Diffusion of cobalt in diamond films synthesized by combustion flame method

It is well known that Cobalt (Co) plays an important role during diamond deposition on cemented carbide substrates (WC). The presence of cobalt on the substrate lead to decrease adhesion and increase the formation of non-diamond compounds phases. However, the diffusion phenomenon of cobalt in diamond coatings is not well understood.We have carried out a detailed study to investigate the diffusion of cobalt during the nucleation and growth of diamond on WC-Co substrate by combustion-flame method, and the influence of it on the structure and quality of the diamond coatings. At high substrate temperature T_s>800 °C, ball-sharp of cobalt with a ball size about 0.7 μm was observed on the top surface of diamond coatings (thickness >50 μm). The constraints in the coating are very high, the Raman peak appearance at 1341.1 cm⁻¹. At relatively low substrate temperature, T_s is about 550 °C, ball sharp of cobalt was not observed by MEB but a lot of cobalt particles dissolution carbon films were detected by EDX.Based on the above results, the influence of cobalt on the structure, the quality and the constraints in the diamond films are discussed, a model suggesting the nucleation and growth mechanisms of diamond, to explain the cobalt diffusion in diamond films, is presented.     

Nucleation and Growth of Diamond Films on Ni-Cemented Tungsten Carbide: II, Effects of Deposition Conditions

Diamond films were deposited by hot-filament chemical vapor deposition (HFCVD) on substrates made of WC sintered with 6 wt% of Ni. The as-ground substrates were scratched with diamond powder (S samples) or scratched and wet-etched (SE samples). Diamond synthesis was carried out at substrate temperatures ranging between 600° and 1050°C, and using 1.0% or 2.0% CH₄ in H₂. The diamond nucleation density, as measured by scanning electron microscopy (SEM) and automatic image analysis (AIA), did not significantly change in the 600°-900°C temperature range, while at substrate temperatures higher than 900°C a steep decrease of the density of nuclei was observed and attributed to the thermal annealing of nucleation sites. The activation energy of the growth process was measured and found to be 21 ± 2 kcal/mol. Neither nucleation density nor growth rate were affected by an increase of CH₄ concentration in the feed gas, while a lack of crystallinity was observed at the higher methane concentration. Raman analysis showed that phase purity of the films was affected mainly by the substrate temperature: the lower the temperature, the better the film quality. The presence of Ni on the substrate surface did not induce the preferential formation of non-diamond carbon phases, as confirmed by comparing the Raman spectra obtained from both S and SE substrates. As a comparison, continuous films were deposited on scratched WC-5 wt% Co substrates under the same experimental conditions. The results indicated that the use of Ni as a binder is preferable to Co.     

Effects of TiMoTa nano-crystalline interlayer on nucleation,adhesion and tribological behaviors of diamond coating

To investigate the influence of the transition layer on diamond nucleation and growth, the TiMoTa multi-alloy interlayers were firstly prepared on WC-6%Co cemented carbide by double glow plasma surface alloying technique, and diamond was then deposited using microwave plasma chemical vapor deposition system. The thickness of the TiMoTa interlayers increased from 1.2 μm to 2.7 μm with the deposition temperature increasing from 800 to 900 °C. Due to the formation of nano-crystalline structure and hard phase, the as-prepared TiMoTa interlayer exhibited high micro-hardness. In the diamond deposition process, the nano-carbide particles preferentially formed at the TiMoTa interlayers can effectively prevent the further diffusion of C, so the surface carbon concentration rapidly accumulates to the critical value required for the nucleation and growth of diamond microcrystals. Finally, a microscale wear-resistant diamond coating with good adhesion was grown on the transition layer, the crack propagation radius of the diamond coating is ～162 μm, and can reach Hf 2–3 grade. Therefore, our prepared TiMoTa nano-crystalline interlayer provides a new path for the development of a high-quality diamond coating with good adhesion on cemented carbide.     

