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.     

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.     

Preparation and characterization of hydroxyapatite coating by magnetron sputtering on Mg–Zn–Ag alloys for orthopaedic trauma implants

The aim of the present paper was to evaluate the effect of hydroxyapatite coatings on the two types of Mg–Zn–Ag alloys as a possible solution to control magnesium alloy degradation. The coatings were prepared by the radio frequency magnetron sputtering method at a deposition temperature of 300 °C. To perform this evaluation, the coated alloys were immersed in a simulated body fluid solution at body temperature (37 ± 0.5 °C) to determine the corrosion resistance through electrochemical and immersion tests. Moreover, the investigation also consisted of the evaluation of microchemical, mechanical, and morphological properties. The deposition temperature of 300 °C was enough to obtain a crystalline hydroxyapatite structure with a Ca/P ratio close to the stochiometric one. The adhesion of coatings was not influenced by the nature of Mg–Zn–Ag alloys, so similar values for both coated alloys were found. The results showed that the coating was homogonous deposited on the Mg–Zn–Ag alloys and the corrosion resistance of uncoated magnesium alloys was improved.     

Preparation and characterisation of bioactive hydroxyapatite–silica composite nanopowders via sol–gel method for medical applications

Abstract

Abstract

This study focuses on preparation and characterisation of hydroxyapatite–silica composite nanopowders with different contents of silica. Hydroxyapatite–silica composite nanopowders with 10, 20, 30 and 40?wt‐% silica were prepared using a sol–gel method at 600°C with phosphoric pentoxide and calcium nitrate tetrahydrate as the source of hydroxyapatite, also tetraethylorthosilicate and methyltriethoxisilane as the source of silica. XRD, FTIR, SEM, EDAX and TEM techniques were used for characterisation and evaluation of the phase composition, crystallinity, crystallite size, functional groups, morphology and composition of the products. Dissolution behaviour of the products was evaluated at predetermined time periods by an atomic absorption spectrometer and a pH meter. Results indicated the presence of nanocrystalline hydroxyapatite phase and amorphous silica nanoparticles in composite nanopowders. Also, by increasing the content of silica in composite nanopowders, the crystallite size and crystallinity of hydroxyapatite phase decreased and the Ca ion release rate changed.     

Surface properties and moisture behaviour of pine and heat-treated spruce modified with alkoxysilanes by sol–gel process

The surface morphology and moisture behaviour of pine (Pinus sylvestris) sapwood and heat-treated spruce (Picea abies) deposited with two types of silane-based sol–gel coatings were studied by atomic force microscopy (AFM) and water contact angle measurement. The chemical composition and distribution of sol–gel coatings on wood surfaces were investigated by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The AFM images revealed that the sol–gel coatings applied by spreading covered the fine structure of the wood substrates. The surface roughness analysis of the AFM topographical images indicated that the sol–gel coatings, especially the one with short aliphatic chain, had a tendency to smooth the wood surface. The XPS results confirmed that the sol–gel coatings had successfully deposited onto pine sapwood and heat-treated spruce changing their surface chemistries. ToF-SIMS images showing Si ion distribution on treated surfaces revealed that the coatings fully covered pine sapwood surfaces. The thin coating layers formed on heat-treated spruce surfaces followed the original wood surface structure. The contact angle measurements indicated that the water repellent properties of both pine and heat-treated spruce were improved to certain extent by the sol–gel coatings.     

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).     

Processing and characterization of elastomeric polycaprolactone triol–citrate coatings for biomedical applications

In this paper we describe the synthesis, processing and characterization of a novel elastic polyester coating created by carrying out catalyst-free polyesterification between biocompatible and non-toxic multifunctional reactants, namely polycaprolactone triol and citric acid. The physico-chemical and surface properties of the resulting polyester coatings and films have been investigated. This new material has been characterized by matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-ToF-MS), nuclear magnetic resonance spectroscopy (NMR), Fourier-transform infra-red spectroscopy (FTIR), water-in-air contact angle measurements, scanning electron microscopy (SEM), thermal analysis (DSC), mechanical tests and swelling experiments. The polymer structure, surface properties (morphology and chemistry), mechanical integrity and hydration of the elastomer can be controlled by simple variation of the initial citric acid concentration in the polymer formation. This feature of the novel polyester material presents a significant development in the production of advanced coatings for biomedical applications.     

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.     

