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.     

Fluidized bed micro-machining and HFCVD of diamond films onto Co-cemented tungsten carbide (WC-Co) hardmetal slabs

The effect of fluidized bed (FB) treatment upon hot filament chemical vapor deposition (HFCVD) of polycrystalline diamond films onto WC-Co hardmetal substrates was investigated. Several scenarios to make the substrates ready for HFCVD were, comparatively, evaluated and the resulting diamond films were examined in terms of their morphology and adhesion. The diamond grain density was measured by scanning electron microscopy. The adhesion of continuous diamond film to substrate was evaluated by the reciprocal of the slope of crack radius-indentation load functions. Surface binder dissolution followed by FB treatment (PF pretreatment) allowed very high diamond nucleation density and smaller grain size. The adhesion of films grown on PF pretreated substrates was found to be very close to that of films deposited on hardmetal slabs pretreated by Murakami's reagent followed by Co etching with Caro's acid and seeded with diamond suspension in an ultrasonic vessel (MPS pretreatment). However, diamond coatings on MPS pretreated samples exhibited a rougher surface morphology as a result of both lower diamond nucleation density and larger substrate surface roughening by Murakami's etching. Based upon experimental findings, our newly developed PF pretreatment was found to be a very promising technique in substrates conditioning as well as in promoting adherent, uniform and smooth diamond coatings onto hardmetal tools and wear parts.     

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.     

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.     

金刚石涂层与硬质合金刀具附着力的研究进展

介绍了国内外在低压合成金刚石涂层刀具中提高薄膜基体附着力的几种典型工艺方法。给出了ＷＣ－Ｃｏ基底刀具预处理对低压合成金刚石薄膜附着力的影响。     

Chemical vapor deposition of highly adherent diamond coatings onto co-cemented tungsten carbides irradiated by high power diode laser

The present investigation deals with the definition of a new eco-friendly alternative to pretreat Co-cemented tungsten carbide (WC-Co) substrates before diamond deposition by hot filament chemical vapor deposition (HFCVD). In particular, WC-5.8 wt %Co substrates were submitted to a thermal treatment by a continuous wave-high power diode laser to reduce surface Co concentration and promote the reconstruction of the WC grains. Laser pretreatments were performed both in N(2) and Ar atmosphere to prevent substrate oxidation. Diamond coatings were deposited onto the laser pretreated substrates by HFCVD. For comparative purpose, diamond coatings were also deposited on WC-5.8 wt %Co substrates chemically etched by the well-known two-step pretreatment employing Murakami's reagent and Caro's acid. Surface morphology, microstructure, and chemical composition of the WC-5.8 wt %Co substrates after the different pretreatments and the deposition of diamond coatings were assessed by surface profiler, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction analyses. Wear performance of the diamond coatings was checked by dry sliding linear reciprocating tribological tests. The worn volume of the diamond coatings deposited on the laser pretreated substrates was always found lower than the one measured on the chemically etched substrates, with the N(2) atmosphere being particularly promising.     

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     

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。     

Enhanced deposition of cubic boron nitride films on roughened silicon and tungsten carbide-cobalt surfaces

We report the influence of substrate surface roughness on cubic boron nitride (cBN) film deposition under low-energy ion bombardment in an inductively coupled plasma. Silicon and cemented tungsten carbide-cobalt (WC-Co) surfaces are roughened by low-energy ion-assisted etching in a hydrogen plasma, followed by deposition in a fluorine-containing plasma. Infrared absorption coefficients are measured to be 22,000 cm⁻¹ and 17,000 cm⁻¹ for sp²-bonded BN and cBN phases, respectively, for our films. For the silicon substrates, the film growth rate and the cBN content in the film increase with increasing the surface roughness, while the amount of sp²BN phase in the film shows only a small increase. A larger surface roughness of the substrate results in a smaller contact angle of water, indicating that a higher surface free energy of the substrate contributes to enhancing growth of the cBN film. For the WC-Co substrates, the film growth rate and the cBN content in the film increase similarly by roughening the surface.     

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.     

Microstructural control of boundary region between CVD diamond film and cemented carbide substrate

Effects of the composition, texture and pretreatment of cemented carbide substrates on the microstructure of the boundary region between CVD diamond film and the substrate were investigated using a microwave plasma CVD in the CO-H₂ system. Optimum CVD conditions for a uniform coating on to the edge part of cutting insert were: microwave power, 550 W; total pressure, 30 Torr; total flow rate, 200 ml/min; CO concentration, 5–20 vol%; treatment time, 3–5 h. An adherent and tough diamond coating was prepared by initial coating at lower CO concentrations and by subsequent coating at higher CO concentrations. A cemented carbide substrate in the binary WC-Co system which comprised fine-grained tungsten carbide and low content of cobalt was suited for preparation of adherent diamond coating. De-cobaltization pretreatment of the substrate surface in acid solution followed by an ultrasonic microflawing treatment enhanced the nucleation density and adherence of diamond film to the substrate. The rotation of substrate was found to be effective for increasing the uniformity and decreasing the grain size of diamond film.     

