Structure and characteristics of amorphous (Ti,Si)–C:H films deposited by reactive magnetron sputtering

The hydrogenated amorphous carbon films doped with Ti and Si ((Ti,Si)–C:H) were deposited on silicon substrates using reactive magnetron sputtering Ti₈₀Si₂₀ composite target in an argon and methane gas mixture. The structures of the films were analyzed by X-ray photoelectron spectroscopy and Visible Raman spectroscopy. The morphologies were observed by atomic force microscope. The friction coefficients of the films were tested on the ball-on-disc tribometer. The results indicate that the sp³/sp² ratios in the films can be varied from 0.18 to 0.63 by changing Ti and Si contents at various CH₄ flow rates. The surface of the films becomes smoother and more compact as the CH₄ flow rate increases. The lowest friction coefficient is as low as 0.0139 for the film with Ti of 4.5 at.% and Si of 1.0 at.%. Especially, the film exhibits a superlow value (μ < 0.01) under ambient air with 40% relative humidity in friction process. The superlow friction coefficient in ambient air may be, attributable to synergistic effects of a combination of Ti and Si in the film.     

Wear-resistant Ti–Al–Ni–C–N coatings produced by magnetron sputtering of SHS-targets in the DC and HIPIMS modes

The hard wear-resistant nanocomposite Ti–Al–Ni–C–N coatings were deposited by direct current magnetron sputtering (DCMS) and high power impulse magnetron sputtering (HIPIMS) in the Ar, Ar+15%N_2, and Ar+25%N₂ atmospheres. The structure of coatings was analyzed using the X-ray diffraction analysis, glow discharge optical emission spectroscopy, and scanning electron microscopy. Mechanical and tribological properties were measured using the nanoindentation and scratch testing as well as by tribological testing using the “pin-on-disc” scheme. Electrochemical corrosion resistance and oxidation resistance of coatings were investigated. The results suggest that the coatings are based on the FCC phases TiCN and Ni₃Al with crystallites size ~3 and ~15 nm, correspondingly. DCMS coatings with optimal composition were characterized by hardness 34 GPa, stable friction coefficient <0.26 and wear rate <5 × 10^-6 mm³N^-1m^-1. Application of HIPIMS mode allowed the increase of adhesion strength, tribological properties and corrosion resistance of coatings.     

Comprehensive study on corrosion protection properties of Al2O3, Cr2O3 and Al2O3–Cr2O3 ceramic coatings deposited by plasma spraying on carbon steel

In this study, individual Al₂O₃ and Cr₂O₃ coatings and Cr₂O₃-25, 50, 75 wt% Al₂O₃ composite coatings were applied on carbon steel by atmospheric plasma spraying method. Corrosion experiments were performed on as-sprayed and epoxy resin sealed coatings including potentiodynamic polarization, electrochemical impedance spectroscopy and long-term immersion in 3.5 wt% NaCl solution. Phase composition and microstructure of the coatings were investigated by x-ray diffraction, optical microscopy and scanning electron microscopy, before and after the corrosion experiment. The results showed that the Cr₂O₃ coating exhibited the best corrosion resistance, due to the densest microstructure and highest adhesion strength. The Cr₂O₃-25 wt% Al₂O₃ coating had the highest interconnected porosities and thus had the least corrosion resistance compared to other coatings. In general, the as-sprayed coatings induced a maximum increase of 3.93 times the polarization resistance (R_p) in the polarization experiment and a 3.5 times increase in the charge transfer resistance (R_ct) in the EIS experiment, which was not significant. Stresses caused by increased volume of corrosion products in the coating-substrate interface resulted in the spallation of Cr₂O₃-25, 50 wt% Al₂O₃ coatings from the substrate over long-term of immersion. The adhesion strength of the coatings was a determining criterion for the long-term durability of the coatings. The sealing treatment resulted in a significant increase in R_p and R_ct.     

Microstructure,mechanical and tribological properties of Ti–B–C–N films prepared by reactive magnetron sputtering

Quaternary Ti–B–C–N thin films are deposited on high-speed steel substrates by the reactive magnetron sputtering (RMS) technique. The microstructure, mechanical and tribological properties of Ti–B–C–N films with different carbon contents (from 28.9 at.% to 54.2 at.%) are explored systematically. The microstructure of Ti–B–C–N films deposited by RMS is consisted mainly of Ti(C, N) nano-crystals embedded into an amorphous matrix of a-C/a-CN/a-BN/a-BC. As the carbon content increases, the crystalline size of the films diminishes, but the hardness linearly increases from 14 GPa to 26 GPa. The friction coefficient of the films sliding against steel GCr15 balls in air decreases with the increase of carbon content, which shows that Ti–B–C–N films with both higher hardness and lower friction coefficient can be obtained by means of increasing the carbon concentration in the films.     

