. The coating was created using a microwave plasma-assisted reaction. Codeposition of impurity diamond film, diamond particles, and soot was prevented by controlling process conditions. Wear tests were carried out using a sapphire ball-on-Co–Cr–Mo disc unidirectional sliding configuration with harsh conditions of high contact stress and slow sliding speed in both no-lubrication, and deionized water lubrication environments. In the case of uncoated Co–Cr–Mo discs, the effect of deionized water lubrication was remarkable and reduced the wear factor by one order of magnitude compared to the no-lubrication tests. The wear factor of carbide coated Co–Cr–Mo discs was slightly smaller than that of uncoated Co–Cr–Mo discs with deionized water lubrication (2.7×10^–6 mm³N^–1m^–1 vs. 4.2×10^–6mm³N^–;1m^–1). The addition of deionized water lubrication did not greatly affect the wear factor of carbide coated Co–Cr–Mo discs. The influence of surface geometry resulting from the brain coral-like surface morphology of carbide layers on wear behavior was analyzed considering stress concentrations and effective contact area.     

CVD nanocrystalline diamond coatings on Ti alloy: A synchrotron-assisted interfacial investigation

Diamond coating on Ti-6Al-4V alloy was carried out using microwave plasma enhanced CVD with a super high CH₄ concentration, and at a moderate deposition temperature close to 500 °C. The nucleation, growth, adhesion behaviors of the diamond coating and the interfacial structures were investigated using Raman, XRD, SEM/TEM, synchrotron radiation and indentation test. Nanocrystalline diamond coatings have been produced and the nucleation density, nucleation rate and adhesion strength of diamond coatings on Ti alloy substrate are significantly enhanced. An intermediate layer of TiC is formed between the diamond coating and the alloy substrate, while diamond coating debonding occurs both at the diamond-TiC interface and TiC-substrate interface. The simultaneous hydrogenation and carburization also cause complex micro-structural and microhardness changes on the alloy substrates. The low deposition temperature and extremely high methane concentration demonstrate beneficial to enhance coating adhesion strength and reduce substrate damage.     

CVD‐Diamantschleifstifte für den Werkzeug‐ und Formenbau. Abrasive Pencils for Tool and Die Making Coated by Diamond CVD

Recently developed compeDIA®‐ abrasive pencils have been produced and tested for the machining of cemented carbide molding tools. In order to produce abrasive pencils, carbide base plates have been grinded and coated with a diamond layer by a Hot‐Filament‐CVD‐process. The testing of the abrasive pencils took place with an ultra‐precision grinding machine on carbide workpieces. Surface roughness of the workpiece and its wheel life were the criteria for evaluation. For the specific adjustment of the grain size of the abrasive pencils, the adequate coating parameters were worked out, and the dependencies on basic influencing variables at coating procedures, such as nominal diameter and grinding length, were calculated. In order to be able to coat the grinded base plates with enough film adhesion, a practical pre‐treatment method was developed and tested, which removes the fringe zone, that was damaged during the grinding process. At present, the costs for the coating process are uneconomically high, though. By means of large‐scale production in connection with an automated pre‐treatment and coating it would be possible to lower the costs so far that they are on the same cost level with other coatings like TiN or TiAlN. The CVD‐Diamond abrasive pencils are very appropriate for tool and die making. It is to be expected that through further development of tools and through process optimization, the quality of the wrought workpiece can be ameliorated and surface finishes of R_a < 0,3 μm can be reached. The wheel life could be increased to appropriate values by optimization of the coating technology. The range of the machining parameters, in which the grinding process can be accomplished expediently without leading to a broken die, have been worked out. Afterwards, a die‐casting component with typically shaped elements was designed and an adequate molding tool prototype was crafted. With that, the basic conditions for tool‐ and die‐making were worked out in order to put into practice a fast and flexible machining of cemented carbide molding tools with the aid of those innovative abrasive pencils. In contrast to the traditional molding tool material made of brass, clear advantages in tool life can be made in the production of miniature serial‐parts by drawing, deep‐drawing or extrusion.     

Development of diamond coated tool and its performance in machining Al-11% Si alloy

An attempt has been made to deposit CVD diamond coating on conventional carbide tool using hot filament CVD process. ISO grade K10 turning inserts with SPGN 120308 geometry were used to deposit diamond coating. This diamond coating well covering the rake surface, cutting edges and flank surfaces could be successfully deposited. The coatings were characterized by SEM, XRD and Raman spectroscopy for coating quality, morphology etc. Performance of diamond coated tool relative to that of uncoated carbide tool was evaluated in turning Al-11% Si alloy under dry environment. The diamond coated tool outperformed the uncoated carbide tool which severely suffered from sizeable built-up edge formation leading not only to escalation of cutting forces but also poorer surface finish. In contrast, the diamond coated tool, owing to chemical inertness of diamond coating towards the work material, did not show any trace of edge built-up even in dry environment and could maintain low level of cutting forces and remarkably improved surface finish. It has been further revealed that success of the diamond coated tool depends primarily on adhesion of the diamond coating with the carbide substrate and this is strongly influenced by the pre-treatment of the carbide substrate surface before coating.     