Nucleation and Growth of Diamond Films on Ni-Cemented Tungsten Carbide: Effects of Substrate Pretreatments

The nucleation and growth of diamond films on Nicemented carbide is investigated. Substrates made of WC with 6 wt% of Ni were submitted to grinding, and then to different pretreatments (scratching, etching, and/or decarburization) before diamond deposition. Diamond synthesis was carried out by hot-filament chemical vapor deposition (HFCVD) using a mixture of CH₄ (1% v/v) and H₂. Depositions were performed for different lengths of time with the substrates at various temperatures. The specimens were analyzed before and after deposition by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and X-ray diffractometry (XRD). Raman spectra showed that the phase purity of the diamond films was not affected by the presence of nickel on the substrate surface. After wet etching pretreatments, the nucleation of diamond was enhanced, mainly at the WC grain boundaries. Continuous films were obtained on scratched and etched substrates. The decarburizing treatment led to the formation of metallic tungsten and of brittle nicke–tungsten carbide phases. These phases reacted in the early stages of diamond film formation with gaseous carbon species with a parallel process which competes with stable diamond nucleus formation. The diamond film formed after long-term deposition on these samples was not continuous.     

Interfacial oxide and carbide phases in the deposition of diamond films on beryllium metal

We have investigated beryllium metal as a substrate for the microwave plasma chemical vapor deposition of diamond films. The dependence of oxide and carbide interfacial phase formation with temperature and their influence on diamond nucleation and growth behavior were studied by thin film X-ray diffraction. Although a native oxide (BeO with the hexagonal wurtzite structure) remains for the range of substrate temperatures studied (700–800°C), the formation of a carbide (Be₂C with the cubic antifluorite structure) is found only above a critical substrate temperature of approximately 750°C. Without the formation of Be₂C, the diamond growth rate is low and a significant amorphous carbon component is observed. Just above the critical temperature, films exhibited high growth rates with high phase-purity diamond. Thick films (>30 μm) grown above the critical temperature were observed to fracture completely within the Be₂C layer, suggesting this to be the weak structural link.     

Effects of cobalt and cobalt oxide buffer layers on nucleation and growth of hot filament chemical vapor deposition diamond films on silicon (100)

An initial study on the nucleation and growth of diamond, using hot filament chemical vapor deposition (HFCVD) technique, was carried out on Co and CoO thin buffer layers on non-carbon substrates (Si (100)), and the results were compared with conventional scratching method. The substrate temperature during the growth was maintained at 750±50 °C. A mixture of CH₄ and H₂ (1: 100 volume %) was used for deposition. The total pressure during the two hour deposition was 30±2 Torr. X-ray photoelectron spectroscopy (XPS) study showed the diamond nucleation at different time periods on the Co and CoO seed layers. It is observed that Co helps in nucleation of diamond even though it is known to degrade the quality of diamond film on W-C substrate. The reason for improvement in our study is attributed to (i) the low content of Co (~0.01%) compared to W-C substrate (~5–6%), (ii) formation of CoSi₂ phase at elevated temperature, which might work as nucleation sites for diamond. SEM analysis reveals a change in the morphology of diamond film grown on cobalt oxide and a significant reduction in the size of densely packed crystallites. Raman spectroscopic analysis further suggests an improvement in the quality of the film grown on CoO buffer layer.     

Adhesion properties of CVD diamond film on binder-less sintered tungsten carbide prepared by the spark sintering process

This paper describes the adhesion property of chemical-vapor-deposited (CVD) diamond film on tungsten carbide (WC) bodies prepared by spark sintering without a binder. WC bodies ranging from 70 to 95% of density ratio have been sintered under different sintering conditions, and their mechanical properties, such as hardness and bending strength, have been measured. High-quality diamond films with a higher nucleation density compared to that on WC–Co have been deposited on this WC substrate using the microwave plasma CVD method. A comparison study using indentation tests shows that the adhesive strength of diamond films on this binder-less sintered WC is remarkably superior to that on WC–Co, which is believed to result from the increase in diamond nucleation density, the enhanced mechanical bonding between the substrate and the diamond film and the well-matching of thermal expansion coefficients caused by the absence of the fatal obstacle of cobalt. Moreover, an increase in adhesive strength has occurred on the binder-less sintered WC with lower density ratios.     