Structural and chemical analysis of amorphous B–N–C thin films deposited by RF sputtering

Ternary Boron–Nitrogen–Carbon (B–N–C) thin films were deposited, onto silicon substrates, by reactive radio frequency (RF) sputtering from a boron carbide (B₄C) target in a gas mixture of nitrogen and argon. The influence of the RF power (P_RF) on the structure and the chemical composition of these films are studied by Fourier transform Infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) measurements. The two techniques reveal the presence of B, C and N atoms in the deposited films. The presence of nitrogen in the atmosphere of the deposition chamber produces ternary B–N–C films composed mainly with a mixture of B–N and CN bonds as revealed by these techniques. The boron content increases while carbon and nitrogen contents decrease with P_RF. The higher proportion of boron atoms produced a strong contribution of the boron nitride in the final compound B–N–C films.     

Surface properties and biological behaviour of Si-DLC coatings fabricated by a multi-target DC–RF magnetron sputtering method for medical applications

The Si-incorporated diamond-like carbon (DLC) coatings deposited on AISI 316 LVM medical steel using magnetron sputtering method are currently not widely described in the literature, especially in terms of their biological response. Therefore, in this study both the haemocompatibility and cytotoxicity, as well as the surface properties of the Si-DLC films prepared by multi-target DC–RF magnetron sputtering were assessed. According to the XPS analysis the content of Si in the obtained coatings varied from ~ 4 at.% up to ~ 16 at.%. SEM investigations showed that the surface of the Si-DLC coatings is uniform and homogenous without any local defects. The surface energy measurements and FTIR analysis demonstrated that hydrophilicity and polarity of the examined surfaces changes with the varying Si-concentration. The evaluation of biological response towards the deposited coatings revealed that the increasing concentration of Si suppresses the platelet adhesion and decreases their activation level. Moreover, the results of the live/dead test indicated that the examined Si-DLC coatings are not cytotoxic, regardless of the Si concentration. Only a slight decrease in the endothelial cells' proliferation was observed with the growing Si content. Hence, it was concluded that the Si-DLC layer with the Si concentration ~ 16 at.% would be the most bio- and haemocompatible.     

Improvement of interface between Al and short carbon fibers by α-Al2O3 coatings deposited by sol–gel technology

This paper describes an investigation on an improvement of the interface between Al and short carbon fibers (SCFs) with α-Al₂O₃ coating by sol–gel technology. The composites of Al/uncoated SCFs and Al/α-Al₂O₃-**coated SCFs were fabricated successfully by vacuum press infiltration. The formation of α-Al₂O₃ coating during calcination was analysed by Fourier transform infrared (FTIR) and X-ray diffraction (XRD). Scanning electron microscopy (SEM), energy-dispersive analysis of X-ray (EDAX) and transmission electron microscope (TEM) were used to observe the coated SCFs and the interface of composites. The results showed that the average thickness of the α-Al₂O₃ coating was about 200–250 nm and the formation of Al₄C₃ at the interface between Al matrix and SCFs was controlled by the α-Al₂O₃ coatings.     

Effect of bias voltage on microstructure and phase evolution of Cr–Mo–N coatings by an arc bonded sputter system

Cr–Mo–N hard coatings were deposited on SKD11 and silicon wafer substrates at various substrate bias voltages by hybrid PVD consisting of arc ion plating and unbalanced magnetron sputtering. The results showed that the microstructure, phase evolution, and mechanical properties of the coatings were significantly altered at the different substrate bias voltage ranging from 0 to −400 V. The X-ray diffraction analysis results revealed that most of the diffraction peaks originated from the Cr–N phase. These peaks were observed at lower positions with no substrate bias and were shifted to higher positions with increasing substrate bias power. The preferred orientation of the (200) plane became dominant accompanying the (220) plane as the bias voltage was increased. Maximum hardness of approximately 30 GPa was obtained at a bias voltage of −200 V. Additionally, wear test results reveal that the lowest coefficient of friction, between 0.4 and 0.5, was obtained from the Cr–Mo–N film formed at a bias voltage of −200 V.     