Mechanical properties and thermal stability of ambient-cured thick polysiloxane coatings prepared by a sol–gel process of organoalkoxysilanes

Ambient-curable polysiloxane coatings were prepared by pre-hydrolysis/condensation of phenyltrimethoxysilane (PTMS) and dimethyldimethoxysilane (DMDMS) in the presence of ammonia solution and subsequently mixing with aminopropyltriethoxysilane (APS). The mechanical properties of coatings were thoroughly examined at both macro- and micro-level and the thermal stability of coatings was characterized by thermogravimetic analysis, both of which were correlated with coating composition and the hydrolysis/condensation degree of polysiloxane oligomer. It was found that pro-hydrolysis step is essential for fabrication of thick crack-free coatings (18–35 μm). Higher DMDMS molar ratio, more APS dosage and lower hydrolysis/condensation degree of polysiloxane oligomer favor enhancing the hardness. Excellent impact resistance (50 cm kg) of coatings was obtained at 5% and 10% APS dosage, despite of the type and structure of polysiloxane oligomer. Whatever, the best scratch resistance of coatings was attained using the polysiloxane oligomer, prepared at PTMS-to-DMDMS molar ratio of 2:8 and water-to-precursor molar ratio of 1:1, and 5% APS dosage. The polysiloxane coatings exhibit high thermal stability, however, which strongly depends on the coating composition.     

Microstructure and mechanical properties of TiB2–B4C ceramics fabricated by hot-pressing

In this study, TiB₂–B₄C composite ceramics were prepared using Y₂O₃ and Al₂O₃ as the sintering aids. Different contents of B₄C were added to seek promoted comprehensive mechanical properties of the composites. The mixed powders were sintered at 1850 °C under a uniaxial loading of 30 MPa for 2 h via hot-pressing. Through the measurement of XRD, SEM and related mechanical properties, the influence of B₄C content on the microstructure and mechanical properties of TiB₂–B₄C composites ceramics was discussed. The experimental results show that TiB₂–B₄C composite ceramics exhibit excellent mechanical properties, which can be attributed to the dense microstructure and fine grain size. In addition, TiB₂–B₄C composite ceramic shows a relatively high comprehensive properties when the addition amount of B₄C is 20 wt%. The relative density, Vickers hardness, fracture toughness and flexural strength are measured to be 99.61%, 27.63 ± 1.73 GPa, 4.77 ± 0.06 MPa m^1/2, 612.5 ± 28.78 MPa, respectively.     

Dependencies of microstructure and stress on the thickness of GdBa2Cu3O7 ? δ thin films fabricated by RF sputtering

GdBa₂Cu₃O_{7 − δ} (GdBCO) films with different thicknesses from 200 to 2,100 nm are deposited on CeO₂/yttria-stabilized zirconia (YSZ)/CeO₂-buffered Ni-W substrates by radio-frequency magnetron sputtering. Both the X-ray diffraction and scanning electron microscopy analyses reveal that the a-axis grains appear at the upper layers of the films when the thickness reaches to 1,030 nm. The X-ray photoelectron spectroscopy measurement implies that the oxygen content is insufficient in upper layers beyond 1,030 nm for a thicker film. The Williamson-Hall method is used to observe the variation of film stress with increasing thickness of our films. It is found that the highest residual stresses exist in the thinnest film, while the lowest residual stresses exist in the 1,030-nm-thick film. With further increasing film thickness, the film residual stresses increase again. However, the critical current (I_c) of the GdBCO film first shows a nearly linear increase and then shows a more slowly enhancing to a final stagnation as film thickness increases from 200 to 1,030 nm and then to 2,100 nm. It is concluded that the roughness and stress are not the main reasons which cause the slow or no increase in I_c. Also, the thickness dependency of GdBa₂Cu₃O_{7 − δ} films on the I_c is attributed to three main factors: a-axis grains, gaps between a-axis grains, and oxygen deficiency for the upper layers of a thick film.     

Microstructure,mechanical and anti-ablation properties of SiCnw/PyC core-shell networks reinforced C/C–ZrC–SiC composites fabricated by a multistep method of chemical liquid-vapor deposition

C/C–ZrC–SiC composites reinforced by SiC nanowire (SiCnw)/pyrocarbon (PyC) core-shell networks were prepared by a multistep method of chemical liquid-vapor deposition (CLVD). The microstructure, mechanical property and ablation resistance were researched. The investigations presented that the PyC was deposited on the SiC nanowires, and the micro-scale core-shell structures were produced. Moreover, these micro-scale structures not only connected with the fibers and matrices, but also filled the pores in the composites. In contrast with C/C–ZrC–SiC composites, the flexural modulus and strength of SiCnw/PyC-C/C–ZrC–SiC composites increased by 36.91% and 44.53%, and the fracture mode was changed from the brittle to pseudo-plastic fracture. After the oxyacetylene torch ablation at two temperatures for 90s, the composites strengthened by SiCnw/PyC core-shell possessed a better resistant ablation. At ablation temperature of 2300 °C, the mass loss rate and linear reduction rate of the composites with core-shell networks decreased by 66.18% and 57.55% in contrast with the non-reinforced composites, and declined by 56.46% and 57.48% at ablation temperature of 3000 °C. The obvious decrease of ablation rates was ascribed to the dense microstructure, the small coefficient of thermal expansion (CTE), the good thermal conductivity, and the resistant ablation roles of SiCnw/PyC core-shell systems.     