Adhesion improvement of diamond coatings on cemented carbide with high cobalt content using PVD interlayer

At present, diamond coating is usually deposited on cemented carbide (WC-Co) tool with low Co content (Co ≤ 6 wt.%). It is more difficult to deposit diamond coating on WC-Co with high Co content because of the strong catalytic effect of Co. However, WC-Co tools with high Co content (Co ≥ 6 wt.%) are more widely used in difficult-to-cut materials machining because of their higher strength and better ductility. In this paper, the research was carried out on the adhesion performance of diamond coating on WC-Co (Co 10 wt.%). The deposition of diamond coating was conducted in hot filament chemical vapor deposition (HFCVD) system with the presence of the strong carbon-forming metallic interlayer (Nb, Cr or Ta), which was prepared using physical vapor deposition (PVD) on WC-Co substrate after chemical etching through a two-step process (Murakami solution and Caro's acid), which is a general way to treat the WC-Co substrate before growth of diamond coating. The results showed that the diamond films grown on the above treated WC-Co substrate have higher nucleation density, purity and adhesion strength than those on WC-Co substrates pretreated only using PVD interlayer or chemical etching. The PVD interlayer restrains the diffusion of Co as a result of high substrate temperature during the diamond film deposition, and consequently prevents the formation of the loosened layer induced by the removal of Co binder phase in the WC-Co substrate. The results also indicated that Nb interlayer leads to the most adhesion improvement of diamond films on the WC-Co inserts among the Nb, Ta and Cr interlayers.     

Influence of H2S addition during diamond deposition on hardmetal substrates

Diamond deposition on hardmetal substrates is an industrial process to increase the wear resistance of tools during machining operations, but till now an increase in diamond layer adhesion is desirable. The main problem during diamond deposition on hardmetal substrates is the Co content in the binder phase.H₂S was used for immobilizing the cobalt on the substrate surface. The H₂S should react with the metallic Co covering its surface with CoS. Because of this the diamond nucleation occurs easier and the Co vapour pressure is also reduced. Similar mechanisms were observed using silicon and boron vapour during substrate pre-treatment.Positive effects of H₂S addition were achieved if the H₂S is added only during the diamond nucleation period. The experiments with continuous H₂S addition were not successful.For comparison diamond deposition on Murakami/Carrot pre-treated substrates were carried out.     

The diffusion behavior of carbon in sputtered tungsten film and sintered tungsten block and its effect on diamond nucleation and growth

Diamond was done on sintered tungsten block with or without sputtered tungsten films. The effects of various depositing conditions, including methane concentration, temperature, pressure, the diamond seeding step and reaction time, on diamond growth were investigated in detail. The results show that the sputtered tungsten film has a dual effect on diamond growth. Firstly, after ultrasonication with diamond slurry, the tungsten film will adsorb a large number of diamond nanoparticles. Therefore, the nucleation density of diamond will be substantially improved. Secondly, the film will be carbonized during the deposition process and the carbon on the surface of the film will decrease. Methane concentration generally does not affect the carbonization level of the tungsten film but higher temperature will lead to a higher level of carbonization. The carbonization process of sputtered tungsten films during deposition is made up of two steps. Also, the nucleation surface of diamond was revealed. The nucleation surface was a layer of ultrasmooth and seamless nanocrystalline diamond film with high-quality and special surface architecture (tiny peaks arrays), which is potential to be applied in MEMS and field-emission devices. A potential method to prepare ultrasmooth nanocrystalline diamond films is proposed.     

