Influence of TaCl5 partial pressure on texture structure of TaC coating deposited by chemical vapor deposition

TaC was deposited on graphite substrate with different TaCl₅ partial pressure at 800 °C and 1200 °C by chemical vapor deposition. Microstructures and texture structures of the prepared coatings were researched with X-ray diffraction and scanning electronic microscopy. When the coating deposition process is controlled by surface reaction kinetics (800 °C), TaCl₅ partial pressure had little influence on the microstructure and texture structure of the coating. When the coating formation process is controlled by diffusion kinetics (1200 °C), the microstructure, texture structure of the prepared TaC grains vary greatly with TaCl₅ partial pressure. In the diffusion controlled process, the increasing of TaCl₅ partial pressure will result in the changing of gas supersaturation, and then the occurrence of secondary nucleation, which is the main reason for the changing of coating morphology and texture structure. With the help of competitive growth in (1 0 0) and (1 1 1) directions, the formation mechanism of the different texture coatings are discussed in detail. In addition, a diffusion model of deposition species around step-edge-corner was also proposed to explain the growth mechanism of the texture coatings.     

Influence of high temperature annealing on the structure, hardness and tribological properties of diamond-like carbon and TiAlSiCN nanocomposite coatings

Diamond-like carbon (DLC) and TiAlSiCN nanocomposite coatings were synthesized and annealed at different temperatures in a vacuum environment. The microstructure, hardness and tribological properties of as-deposited and annealed DLC-TiAlSiCN nanocomposite coatings were characterized by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Raman spectroscopy, nano-indentation and friction tests. The TEM results reveal that the as-deposited DLC-TiAlSiCN coating has a unique nanocomposite structure consisting of TiCN nanocrystals embedded in an amorphous matrix consisting of a-Si₃N₄, a-SiC, a-CN and DLC, and the structure changed little after annealing at 800 °C. However, XPS and Raman results show that an obvious graphitization of the DLC phase occurred during the annealing process and it worsened with annealing temperature. Because of the graphitization, the hardness of the DLC-TiAlSiCN coating after annealing at 800 °C decreased from 45 to 36 GPa. In addition, the DLC-TiAlSiCN coating after annealing at 800 °C has a similar friction coefficient to the as-deposited coating.     

Fabrication of protective tantalum carbide coatings on carbon fibers using a molten salt method

Protective tantalum carbide (TaC) coatings were fabricated successfully on carbon fibers in the temperature range of 950-1100 °C using a molten salt method. A salt mixture composed of LiCl-KCl-KF was used as a reaction medium in which the tantalum and the carbon fiber substrates reacted to form the TaC coatings. The structure and morphology of the TaC coatings were characterized by XRD, SEM and EDX analyses. The results show that the reaction temperature and time have significant influence on the thickness, integrity and surface morphology of the TaC coatings. A uniform, adherent and crack-free TaC coating can be obtained by controlling the reaction temperature and time. Thermo-gravimetric analysis indicated that the oxidation resistance of the carbon fibers was improved remarkably by coating them with a high-quality TaC layer.     

Ablation properties of carbon/carbon composites with tungsten carbide

The ablation properties and morphologies of carbon/carbon (C/C) composites with tungsten carbide (WC) filaments were investigated by ablation test on an arc heater and scanning electron microscopy. And the results were compared with those without tungsten carbide (WC) filaments tested under the same conditions. It shows that there is a big difference between C/C composites with and without WC filaments on both macroscopic and microscopic ablation morphologies and the ablation rates of the former are higher than the latter. It is found that the ablation process of C/C composites with WC filaments includes oxidation of carbon fibers, carbon matrices and WC, melting of WC and WO₃, and denudation of WC, WO₃ and C/C composites. Oxidation and melting of WC leads to the formation of holes in z directional carbon fiber bundles, which increases the coarseness of the ablation surfaces of the composites, speeds up ablation and leads to the higher ablation rate. Moreover, it is further found that the molten WC and WO₃ cannot form a continuous film on the ablation surface to prevent further ablation of C/C composites.     