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。     

The nature of stresses in hot-filament chemical vapour deposited diamond thin films on WC substrates

The nature of film stresses in hot-filament chemical vapour deposited (HFCVD) diamond thin films on tungsten carbide substrates, is reported. Commercial WC substrates were subjected to various surface treatments. Subsequently, they were coated with a diamond film and examined for stresses using X-ray diffraction. All but one of the stress measurements indicated various levels of compressive stresses in the film and at the film–substrate interface. These stresses are compared with those obtained by other researchers. Intrinsic film stresses were also computed for diamond films and found to be tensile. WC drills, of 0.125 in. diameter, were also diamond coated and the stress levels measured along drill flanks and flutes. Significant variations were found in these stresses, and the results were analysed from a film–substrate adhesion perspective.     

Application of diamond films from CO-H2 plasma to tool blade coating

Diamond films were coated on WC-Co alloy tool blades using a microwave plasma of CO-H₂ mixed gas. Diamond film prepared at a CO concentration of 10% had good properties: Vickers hardness % 8500 kg mm^–2 and adhesion force 1.7 kg mm^–2. No peel-off of the diamond film was observed after a cutting test of an Al-Si alloy rod at a cutting speed of 450 m min^–1 for 0.5 h. It is thought that the high quality of the film originated from the selective etching of cobalt from the tool blade surface by CO-H₂ plasma.     

Analysis of surface preparation treatments for coating tungsten carbide substrates with diamond thin films

The effect of various substrate surface treatments on (i) the pre-growth topography and composition of the treated substrate, and (ii) the quality of diamond thin films produced by hot-filament chemical vapour deposition on tungsten carbide substrates, is reported. Two different substrate grain sizes were subjected to various surface treatments. They were then examined for surface material composition and topography using scanning electron microscopy and X-ray diffraction (XRD). Subsequently, diamond films were deposited on the samples and their quality analysed by Raman spectroscopy and XRD techniques. These analyses do not indicate a strong dependence between the substrate grain size and film quality. However, the surface-treatment method affects the resulting substrate surface topography and film quality. This revised version was published online in November 2006 with corrections to the Cover Date.     

Chemical vapour deposition of microdrill cutting edges for micro- and nanotechnology applications

Conventional cemented tungsten carbide-cobalt (WC-Co) microdrills generally have a low cutting efficiency and short lifetime mainly because they operate at very high cutting speeds. Since it is relatively expensive to make microtools it is highly desirable to improve their lifetime and in-service performance. Microtools used to make microelectronic and mechanical systems (M.E.M.S) devices with sharp cutting edges, such as milling or drilling tools need protective coating in order to extend life and improve performance. One method of achieving this objective is to use a suitable surface engineering technology to deposit a hard wear resistant coating, such as diamond. Diamond has excellent mechanical properties, such as ultra-high hardness and a low friction coefficient. One of the most promising surface treatment technologies for depositing diamond onto complex shaped components is chemical vapour deposition (CVD). However, CVD of diamond coatings onto the cemented WC-Co tool has proved to be problematic. Binder materials such as cobalt can suppress diamond nucleation resulting in poor adhesion between the coating and substrate. In this paper the effects of pre-treated substrate material on the coating structure are reported. The morphology and the crystallinity of the as-grown films was characterised by using scanning electron microscopy (SEM). Raman spectroscopy was used to assess the carbon-phase purity and give an indication of the stress levels in the as-grown polycrystalline diamond films. The diamond coated tools have potential applications in micro- and nanomachining of micro- and nano-sized components used in M.E.MS.     

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.     

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.     

Diamond films deposited on WC-Co substrates by use of barrier interlayers and nano-grained diamond seeds

Results on the structure, composition and properties of diamond films deposited onto WC-Co cemented carbides via special multilayer barrier interlayers preliminary seeded by nano-grained diamond particles are presented. The barrier interlayers comprise a layer adjacent to the substrate, which completely prevents substrate decarburization and Co diffusion from the substrate, and a diamond-bonding layer needed to obtain an enhanced adhesion of the PACVD diamond coating. Preliminary seeding the barrier interlayers with nano-grain diamond particles by use of a laser ablation technique allows a fine-grained, uniform and highly adherent diamond coating of high quality to be deposited by use of a conventional PACVD technique. Results on the nature of the interaction between the diamond nano-grained seeds and barrier interlayer are also presented.     

Diamond film adhesion onto sub-micrometric WC-Co substrates

Different chemical etching procedures (CF₄ plasma, Aqua regia, and two-step Murakami/Aqua regia) were compared as surface pre-treatments for CVD diamond deposition onto sub-micrometric WC-Co hardmetal grades with cobalt contents of 3.5 and 5.75 wt% Co. Adhesion tests by static indentation up to 1100 N revealed the superior behaviour of the latter when pre-treated by the combined two-step etching for which no film spalling-off is observed at the maximum applied load. An interfacial crack resistance of about 1.6 kgf/μm was estimated anticipating high adhesion levels.