Effects of surface pretreatments on the deposition of adherent diamond coatings on cemented tungsten carbide substrates

Well-adhered microcrystalline diamond (MCD) coatings have been deposited on WC–Co substrates by the microwave plasma enhanced chemical vapor deposition (MPECVD) method. A multi-interlayer system Cr/CrN/Cr was deposited on the cemented carbide substrate before diamond deposition to act as a diffusion barrier. The interlayer-coated substrate was shortly peened by friable diamond powders with an average size of 150 μm to roughen the surface. Diamond coatings deposited on short peened substrates show higher nucleation density and stronger adhesion properties. The X-ray diffraction (XRD) pattern showed that an additional carbide compound layer (Cr₃C₂ and Cr₇C₃) was formed during the CVD diamond deposition to work as an intermediate bonding layer for better adhesion. Rockwell indentation tests with a load of 1470 N were conducted to investigate the coating's adhesion. No delamination outside of the indentation zone was observed for the diamond coating deposited on the roughened sample. Electron probe microanalysis (EPMA) results showed that the delamination in the indentation zone occurred mainly at the diamond/Cr interface and very little Co (less than 1 wt.%) was detected on the Cr failure surface. This suggests that during the CVD process Co/C inter-diffusion was successfully prevented by the Cr/CrN/Cr buffer layers.     

Room-Temperature Thermal Conductivity of Cemented Transition-Metal Carbides

Measurements are reported of the room-temperature thermal conductivity of cemented multicarbides (WC-TiC _x -NbC _x -TaC _x /Co) and straight tungsten carbide (WC/Co), which are widely used tool materials. The thermal conductivity of cemented titanium carbide was found to be lower than that of cemented tungsten carbide. The difference is attributed to strong phonon and electron scattering from carbon atom vacancies in the nonstoichiometric cubic carbide TiC _x ; these defects are absent in stoichiometric hexagonal WC. Higher binder contents in tungsten carbide samples lowered the overall thermal conductivity. Scattering of electrons and phonons by C and W atoms in solid solution in the binder phase presumably reduces its thermal conductivity. No dependence on grain size was detected.     

The effect of tungsten buffer layer on the stability of diamond with tungsten carbide–cobalt nanocomposite powder during spark plasma sintering

WC–Co nanocomposite powder produced by spray pyrolysis–continuous reduction and carbonization technology, diamond coated with tungsten (W) by vacuum vapor deposition and uncoated diamond were used in this study. This work adopted the spark plasma sintering (SPS) process to prepare diamond-enhanced ultrafine WC–Co cemented carbide composite material. The effects of W buffer on the stability of diamond with WC–Co nanocomposite powder during SPS were investigated. Results showed that the uncoated diamond was mechanically embedded in WC–Co cemented carbide matrix, while the diamond coated with tungsten was combined chemically with WC–Co cemented carbide matrix. Moreover, there was a transitional layer between the diamond and the matrix which could improve the thermal stability of the diamond, prevent carbon atom of the diamond from dissolving in Co phase and increase the bonding strength of the interface between the diamond and the matrix.     

影响金刚石膜刀具涂层形貌的因素分析

采用高分辨金相显微镜对硬质合金刀生上沉各的ＣＶＤ金刚石薄膜进行了表面形貌和膜／基横截面组织形貌的观察;并利用该显微镜配备的功能测量了金刚石颗粒大小,膜厚;利用显微镜正焦／过焦观察判断了金刚石薄膜的成膜状况。初步观察结果表明：甲烷浓度和基体钴含量对金刚石薄膜的表面形貌和膜／基横截面组织形貌有显著的影响。     

The effect of pulse-reverse electroplating bath temperature on the wear/corrosion response of Ni-Co/tungsten carbide nanocomposite coating during layer deposition

