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.     

Characterization of (Ti1−xAlx)N films prepared by radio frequency reactive magnetron sputtering

(Ti_1−xAl_x)N films were deposited by radio frequency reactive magnetron sputtering on a high speed steel substrate. The structure and composition of the coatings were analysed by various techniques. Hardness and adhesion of the films were investigated using Vickers micro-indentation and scratch test respectively, whereas their tribological properties were studied using a pin-on-disk tribometer. The results show that increasing aluminium content leads to increase hardness of the films and to decrease their wear resistance when sliding against a magnesia-stabilized zirconia ball. On the contrary, no clear dependence of the film adhesion on the aluminium concentration was detected.     

Improving energy density of crystalline–amorphous multilayer films deposited on Ti foils by structural modulation

Dielectric capacitors are one of the most important energy-storage components specifically used for various high-power pulse applications. However, the low energy-storage density (U_e) of dielectrics used today limits their application. In this study, crystalline–amorphous multilayer films of crystalline Sr_0.85Bi_0.1TiO₃ (SBT)/amorphous SBT/amorphous Al₂O₃ (S_c–(8−n)S_a–nA_a) were fabricated on flexible Ti foils using the sol–gel method. An enhancement in energy density was achieved by adjusting the thicknesses of the amorphous SBT and Al₂O₃ (AO) layers. The crystalline SBT layer contributes to an increase in the dielectric constant and the amorphous AO layer to an increase in the breakdown strength. Moreover, the AO layers that are inserted are capable of suppressing the leakage current by eliminating the space charge limited conductance mechanism and thereby effectively decreasing the probability of breakdown of the SBT layers. A lower leakage current and higher breakdown strength can be further achieved using an Al electrode instead of the Au electrode. A large energy density of 27.2 J cm⁻³ can be realized via the crystalline–amorphous multilayer films with the Al electrode, which represents an enhancement of ~234% over that of the amorphous SBT film (8.14 J cm⁻³). In addition to the high energy-storage enhancement, this study also presents a promising method that can be used to fabricate flexible multilayer films for lightweight and high energy density applications and for devices used to service high-temperature conditions.     

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.     

Effect of Si content on the microstructure and properties of Ti–Si–C composite coatings prepared by reactive plasma spraying

In this study, Ti–Si–C composite coatings were synthesized via plasma spraying of agglomerated powders prepared by a spray drying/precursor pyrolysis technology using Ti, Si, and sucrose powders. The influence of Si content, ranging from 0 wt% to 24 wt%, on the microstructure, mechanical properties, and oxidation resistance of the composite coatings was investigated. Results show that the phase composition of the Ti–Si–C composite coatings changes with the increasing Si content. The coatings without Si addition consist of TiC and Ti₃O; the coatings with 6–18 wt% Si are composed of TiC, Ti₅Si₃, and Ti₃O; the coatings with Si content of 24 wt% form only TiC and Ti₅Si₃ phases. As the Si content increases, the hardness of the Ti–Si–C composite coatings increases first and then decreases, depending on the intrinsic hardness of the ceramic phases, the brittleness of Ti₅Si₃, and the defects such as pores and cracks. The Ti–Si–C composite coatings have high wear resistance due to the in-situ synthesized high-hardness TiC and Ti₅Si₃. Owing to the high brittleness of Ti₅Si₃, the increasing Si content leads to higher wear volume loss at room temperature, which can be partially improved in high-temperature wear tests. The oxidation resistance of Ti–Si–C composite coatings increases with the increase of Si content, and the higher the oxidation temperature, the more obvious the influence of the Si addition on oxidation resistance.     

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.     

Boron carbide films deposited by a magnetron sputter–ion plating process: film composition and tribological properties

Amorphous boron carbide films were deposited onto silicon substrates by a magnetron sputter–ion plating process in an argon plasma atmosphere (0.25 Pa) using a B₄C target. The substrates were polarized with a d.c. bias voltage in the range from 0 to −100 V. The film composition and the presence of contaminants were determined by ion beam analysis (IBA). The nanoscale tribological properties were investigated by atomic force microscopy (AFM). IBA revealed that the boron/carbon atomic ratio is around 4 and that oxygen contamination does not exceed 10 at.%. The hydrogen content is below 2 at.%. The film density is nearly the bulk value for all biases applied to the substrate. AFM measurements show that the surface roughness decreases with increase of bias from 0.85 to 0.15 nm. The friction coefficient obtained by lateral force measurements follows the same trend, decreasing with increasing bias from 0.25 to 0.1. Wear measurements were performed and the wear depth decreased for films with lower friction coefficients. A mechanism based on the removal of a modified B₄C surface layer is proposed to explain the wear results.     

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).     