Synthesis,characterization, and infrared-emissivity study of Ni–P–CB nanocomposite coatings by electroless process

The Ni–P–CB (carbon black) nanocomposite coatings have been successfully deposited on an ABS plastic matrix via electroless plating process. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) spectrometry techniques were employed to examine the surface morphology and structure of the as-plated coating. Energy dispersive spectroscopy (EDS) was adopted to obtain the component analysis of the Ni–P–CB composite coating, and the infrared emissivity of the coating was determined by the IRE-I Infrared Emissometer. SEM and XRD results indicated that the nanoparticles were dispersed homogeneously in the Ni–P coating; the result of EDS showed that the increased rate of CB content is in correspondence with its concentration. In the case that CB concentration is lower than 4 g/L, the increase rate is sharp, whereas when the concentration is higher than 4 g/L, the increase rate is reduced significantly. Furthermore, study of infrared emissivity shows that the nanocomposite coatings possessed low emissivity value. A comparison of the infrared emissivity dependence on surface resistivity obtained from the analysis of the experimental results and those calculated using the Hagen–Rubens relation indicates that the Hagen–Rubens relation is good for modeling the infrared emissivity of the Ni–P–CB nanocomposite coatings.     

Direct synthesis of NiAl intermetallic matrix composite with TiC and Al2O3 reinforcements by mechanical alloying of NiO–Al–Ti–C powder mixture

NiAl intermetallic matrix nanocomposite with TiC and Al₂O₃ was directly fabricated by mechanical alloying of NiO, Al, graphite, and Ti as the starting powder mixture. The phase and morphological evaluations during mechanical alloying were characterized by X-ray diffraction and scanning electron microscopy equipped by energy-dispersive X-ray spectroscopy, respectively. The thermal behavior of the 40 h milled powder was obtained via differential thermal analysis. Followed by 10 h milling, no new phases were formed; but after 20 h milling, Al reduced a fraction of NiO, NiAl and Al₂O₃ were formed, and the released energy promoted TiC formation. When milling time reached 40 h, the remained raw materials were completely consumed and NiAl/TiC–Al₂O₃ nanocomposite was formed. Therefore, the main stage to synthesize NiAl/TiC–Al₂O₃ nanocomposite was the reduction of NiO by Al. The microstructural evaluation revealed formation of a homogeneously distributed composite and thermal analysis showed that the synthesized product was stable.     

Dielectric properties of composition spread SiO2–Al2O3 mixed phase thin films deposited at room temperature by off-axis RF magnetron sputtering

The dielectric properties of composition spread SiO₂–Al₂O₃ thin films deposited by off-axis radio-frequency magnetron sputtering at room temperature were explored to obtain optimized compositions, which have low dielectric constants and losses. The specific points (compositions) showing superior dielectric properties of low dielectric constants (8.13 and 9.12) and losses (tanδ ～0.02) at 1 MHz were found in area of the distance of 25.0 mm (Al₂Si₃O₈) and 42 mm (Al_2.4Si₃O₈) apart from SiO₂ target side in 75 mm × 25 mm sized Pt/Ti/SiO₂/Si(1 0 0) substrates, respectively. The specific thin films were amorphous phase and the compositions were Al₂Si₃O₈ (k ～8.13) and Al_2.4Si₃O₈ (k ～9.12).     

Improving the tribological properties of plasma sprayed NiAl–Bi2O3–Ag–Cr2O3 composite coatings by hot isostatic pressing

In this study, the hot isostatic pressing (HIP) process was adopted to enhance the tribological response of plasma-sprayed NiAl–Bi₂O₃–Ag–Cr₂O₃ coatings under different temperature conditions. The HIP process was performed at a temperature of 800 °C, under a pressure of 100 MPa using argon gas. When compared with as-sprayed NiAl–Bi₂O₃–Ag–Cr₂O₃ composite coatings, the results revealed that the post-HIP process greatly reduced the porosity to a sufficiently low level of 2.7%, and led to a significant transformation from the splat lamellar to composition homogeneity across the entire coating. As highlighted in the hot isostatically pressed (HIPed) coating, more NiBi intermetallic compounds emerged. The mechanical hardness and adhesive strength increased considerably by 15.9% and 22.7%, respectively. The HIPed coating exhibited improved running stability in friction when exposed to different temperatures. In particular, the wear resistance increased significantly by one level of magnitude at the temperature range of room temperature (25 °C) to 400 °C, compared to the as-sprayed composite coating. This was attributed to the presence of the NiBi intermetallic compound and structural restoration after the HIP process. A protective tribo-layer was always present under alternating temperature conditions, and this allowed for continuous inhibition of wear. The mechanical evolution of the tribo-layer was further determined to clarify its effect on the resulting tribological behavior of the HIPed NiAl–Bi₂O₃–Ag–Cr₂O₃ coatings.     