In this article, the effect of bath temperature during layer deposition on the electrochemical/abrasion responses of Ni-Co/tungsten carbide nanocomposite coating has been investigated. The Ni-Co/tungsten carbide nanocomposite coating was obtained using simultaneous deposition of tungsten carbide nanoparticles in three Ni-Co bath temperatures of 20, 40, and 60?°C. Afterwards, in order to characterize the obtained coatings, Field Emission Scanning Electron Microscopy (FE-SEM) and Transmission Electron Microscopy (TEM), X-Ray diffraction (XRD), MAP analysis, potentiodynamic polarization and electrochemical impedance spectroscopy methods in 3.5?wt% NaCl, and also abrasion test using a pin on disc method were carried out. The results of this study revealed that the deposition obtained from Ni-Co bath contains tungsten carbide nanoparticles and results in strong (200) and hard (111) textures in the coating at different temperatures. Also increasing the bath temperature from 20 to 40?°C results in the absorption of cobalt and tungsten carbide nanoparticles, as well as reducing the nickel content and corrosion resistance in the coating, and on one hand it increases the abrasion resistance of the coating. However, a bath-temperature increase from 40 to 60?°C results in reducing the absorption of cobalt and tungsten carbide nanoparticles, and increasing the nickel content and corrosion resistance in the coating as well as reducing the abrasion resistance of the coating.     

Cubic boron nitride films for industrial applications

The effects of kinetic energy, chemical nature of substrates and temperature on the synthesis of cBN films are explored to obtain cBN films with industrial quality. Carbon including amorphous carbon, nanocrystalline and polycrystalline diamond enables deposition of stable, thick and adherent cBN films with characteristic Raman signature. Although temperature has been designated as an unimportant parameter, the deposition at higher temperatures yields higher quality of cBN films. The higher temperature (800 °C) was also employed at cBN deposition on diamond coated tungsten carbide (WC) cutting inserts using plasma enhanced chemical vapor deposition (PECVD). The quality of cBN films grown by PECVD significantly overcomes that prepared by physical vapor deposition (PVD) which is affected in large extent by the lower kinetic energies of particles used in PECVD. The low kinetic energy of particles induces surface growth mechanism which differs from the growth models previously proposed.     

High-Temperature Reaction Between Cemented Tungsten Carbide and Copper

Interdiffusion in the system cemented tungsten carbide-molten copper has been studied in the range ≤1120°C with special emphasis on the effects of WC grain size and Co content. Techniques used for analyzing the diffusion layers obtained are EPMA, optical microscopy, and microhardness measurement. A Cu-bonded WC layer develops with simultaneous diffusion of Co from the cemented carbide into the bulk copper. The Cu-bonded WC layer grows until a Co-rich layer forms at the Cu/WC-Co interface; further heating pushes the Cu-bonded WC layer deep into the bulk cemented carbide without any significant change in layer thickness. When the WC grain size is reduced and the cobalt content increased, the penetration of copper into cemented carbides increases. A tentative mechanism of interdiffusion has been proposed based on the experimental results.     

A study of diamond film deposition on WC–Co inserts for graphite machining: Effectiveness of SiC interlayers prepared by HFCVD

Thin silicon carbide (SiC) films were deposited from tetramethylsilane/hydrogen gas mixture on Co-cemented tungsten carbide (WC–Co) inserts by using Hot-Filament Chemical Vapour Deposition (HFCVD) technique. Grazing incidence X-Ray Diffraction (XRD) confirmed that the films were composed of cubic silicon carbide (β-SiC) and that small amounts of dicobalt silicide (Co₂Si) were formed. These films were used as interlayers for subsequent CVD of diamond films. XRD and combined Scanning and Transmission Electron Microscopies showed that the binder phase reacted during CVD to form cobalt silicides. However, these intermetallic compounds did not have bad effects on diamond adhesion. Dry turning of graphite was chosen to check the multilayer (SiC + diamond) film performance. For the sake of comparison, machining tests were also carried out under identical conditions using commercial sintered diamond (PCD) inserts and WC–Co diamond coated inserts with no interlayer. The wear mechanism of the tools has been identified and correlated with the criterion used to evaluate the tool life. The results showed that multilayer (SiC + diamond) coatings exhibited the longest tool lives. Therefore, thin SiC interlayers proved to be a new viable alternative and a suitable option for adherent diamond coatings on cemented carbide components and cutting tools.     