(Ti,Al,Si,C)N nanocomposite coatings synthesized by plasma-enhanced magnetron sputtering

Materials’ surface service property could be enhanced by transition metal nitride hard coatings due to their high hardness, wear and high temperature oxidation resistance, but the higher friction coefficient (0.4-0.9) of which aroused terrible abrasion. In this work, quinternary (Ti,Al,Si,C)N hard coating 3-4 μm was synthesized at 300 °C using plasma enhanced magnetron sputtering system. It was found that the coating's columnar crystals structure was restrained obviously with the increase of C content and a non-columnar crystals growth mode was indicated at the C content of 33.5 at.%. Both the XRD and TEM showed that the (Ti,Al,Si,C)N hard coatings had unique nanocomposite structures composed of nanocrystalline and amorphous nc-(Ti,Al)(C,N)/nc-AlN/a-Si₃N₄/a-Si/a-C. However, the coatings were still super hard with the highest hardness of 41 GPa in spite of the carbon incorporation. That a-C could facilitate the graphitization process during the friction process which could improve the coating's tribological performance. Therefore, that nanocomposite (Ti,Al,Si,C)N coatings with higher hardness (>36 GPa) and a lower friction coefficient (<0.2) could be synthesized and enhance the tribological performance and surface properties profoundly.     

In situ formation of low friction ceramic coatings on carbon steel by plasma electrolytic oxidation in two types of electrolytes

In situ formation of ceramic coatings on Q235 carbon steel was achieved by plasma electrolytic oxidation (PEO) in carbonate electrolyte and silicate electrolyte, respectively. The surface and cross-section morphology, phase and elemental composition of PEO coatings were examined by means of scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS). The bond strength of the coating was determined using a direct pull-off test. The hardness as well as tribological properties of the ceramic coating was primarily studied. The results indicated that the coating obtained in carbonate electrolyte was Fe₃O₄, while the coating achieved from silicate electrolyte was proved to be amorphous. Both kinds of coatings showed coarse and porous surface. The Fe₃O₄ coatings obtained in carbonate electrolyte showed a high bonding strength to the substrate up to 20 ± 2 MPa and the value was 15 ± 2 MPa for the amorphous coatings obtained in carbonate electrolyte. The micro hardness of the amorphous coating and the Fe₃O₄ coating was 1001 Hv and 1413 Hv, respectively, which was more than two and three times as that of the Q235 alloy substrate (415 Hv). The friction coefficient exhibited by amorphous coating and Fe₃O₄ coating was 0.13 and 0.11, respectively, both lower than the uncoated Q235 substrate which ranged from 0.17 to 0.35.     

Microstructure and properties of Ni-Co/nano-Al2O3 composite coatings by pulse reversal current electrodeposition

Ni-Co/nano-Al₂O₃ (Ni-Co/Al₂O₃) composite coatings were prepared under pulse reversal current (PRC) and direct current (dc) methods respectively. The microstructure of coatings was characterized by means of XRD, SEM and TEM. Both the Ni-Co alloy and composite coatings exhibit single phase of Ni matrix with face-centered cubic (fcc) crystal structure, and the crystal orientation of the Ni-Co/Al₂O₃ composite coating was transformed from crystal face (2 0 0) to (1 1 1) compared with alloy coatings. The hardness, anti-wear property and macro-residual stress were also investigated. The results showed that the microstructure and performance of the coatings were greatly affected by Al₂O₃ content and the electrodeposition methods. With the increasing of Al₂O₃ content, the hardness and wear resistance of the composite coatings enhanced. The PRC composite coatings exhibited compact surface, high hardness, better wear resistance and lower macro-residual stress compared with that of the dc composite coatings.     

Nanolayered multilayer coatings of CrN/CrAlN prepared by reactive DC magnetron sputtering

Single-phase CrN and CrAlN coatings were deposited on silicon and mild steel substrates using a reactive DC magnetron sputtering system. The structural characterization of the coatings was done using X-ray diffraction (XRD). The XRD data showed that both the CrN and CrAlN coatings exhibited B1 NaCl structure with a prominent reflection along (2 0 0) plane. The bonding structure of the coatings was characterized by X-ray photoelectron spectroscopy and the surface morphology of the coatings was studied using atomic force microscopy. Subsequently, nanolayered CrN/CrAlN multilayer coatings with a total thickness of approximately 1 μm were deposited on silicon substrates at different modulation wavelengths (Λ). The XRD data showed that all the multilayer coatings were textured along {2 0 0}. The CrN/CrAlN multilayer coatings exhibited a maximum nanoindentation hardness of 3125 kg/mm² at a modulation wavelength of 72 Å, whereas single layer CrN and CrAlN deposited under similar conditions exhibited hardness values of 2375 and 2800 kg/mm², respectively. Structural changes as a result of heating of the multilayer coatings in air (400-800 °C) were characterized using XRD and micro-Raman spectroscopy. The XRD data showed that the multilayer coatings were stable up to a temperature of 650 °C and peaks pertaining to Cr₂O₃ started appearing at 700 °C. These results were confirmed by micro-Raman spectroscopy. Nanoindentation measurements performed on the heat-treated coatings revealed that the multilayer coatings retained hardness as high as 2250 kg/mm² after annealing up to a temperature of 600 °C.     