Enhanced electrochemical properties of LiFePO4–silicon composites as positive electrode materials fabricated using a solid-state method

LiFePO₄–silicon composites were fabricated by using a solid-state method for applying positive electrodes in lithium ion batteries. The LiFePO₄–silicon composites were characterized with X-ray diffraction and field emission scanning electron microscopy. Their electrochemical properties were investigated with cyclic voltammetry, electrochemical impedance spectroscopy, and charge–discharge tests. The added silicon not only suppressed the surface corrosion caused by the decreasing H⁺ concentration in the electrolyte, but it also acted as a barrier between the LiFePO₄ particles and LiPF₆ electrolyte, thereby preventing the dissolution of Fe²⁺ in the electrode and enhancing the electrolyte/active material interactions. This resulted in improved lithium-ion transfer kinetics and excellent positive electrode performance, especially at high current densities and different operating temperatures (0, 25, and 50 °C). At 25 °C, the LiFePO₄ composite containing 2 wt% of silicon delivered the best electrochemical performance with a lithium-ion diffusion coefficient of 1.81×10⁻⁹ cm² s⁻¹, a specific discharge capacity of 143 mA h g⁻¹ for the initial cycle, and a capacity retention of 98% after 100 cycles. In contrast, the corresponding values for the pure LiFePO₄ were 1.19×10⁻¹¹ cm² s⁻¹, 115 mA h g⁻¹, and a capacity retention of 76% after 100 cycles, respectively.     

Structural,thermal and dielectric properties of AlN–SiC composites fabricated by plasma activated sintering

Highly dense AlN–SiC composites with various SiC additions (0–50?wt-%) were fabricated at 1800°C by plasma activated sintering. The effect of SiC addition on structural, thermal and dielectric properties as well as microwave absorbing performance of the composites was investigated. The thermal conductivity decreases with increasing SiC addition, from 68.7 W (m?K)^?1 for 0?wt-% SiC to 19.38?W (m?K)^?1 for 50?wt-% SiC. On the contrary, the permittivity and dielectric loss increase gradually, from 7.6–8.5 to 22–26.7 and from 0.02–0.1 to 0.2–0.53, respectively. AlN–SiC composite with better thermal and dielectric properties in 30?wt-% SiC, whose thermal conductivity and dielectric loss are found to be 24.88?W (m?K)^?1 and 0.15–0.74, respectively. Furthermore, the composite exhibits microwave absorbing performance with the minimum reflection loss (RL) of ?16.5 dB at 15.5 GHz and the frequency range of 2.6 GHz for RL below ?10 dB (90% absorption).     

Densification behaviour and mechanical properties of B4C–SiC intergranular/intragranular nanocomposites fabricated through spark plasma sintering assisted by mechanochemistry

High-performance B₄C–SiC nanocomposites with intergranular/intragranular structure were fabricated through spark plasma sintering assisted by mechanochemistry with B₄C, Si and graphite powders as raw materials. Given their unique densification behaviour, two sudden shrinkages in the densification curve were observed at two very narrow temperature ranges (1000–1040 °C and 1600–1700 °C). The first sudden shrinkage was attributed to the volume change in SiC resulting from disorder–order transformation of the SiC crystal structure. The other sudden shrinkage was attributed to the accelerated densification rate resulting from the disorder–order transformation of the crystal structure. The high sintering activity of the synthesised powders could be utilised sufficiently because of the high heating rate, so dense B₄C–SiC nanocomposites were obtained at 1700 °C. In addition, the combination of high heating rate and the disordered feature of the synthesised powders prompted the formation of intergranular/intragranular structure (some SiC particles were homogeneously dispersed amongst B₄C grains and some nanosized B₄C and SiC particles were embedded into B₄C grains), which could effectively improve the fracture toughness of the composites. The relative density, Vickers hardness and fracture toughness of the samples sintered at 1800 °C reached 99.2±0.4%, 35.8±0.9 GPa and 6.8±0.2 MPa m^1/2, respectively. Spark plasma sintering assisted by mechanochemistry is a superior and reasonable route for preparing B₄C–SiC composites.     