Tribological properties and cutting performance of boron and silicon doped diamond films on Co-cemented tungsten carbide inserts

Boron and silicon doped diamond films are deposited on the cobalt cemented tungsten carbide (WC-Co) substrate by using a bias-enhanced hot filament chemical vapor deposition (HFCVD) apparatus. Acetone, hydrogen gas, trimethyl borate (C₃H₉BO₃) and tetraethoxysilane (C₈H₂₀O₄Si) are used as source materials. The tribological properties of boron-doped (B-doped), silicon-doped (Si-doped) diamond films are examined by using a ball-on-plate type rotating tribometer with silicon nitride ceramic as the counterpart in ambient air. To evaluate the cutting performance, comparative cutting tests are conducted using as-received WC-Co, undoped and doped diamond coated inserts, with high silicon aluminum alloy materials as the workpiece. Friction tests suggest that the Si-doped diamond films present the lowest friction coefficient and wear rate among all tested diamond films because of its diamond grain refinement effect. The B-doped diamond films exhibit a larger grain size and a rougher surface but a lower friction coefficient than that of undoped ones. The average friction coefficient of Si-doped, B-doped and undoped diamond films in stable regime is 0.143, 0.193 and 0.233, respectively. The cutting results demonstrate that boron doping can improve the wear resistance of diamond films and the adhesive strength of diamond films to the substrates. Si-doped diamond coated inserts show relatively poor cutting performance than undoped ones due to its thinner film thickness. B-doped and Si-doped diamond films may have tremendous potential for mechanical application.     

A kinetic model of diamond nucleation and silicon carbide interlayer formation during chemical vapor deposition

The presence of thin silicon carbide intermediate layers on silicon substrates during nucleation and the early stages of diamond deposition have been frequently reported. It is generally accepted that the intermediate layer is formed by the bulk diffusion of carbon atoms into the silicon carbide layer and the morphology and orientation of the diamond film subsequently grown on the intermediate layer are strongly affected by that layer. While there have been considerable attempts to explain the mechanism for intermediate layer formation, limited quantitative data are available for the layer formation under the operating conditions conducive to diamond nucleation.This study employs a kinetic model to predict the time evolution of a β-SiC intermediate layer under the operating conditions typical of diamond nucleation in hot filament chemical vapor deposition reactors. The evolution of the layer is calculated by accounting for gas-phase and surface reactions, surface and bulk diffusions, the mechanism for intermediate layer formation, and heterogeneous diamond nucleation kinetics and of its dependence on the operating conditions such as substrate temperature and inlet gas composition. A comparison between the time scales for intermediate layer growth and diamond nuclei growth is also performed. Discrepancies in published adsorption energies of gaseous hydrocarbon precursors on the intermediate layer—ranging from 1.43 to 4.61 eV—are examined to determine the most reasonable value of the adsorption energy consistent with observed saturated thicknesses, 1–10 nm, of the intermediate layer reported in the literature. The operating conditions that lead to intermediate layer growth followed by diamond deposition vs. those that yield heteroepitaxial diamond nucleation without intermediate layer formation are discerned quantitatively. The calculations show that higher adsorption energies, 3.45 and 4.61 eV, lead to larger surface number densities of carbon atoms, lower saturated nucleation densities, and larger intermediate layer thicknesses. The observed saturated thicknesses of the intermediate layer may be reproduced if the true adsorption energy is in the range of 3.7–4.5 eV. The intermediate layer thickness increases by increasing substrate temperature and inlet hydrocarbon concentration and the dependence of the thickness on substrate temperature is especially significant. Heteroepitaxial diamond nucleation without intermediate layer formation reported in experimental results can be readily explained by the significant decrease of the intermediate layer thickness at lower substrate temperatures and at higher diamond nucleation densities. Further, the present model results indicate that the intermediate layer thickness becomes saturated when growing diamond nuclei cover a very small surface area of that layer.