Preparation and properties of electroless Ni-P-SiO2 composite coatings

Dispersible SiO₂ nanoparticles were co-deposited with electroless Ni-P coating onto AISI-1045 steel substrates in the absence of any surfactants in plating bath. The resulting Ni-P/nano-SiO₂ composite coatings were heat-treated for 1 h at 200 °C, 400 °C, and 600 °C, respectively. The hardness and wear resistance of the heat-treated composite coatings were measured. Moreover, the structural changes of the composite coatings before and after heat treatment were investigated by means of X-ray diffraction (XRD), while their elemental composition and morphology were analyzed using an energy dispersive spectrometer (EDS) and a scanning electron microscope (SEM). Results show that co-deposited SiO₂ particles contributed to increase the hardness and wear resistance of electroless Ni-P coating, and the composite coating heat-treated at about 400 °C had the maximum hardness and wear resistance.     

Microstructure and friction and wear behavior of laser boronizing composite coatings on titanium substrate

Three kinds of laser boronizing composite coatings were in situ synthesized on Ti substrate by using powders of B, BN and B₄C as starting materials. Microstructures of the laser boronizing composite coatings were investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM); and their worn surface morphologies were also observed by using SEM. Moreover, the friction and wear behavior of the boronizing composite coatings under dry sliding condition were evaluated using a UMT-2MT friction and wear tester. It was found that all the three types of laser boronizing composite coatings had higher microhardness and better wear resistance than pure Ti substrate; and their microstructure and wear resistance varied with varying pre-placed powders of B, BN, and B₄C. Under the same dry sliding test conditions, the wear resistance of the three kinds of laser boronizing composite coatings, i.e., sample 1 prepared from pre-placed B, sample 2 obtained from pre-placed BN, and sample 3 fabricated from pre-placed B₄C, is ranked in an order of sample 1 > sample 2 > sample 3, which, surprisingly, well conforms to their order of hardness and friction coefficients.     

Effect of the dispersibility of ZrO2 nanoparticles in Ni-ZrO2 electroplated nanocomposite coatings on the mechanical properties of nanocomposite coatings

ZrO₂ nanoparticles was uniformly co-deposited into a nickel matrix by electroplating of nickel from a Watts bath containing particles in suspension which were monodispersed with dispersant under DC electrodeposition condition. It was found that morphology, orientation and hardness of the nanocomposite coatings with monodispersed ZrO₂ nanoparticles had lots of difference from the nanocomposite coatings with agglomerated ZrO₂ nanoparticles and pure nickel coatings. Especially, the result of hardness showed that only a very low volume percent (less than 1 wt.%) of monodispered ZrO₂ nanoparticles in Ni-ZrO₂ nanocomposite coatings would result in higher hardness of the coatings. The hardness of Ni-ZrO₂ nanocomposite coatings with monodispersed and agglomerated ZrO₂ nanoparticles were 529 and 393 HV, respectively. The hardness value of the former composite coatings was over 1.3 times higher than that of the later. All these composite coatings were two-three times higher than that of pure nickel plating (207 HV) prepared under the same condition. The strengthening mechanisms of the Ni-ZrO₂ nanocomposite coatings based on a combination of grain refinement strengthening from nickel matrix grain refining and dispersion strengthening from dispersion state of ZrO₂ nanoparticles in the coatings.     

The effects of Si3N4 interlayer on the thermal stability and hardness of Ti/TiNx (x = 0.5-1) nanolayered coatings

The polycrystalline Ti/TiN_x multilayer films were deposited by magnetron sputtering, and the as-deposited multilayer coatings were annealed at 500-800 °C for 2-4 h in vacuum. We investigated the effects of annealing temperature and annealing time on the microstructural, interfacial, and mechanical properties of the polycrystalline Ti/TiN_x multilayer films. It was found that the hardness increased with annealing temperature. This hardness enhancement was probably caused by the preferred crystalline orientation TiN(1 1 1). The X-ray reflectivity measurements showed that the layer structure of the coatings could be maintained after annealing at 500 °C and the addition of the Si₃N₄ interlayer to Ti/TiN_x multilayer could improve the thermal stability to 800 °C.     