Fabrication and properties of 2D C/C–ZrB2–ZrC–SiC composites by hybrid precursor infiltration and pyrolysis

Abstract

Two dimensional C/C–ZrB₂–ZrC–SiC composites were fabricated through precursor infiltration and pyrolysis process using a mixture of polycarbosilane and ZrB₂ precursor and ZrC precursor as the impregnant. The microstructures, mechanical properties and ablation properties of the composites were investigated. The results showed that the homogeneity of the composite improved on using novel precursors that can dissolve with polycarbosilane through the formation of nanocomposite matrix. The flexural strength and fracture toughness first increased and then decreased on increasing the pyrocarbon content in the composite. Compared with the C/C–SiC composite, the ablation resistance of C/C–ZrB₂–ZrC–SiC composite was greatly enhanced. The mass loss rate and linear recession rate exposed to the plasma torch were 1?7 mg/s and 1?8 μm/s, respectively. The formation of a ZrO₂–SiO₂ glassy layer on the surface significantly contributed to the excellent ablative property of the composite.     

Effects of air annealing treatments on the microstructure,components, and mechanical properties of magnetron sputtered Al2O3–Cr2O3–ZrO2 composite coatings

To investigate the effects of air annealing on the microstructure, components, and mechanical properties of ceramic composite coatings, Al₂O₃–Cr₂O₃–ZrO₂ composite coatings were prepared on silicon substrate using radio frequency magnetron sputtering at room temperature, and then air-annealed in a temperature range of 450–850 °C for 30 min. The results indicated that the phase-structure and superficial characteristics, including morphology and surface roughness, were not visibly altered in the annealed coatings up to 600 °C; the elemental component distributions remained uniform. The improvement in the mechanical properties was attributed to the growth of oxide grains. There were no significant changes in the components of Al, Cr, Zr, and O in the annealed coatings. However, an increase in the Cr component and a decrease in the Zr component occurred on the coating surface; the overall structure of the composite coatings possessed a favorable heat resistance. Upon annealing at 750 °C, the thermally-driven formation of uniform and refined nanoparticles on the coating surface was responsible for the effective enhancement of the mechanical properties. Furthermore, annealing at 850 °C induced the enlargement of the precipitated Cr₂O₃ nanoparticles and the generation of micro-defects, resulting in a drastic morphological evolution, an evident increase in the surface roughness, and a significant decrease in the mechanical properties. This study provides new perspectives on designing novel thermal barrier coatings and understanding the role of high temperature air annealing on the microstructural transformation.     

Characterization and adhesion strength study of detonation-sprayed MoB–CoCr alloy coatings on 2Cr13 stainless steel substrate

A novel MoB–CoCr alloy coating was deposited onto stainless steel (2Cr13) substrate using a detonation gun (D-gun) spraying technique. Microstructures of the powder and coating were investigated by X-ray diffraction (XRD), scanning election microscopy (SEM), and transmission electron microscopy (TEM), and a quantitative determination of the adhesion strength of the coating was calculated by combination of modified four-point bending (4PB) test and finite element analysis (FEA) simulation. The results show that the coating mainly consists of ternary transition metal boride matrix phases (CoMo₂B₂, MoCoB) and binary borides (MoB and CrB). Nanocrystalline grains with a size of 50–100 nm were observed in the coating. The average energy release rate and phase angle are 191.2 J m⁻² and 41.7o, respectively, which show strong bond strength compared to other reported values.     

Development and protection evaluation of two new,advanced ceramic composite thermal spray coatings,Al2O3–40TiO2 and Cr3C2–20NiCr on carbon steel petroleum oil piping