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.     

Complex study of protective Cr3C2–NiAl coatings deposited by vacuum electro-spark alloying,pulsed cathodic arc evaporation,magnetron sputtering,and hybrid technology

Coatings were obtained by vacuum electro-spark alloying (VESA), pulsed cathodic arc evaporation (PCAE), magnetron sputtering (MS) techniques and VESA-PCAE-MS hybrid technology using Cr₃C₂–NiAl electrodes. The structure of the coatings was analyzed using scanning and transmission electron microscopy, X-ray diffraction and energy-dispersive spectroscopy. Mechanical properties were determined by nanoindentation, while tribological properties were assessed using pin-on-disk tribometer. Corrosion resistance was estimated by voltammetry in 1 N H₂SO₄ and 3.5%NaCl solutions. Oxidation resistance tests were performed at 800°С in air. The VESA coating had the highest thickness, low friction coefficient and high wear resistance. PCAE coating demonstrated the highest hardness (24 GPa) and elastic recovery (59%), oxidation resistance and superior corrosion resistance both in 1 N H₂SO₄ (i_corr = 70 μА/cm²) and 3.5%NaCl (i_corr = 0.74 μА/cm²) solutions. The MS coating had average mechanical properties and low corrosion current density (71 μА/cm²) in 1 N H₂SO₄. Deposition of coatings using VESA-PCAE-MS hybrid technology led to an increase in corrosion and oxidation resistance at least by 1.5 times in comparison with the VESA coating.     

Effects of the pretreatment of a cemented carbide surface on its properties and on the properties of diamond coatings deposited by oxygen–acetylene flame CVD

The influence of the pretreatment of the WC (6% Co) surface on its properties (i.e. roughness, grain size and chemical composition) and on the properties of flame-deposited coatings have been studied. The surface treatments included the action of an oxidizing oxygen/acetylene flame at 1000 °C, scratching with diamond particles (14–20 μm), mixture with iron (<45 μm) in an ultrasound bath, and seeding with a nm-sized diamond suspension. An acid treatment was included in the pretreatment sequence. It is found that the oxidizing flame and the seeding decrease the surface roughness of the substrate as well as the diamond coatings, at the same time increasing the adhesion of the coating. Ultrasound scratching with the diamond/iron suspension increases the roughness of both the substrate and the diamond coating and decreases the adhesion of the coating. Scratching with diamond particles shows a similar but lesser effect. Except for scratching with diamond, all the surface pretreatment procedures lead to an increase in the density of diamond particles: this increase is greatest for seeding. Our results indicate that good adhesion and a small surface roughness are best obtained by the use of an oxidizing flame followed by acid treatment and seeding with nanoparticles.     

Microstructure,mechanical and tribological properties of Mo–V–Cu–N coatings prepared by HIPIMS technique

A combination of high wear-resistance and low-friction is crucial for improving the wear performance of self-lubricating coatings, which is generally determined by an excellent lubricating effect and mechanical strength. In this study, the Mo–V–Cu–N coatings were prepared by HIPIMS technique with a spliced target of Mo–V–Cu at various charge voltages. The results revealed that Mo–V–Cu–N coatings presented a solid solution phase of B1–MoVN with (200) preferred orientation, and the preferred orientation was enhanced at high charge voltages. Whereas the Cu atoms formed an amorphous phase in Mo–V–Cu–N coatings due to a low Cu content of 2.3–3.6 at.%. As the charge voltage increased to 750 V, more charged metallic ions were accelerated and bombarded substrate surface efficiently, forming smooth and dense Mo–V–Cu–N coatings with a high hardness of 31.0 GPa. All the coatings presented a low friction coefficient of 0.34–0.39 due to the formation of MoO₂, VO₂ and CuO mixed oxides, and the wear mechanism was dominated by abrasive and tribo-oxidation wear at room temperature.     

Microstructure analysis and mechanical properties of a new class of Al2O3–WC nanocomposites fabricated by spark plasma sintering

We report the synthesis of a new class of Al₂O₃–WC nanocomposites for the first time by using metal–organic chemical vapor deposition process in a spouted bed followed by spark plasma sintering technique. The microstructure and mechanical properties of these prepared nanocomposites have been analyzed for various sintering parameters. From microstructure observation, it is found that the nanosized WC particles are dispersed within alumina matrix grains and intergrains. The microstructure of transgranular and step-wise fracture surface are found in these nanocomposites. The basic mechanical properties like density, hardness, and toughness also have been analyzed and the results are interpreted by correlating with that of corresponding microstructures.