Synthesis and characterization of nano-crystalline CVD diamond film on pure titanium using Ar/CH4/H2 gas mixture

Titanium and Ti alloys have poor tribological properties and deposition of a well adherent diamond coating is a promising way to solve this problem. But diamond film deposition on pure titanium and Ti alloys is always difficult due to the high diffusion coefficient of carbon in Ti, the large mismatch in their thermal expansion coefficients, the complex nature of the interlayer formed during diamond deposition, and the difficulty of achieving very high nucleation density. A nano-crystalline diamond (NCD) film can resolve Ti and Ti alloys weak tribological performance due to its smooth surface. A well-adhered NCD film was successfully deposited on pure Ti substrate by using a microwave plasma assisted chemical vapor deposition (MWPCVD) system in the environment of Ar, CH₄ and H₂ gases at a moderate temperature. Detailed experimental results on the preparation, characterization and successful deposition of the NCD film on pure Ti are discussed.     

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.     

等离子体刻蚀处理对金刚石膜粘附性能的影响

采用直流等离子体射流ＣＶＤ法在ＹＧ８质合金基体上成功地合成了多晶金刚薄膜。通常基体表面经金刚石磨盘研磨、稀硝酸化学侵蚀脱钴预处理后，沉积的金刚石薄膜的的粘附性能仍不理想。本文首次采用原位的Ａｒ－Ｈ２等离子体射流对基体表面进行适当的轰击、刻蚀处理，显著粗化了基体表面，并使基体表面显微组织和化学成分发生重大变化，并且在合适的沉积工艺条件下，沉积的金刚石膜的粘附性能显著提高。借助ＸＲＤ、ＳＥＥＭ、ＴＥＭ     

Nanopatterning of diamond films with composite oxide mask of metal octylates in electron beam lithography

The fabrication of diamond nanopatterns by electron cyclotron resonance (ECR) oxygen plasma with a composite metal octylate mask was investigated using electron beam lithography technology. A high etching selectivity of 14 was obtained with Bi₄Ti₃O₁₂ octylate film as a mask under the plasma-etching conditions of microwave power of 300 W and oxygen gas flow rate of 3 sccm. The metal naphthenates and metal octylates exhibited negative exposure characteristics. The sensitivity of metal naphthenates (1.2×10^–3 C cm^–2) was ten times lower than that of polymethyl methacrylate (PMMA) resist, while that of octylates (8.0×10^–5 C cm^–2) was in good agreement with that of PMMA resist (6.0×10^–5 C cm^–2). The resulting minimum chemical vapor deposited (CVD) diamond line-width of 100 nm with a height of approximately 1 m was fabricated with a Bi₄Ti₃O₁₂ octylate mask.     

Nanocrystalline diamond growth on different substrates

Nanocomposite films consisting of diamond nanoparticles of 3-5 nm diameter embedded in an amorphous carbon matrix have been deposited by means of microwave plasma chemical vapour deposition (MWCVD) from CH₄/N₂ gas mixtures. Si wafers, Si coated with TiN, polycrystalline diamond (PCD) and cubic boron nitride films, and Ti-6Al-4V alloy have been used as substrates. Some of the substrates have been pretreated ultrasonically with diamond powder in order to enhance the nucleation density n_nuc. It turned out that n_nuc depends critically on the chemical nature of the substrate, its smoothness and the pretreatment applied. No differences to the nucleation behaviour of CVD PCD films were observed. On the other hand, the growth process seems to be not affected by the substrate material. The crystallinity (studied by X-ray diffraction) and the bonding environment (investigated by Raman spectroscopy) show no significant differences for the various substrates. The mechanical and tribological properties, finally, reflect again the influence of the substrate material: on TiN, a lower hardness was measured as compared to Si, PCD and c-BN, whereas the adhesion of c-BN/nanocrystalline diamond (NCD) system was determined by that of the c-BN film on the underlying Si substrate.     

Adhesion of diamond coatings on cemented carbides

Precise quantification of the adhesion of diamond coatings on cemented carbide (WC-Co) inserts is important for industrial applications. Adhesion is strongly influenced by the surface roughness, surface reactivity, catalytic effect of Co during diamond chemical vapour deposition (CVD) and by stresses developed in the film and at the bonding interface.

In this work we investigated the adhesion of diamond coatings on WC-Co by using Rockwell-C indentation. Various surface modifications were studied: Co leaching; replacement of Co by Cu; WC-Co decarburization and deposition of Ti intermediate layer prior to diamond CVD. Turning tests with diamond coated inserts for machining of Al alloy were carried out.