A study of TaxC1−x coatings deposited on biomedical 316L stainless steel by radio-frequency magnetron sputtering

In this paper, Ta_xC_1−x coatings were deposited on 316L stainless steel (316L SS) by radio-frequency (RF) magnetron sputtering at various substrate temperatures (T_s) in order to improve its corrosion resistance and hemocompatibility. XRD results indicated that T_s could significantly change the microstructure of Ta_xC_1−x coatings. When T_s was <150 °C, the Ta_xC_1−x coatings were in amorphous condition, whereas when T_s was ≥150 °C, TaC phase was formed, exhibiting in the form of particulates with the crystallite sizes of about 15-25 nm (T_s = 300 °C). Atomic force microscope (AFM) results showed that with the increase of T_s, the root-mean-square (RMS) values of the Ta_xC_1−x coatings decreased. The nano-indentation experiments indicated that the Ta_xC_1−x coating deposited at 300 °C had a higher hardness and modulus. The scratch test results demonstrated that Ta_xC_1−x coatings deposited above 150 °C exhibited good adhesion performance. Tribology tests results demonstrated that Ta_xC_1−x coatings exhibited excellent wear resistance. The results of potentiodynamic polarization showed that the corrosion resistance of the 316L SS was improved significantly because of the deposited Ta_xC_1−x coatings. The platelet adhesion test results indicated that the Ta_xC_1−x coatings deposited at T_s of 150 °C and 300 °C possessed better hemocompatibility than the coating deposited at T_s of 25 °C. Additionally, the hemocompatibility of the Ta_xC_1−x coating on the 316L SS was found to be influenced by its surface roughness, hydrophilicity and the surface energy.     

Microstructure and mechanical properties of alumina coatings prepared by double glow plasma technique

Low-temperature growth (600 °C) of α-Al₂O₃ coatings on the stainless steel substrate by double glow plasma technique was achieved. The compositions and microstructures of the coatings prepared at different oxygen flow rates were characterized, respectively, by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectrometry. A phenomenological mechanism for the formation of the Al₂O₃ ceramic coatings during the oxidation process was proposed on the basis of the experimental results. It was obvious that the oxygen flow rates had a great effect on the surface structure of the prepared Al₂O₃ coatings. The dense and smooth Al₂O₃ coatings were prepared at the oxygen flow rate of 15 sccm. In addition, the correlations between the mechanical properties of Al₂O₃ coating and oxygen flow rates were also discussed. The coating prepared at 15 sccm oxygen flow rate exhibited the best mechanical properties with a maximum hardness of 31 GPa and elastic modulus of 321 GPa. The corresponding critical load of scratch adherence for this sample was 47 N.     

Electrochemically assisted co-deposition of calcium phosphate/collagen coatings on carbon/carbon composites

Calcium phosphate (CaP)/collagen coatings were prepared on the surface of carbon/carbon (C/C) composites by electrochemically assisted co-deposition technique. The effects of collagen concentration in the electrolyte on morphology, structure and composition of the coatings were systematically investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The adhesive strength of the coatings was also evaluated by scratch tests and tensile bond tests. It was demonstrated that the coatings of three-dimensional collagen network structure was formed on the C/C composites from the electrolyte containing collagen. The surface of the collagen network was covered by uniform CaP aggregates. The coatings were actually composites of CaP and collagen. Hydroxyapatite (HA) was a favorable composition in the coatings with the increase of the collagen concentration in the electrolyte. The formed collagen network increased the cohesive and adhesive strength of the coatings. The adhesive strength between the coatings and substrates increased as the collagen concentration in the electrolyte increased. The coatings prepared at the collagen concentration of 500 mg/L in the electrolyte were not scraped off until the applied load reached 32.0 ± 2.2 N and the average tensile adhesive strength of the coatings was 4.83 ± 0.71 MPa. After C/C coated with composite coatings (500 mg/L) being immersed in a 10⁻³ M Ca (OH)₂ solution at 30-33 °C for 96 h, nano-structured HA/collagen coatings similar to the natural human bone were obtained on the C/C.     