Carbon steel is the most commonly used material in the petroleum industry owing to its high performance and relatively low cost compared with highly alloyed materials. The corrosion resistance of carbon steel in aqueous solutions is dependent on the surface layer created on carbon steel. This layer often consists of siderite (FeCO₃) and cementite (Fe₃C), but it is neither compact nor dense. To improve the carbon steel surface resistance against corrosion and wear, a compact and dense layer can be deposited onto the surface by thermal spray coating. In this research, Al₂O₃–40TiO₂ and Cr₃C₂–20NiCr were deposited onto mechanical part surfaces by HVOF spray technique. The present study describes and compares the electrochemical behavior of carbon steel, Cr₃C₂–20NiCr and Al₂O₃–40TiO₂ in 3.5% NaCl using open-circuit potential measurement (OCP) and electrochemical impedance microscopy (EIS) for 36 days. The tribological and mechanical properties are also investigated using a tribometer (pin-on-disc). The results indicate that these chemical composition coatings facilitated significant anti-corrosion and anti-wear improvement. However, the samples coated with Al₂O₃–40TiO₂ exhibited the lowest corrosion rate. In terms of wear performance, both coated samples displayed similar behavior under different loads. Scanning electron microscopy (SEM) showed the distinctive microstructure of the HVOF-sprayed samples before and after corrosion and wear testing.     

Effect of silicon/graphite ratio and temperature on oxidation protective properties of SiC/ZrB2–SiC coatings prepared by pack cementation

To investigate the silicon/graphite ratio and temperature on preparation and properties of ZrB₂–SiC coatings, ZrB₂, silicon, and graphite powders were used as pack powders to prepare ZrB₂–SiC coatings on SiC coated graphite samples at different temperatures by pack cementation method. The composition, microstructure, thermal shock, and oxidation resistance of these coatings were characterized and assessed. High silicon/graphite ratio (in this case, 2) did not guarantee higher coating density, instead could be harmful to coating formation and led to the lump of pack powders, especially at temperatures of 2100 and 2200 °C. But residual silicon in the coating is beneficial for high density and oxidation protection ability. The SiC/ZrB₂–SiC (ZS50-2) coating prepared at 2000 °C showed excellent oxidation protective ability, owing to the residual silicon in the coating and dense coating structure. The weight loss of ZS50-2 after 15 thermal shocks between 1500 °C and room temperature, and oxidation for 19 h at 1500 °C are 6.5% and 2.9%, respectively.     

Synthesis of ZrB2–ZrC hybrid powders via boro-carbothermal reduction of ZrO2 by B4C and carbon black

ZrB₂–ZrC hybrid powders were synthesized by a novel two-step reduction on basis of ZrO₂ + B₄C + C→ ZrC + ZrB₂ + CO reaction in Ar atmosphere, using ZrO₂, B₄C, and carbon black powders as starting materials. Thermodynamics of relevant reactions were evaluated. Effects of excess additions of B₄C and C on phase constituents were investigated. Morphology and chemistry of the powder products were characterized by scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS) and transmission electron microscopy (TEM). The results showed that ZrB₂–ZrC hybrid powders with no obvious impurity content could be obtained after heating at 1350 °C for 1 h followed by further reaction at 1700 °C for 1 h with 16 wt% B₄C + 8 wt% C excess addition. Relative contents of the ZrB₂: ZrC phase in the product powders could be conveniently regulated by varying the B₄C and C content in the starting compositions. The resultant powders had good oxidation resistance with an oxidation activation energy value of 433 kJ/mol. Good sinterability of the powder products was demonstrated by hot pressing at 1950 °C for 60min under 30 MPa pressure, which resulted in fully dense ZrB₂–ZrC composite ceramics with Vickers hardness value larger than 18.3 ± 0.6 GPa.     

Influence of layer number and sintering temperature on microstructural,tribological, and corrosion behavior of Al2O3–TiO2 multilayer coatings

The effects of layer number (2, 4, and 6-layer) and sintering temperature (800, 900, 1000, and 1100 °C) on the microstructure, wear, and corrosion properties of Al₂O₃–TiO₂ multilayer coatings deposited on 316L stainless steel plates using the sol-gel dip coating technique were investigated. The wear characteristics were measured through ball-on-disc type dry sliding tests using an Al₂O₃ ball under a 1 N load, whereas the corrosion features were determined by potentiodynamic polarization tests conducted in a 3.5 wt% NaCl solution. Anatase, rutile, α-Al₂O₃, and γ-Al₂O₃ phases were obtained in the hybrid coatings, depending on the sintering temperatures. However, at 1100 °C, the coating did not adhere well to the substrate due to passive oxide film formation on the 316L plate, leading to spalling. Besides, the surface homogeneity deteriorated in the 6-layer coated sample due to higher organic removal and residual stresses. The corrosion rate decreased with the increasing number of layers, but the sensitivity to corrosion varied due to changes in surface properties. The 4-layer coated sample sintered at 1000 °C achieved the highest wear strength (improved by up to 71.1%) and corrosion resistance (increased by up to 90.4%) due to its decreased porosity and homogeneously distributed finer particles.