Preparation of ZrC nano-particles reinforced amorphous carbon composite coating by atmospheric pressure chemical vapor deposition

To eliminate cracks caused by thermal expansion mismatch between ZrC coating and carbon-carbon composites, a kind of ZrC/C composite coating was designed as an interlayer. The atmospheric pressure chemical vapor deposition was used as a method to achieve co-deposition of ZrC and C from ZrCl₄-C₃H₆-H₂-Ar source. Zirconium tetrachloride (ZrCl₄) powder carrier was especially made to control accurately the flow rate. The microstructure of ZrC/C composite coating was studied using analytical techniques. ZrC/C coating shows same morphology as pyrolytic carbon. Transmission electron microscopy (TEM) shows ZrC grains with size of 10-50 nm embed in turbostratic carbon. The formation mechanism is that the growth of ZrC crystals was inhibited by surrounding pyrolytic carbon and kept as nano-particles. Fracture morphologies imply good combination between coating and substrate. The ZrC crystals have stoichiometric proportion near 1, with good crystalline but no clear preferred orientation while pyrolytic carbon is amorphous. The heating-up oxidation of ZrC/C coating shows 11.58 wt.% loss. It can be calculated that the coating consists of 74.04 wt.% ZrC and 25.96 wt.% pyrolytic carbon. The average density of the composite coating is 5.892 g/cm³ by Archimedes’ principle.     

Preparation and ablation properties of ZrC-SiC coating for carbon/carbon composites by solid phase infiltration

A novel ZrC-SiC coating was prepared on carbon/carbon (C/C) composites surface by solid phase infiltration and the ablation properties of the ZrC-SiC coated C/C composites under oxyacetylene flame were studied. The results show that the coating prepared on the condition of optimum process parameters exhibits dense surface and outstanding anti-ablation ability. After ablation for 20 s, the mass ablation rates of the coated C/C composites can be lowered to 2.36 × 10⁻³ g/s, 37.1% reduction compared with uncoated C/C composites. The oxide layer composed of ZrO₂ and SiO₂ acts as oxygen diffusion barrier and the evaporation of ZrO₂ and SiO₂ absorbs a great amount of heat from the flame and reduces the erosive attack on the coating.     

Ni-Co-TiO2 nanocomposite coating prepared by pulse and pulse reversal methods using acetate bath

Ni-Co/nano TiO₂ (Ni-Co-TiO₂) composite coatings were prepared under pulse current and pulse reverse current methods using acetate bath. The microstructure and corrosion resistance of the coatings were characterized by means of XRD, SEM and EIS. Both the Ni-Co alloy and composite coatings exhibited single phase of Ni matrix with face centered cubic (fcc) crystal structure. The crystal orientation of the Ni-Co-TiO₂ composite coating was transformed from crystal face (2 0 0) to (1 1 1) compared with Ni-Co alloy coatings. The results showed that the microstructure and performances of the coatings were greatly affected by TiO₂ content on the deposits prepared by PC and PRC methods. The microhardness and corrosion resistance were enhanced in the optimum percentage of TiO₂ composite coatings. The PRC composite coatings were exhibited from compact surface, higher microhardness and good corrosion resistance compared with that of the PC composite coating.     

Effects of CPII implantation on the characteristics of diamond-like carbon films

A diamond-like carbon film (DLC) was successfully synthesized using a hybrid PVD process, involving a filter arc deposition source (FAD) and a carbon plasma ion implanter (CPII). A quarter-torus plasma duct filter markedly reduced the density of the macro-particles. Graphite targets were used in FAD. Large electron and ion energies generated from the plasma duct facilitate the activation of carbon plasma and the deposition of high-quality DLC films. M2 tool steel was pre-implanted with 45 kV carbon ions before the DLC was deposited to enhance the adhesive and surface properties of the film. The ion mixing effect, the induction of residual stress and the phase transformation at the interface were significantly improved. The hardness of the DLC increased to 47.7 GPa and 56.5 GPa, and the wear life was prolonged to over 70 km with implantation fluences of 1 × 10¹⁷ ions/cm² and 2 × 10¹⁷ ions/cm², respectively.     

Deposition of TiSiN coatings by arc ion plating process

Titanium silicon nitride (TiSiN) thin films were deposited on tungsten cemented carbide tools by cathode arc ion plating (AIP) process using alloy TiSi targets. The effects of silicon addition and negative substrate bias on the development of the textures of films were studied systematically by varying the bias voltage from −20 to −200 V. The structural features of the films were investigated in detail using X-ray diffraction. The effect of the texture on such mechanical properties as hardness and adhesion of the films was also studied. A maximum hardness of 42 GPa was obtained at a DC substrate bias of −150 V. The characteristics of TiSiN thin films exhibited excellent adhesion of over 150 N. The cutting performance of end-mills and drillers was evaluated by milling and drilling of highly hardened material under high-speed cutting conditions. The results reveal that cutting tools with TiSiN coatings markedly outperformed those with TiN coatings, and the uncoated cutting tools. TiSiN coating increased the cutting lifetime to seven times that of the uncoated one.