Carbonation of C–S–H and C–A–S–H samples studied by 13C, 27Al and 29Si MAS NMR spectroscopy

Synthesized calcium silicate hydrate (C–S–H) samples with Ca/Si ratios of 0.66, 1.0, and 1.5 have been exposed to atmospheric CO₂ at room temperature and high relative humidity and studied after one to 12 weeks. ²⁹Si NMR reveals that the decomposition of C–S–H caused by carbonation involves two steps and that the decomposition rate decreases with increasing Ca/Si ratio. The first step is a gradual decalcification of the C–S–H where calcium is removed from the interlayer and defect sites in the silicate chains until Ca/Si = 0.67 is reached, ideally corresponding to infinite silicate chains. In the seconds step, calcium from the principal layers is consumed, resulting in the final decomposition of the C–S–H and the formation of an amorphous silica phase composed of Q³ and Q⁴ silicate tetrahedra. The amount of solid carbonates and of carbonate ions in a hydrous environment increases with increasing Ca/Si ratio for the C–S–H, as shown by ¹³C NMR. For C–A–S–H samples with Ca/Si = 1.0 and 1.5, ²⁷Al NMR demonstrates that all aluminium sites associated with the C–S–H are consumed during the carbonation reactions and incorporated mainly as tetrahedral Al(–OSi)₄ units in the amorphous silica phase. A small amount of penta-coordinated Al sites has also been identified in the silica phase.     

Fullerene (C60)–transitional metal (Ti) composites: Structural and biological properties of the thin films

Thin films of the binary C₆₀/Ti composites (with various phase ratios) were deposited on the Si(001) wafers and microscopic glass coverslips in continuous and micropatterned forms. The composites acquired a nanogranular structure with granules of about 50 nm in size. The RBS inspection confirmed homogeneous distribution of the phases and also the presence of oxygen. The Raman study suggested polymerization of the C₆₀/Ti composites into polymeric structures. The hybrid substrates were tested on biocompatibility—the films were seeded with human osteoblast-like MG 63 cells, and their proliferation was analyzed for 7 days. It has been found that the C₆₀/Ti composites can be counted as good supports for the adhesion of the selected MG 63 cells. The composites exhibited similar biocompatibility as the mix of amorphous carbon and titanium, but different than fullerene (C₆₀) solids.     

Corrosion,wear and wear–corrosion behavior of graphite-like a-C:H films deposited on bare and nitrided titanium alloy

This work presents a comparative wear, corrosion and wear–corrosion (the last one in a simulated physiological solution) study of graphite-like a-C:H (GLCH) films deposited on bare and nitrided Ti6Al4V alloy. Films, deposited by r.f. PACVD, presented low porosity and promoted high corrosion resistance. The friction coefficient of the films was very low with appreciable wear resistance at room conditions. However, due to the simultaneous action of both load and the corrosive environment in wear–corrosion tests a marked reduction in the coating lifetime was observed. Unexpectedly, films deposited on the nitrided alloy presented a lifetime at least ten times shorter than that of films on bare alloy. We explain such a result in terms of film/substrate interaction. The weak GLCH/nitrided alloy interaction facilitates fluid penetration between the film and the substrate which leads to a fast film delamination. Such an interpretation is supported by force curve measurements, which show that the interaction between GLCH and nitrided alloy is four times weaker than that between GLCH and bare alloy.     

Improving hardness and toughness of plasma sprayed Ti–Si–C nano-composite coatings by post Ar-annealing

Ti–Si–C (TSC) composite coatings were fabricated by plasma spraying using Ti/Si/graphite agglomerates as feedstock. Ar-annealing was carried out to reduce the intrinsic defects and increase the performance of the as-sprayed TSC coating. The effects of the annealing temperature (500–900 °C) on the microstructures and mechanical performances of the TSC coatings were investigated. All TSC coatings consisted of TiC, Ti₅Si₃ and MAX phase Ti₃SiC₂. With the increase in temperature (>700 °C), TiC became predominant, while the Ti₃SiC₂ phase content increased, which was accompanied by a decrease in Ti₅Si₃ content. The high -temperature annealing (>700 °C) led to a homogenous microstructure with a relatively low porosity and increased number of micro-cracks. Notably, the hardness and fracture toughness of the TSC coating were simultaneously increased after the annealing, from 1164 HV to 1.96 MPa m^1/2 to 1560 HV and 3.45 MPa m^1/2, respectively. The formation of nanoscale TiC and Ti₅Si₃ with a network distribution, uniform and dense microstructure, and toughening effects of Ti₃SiC₂ and micro-cracks provided the high mechanical performances of the TSC composite coatings.     

Comparison of a-C:H films deposited from methane–argon and acetylene–argon mixtures by electron cyclotron resonance–chemical vapor deposition discharges

Hydrogenated amorphous carbon (a-C:H) films are deposited from methane–argon and acetylene–argon gas mixtures in a microwave electron cyclotron resonance plasma reactor. The films deposited with the two different gas mixtures under similar input parameter conditions have substantially different properties, including deposition rate, mass density, optical absorption coefficient, refractive index, optical bandgap and hydrogen content. The deposition parameters varied include rf-induced dc substrate bias voltage (0 to −60 V), pressure (1–5 mTorr) and argon/hydrocarbon gas flow ratio (0–1.0). The discharge properties of the two different gas mixtures, including electron temperature, ion saturation current, and residual gas composition of the exit gas flow, are measured to help explain the different deposition results from the two different gas mixtures. The use of lower pressures is found to be critical for obtaining denser, lower hydrogen content films from acetylene. For the methane-deposited films the addition of argon to the discharge increased the film's mass density and lowered the hydrogen content. In both methane- and acetylene-based deposition processes the rf-induced bias is also a critical determining factor of film properties.     

Colored amorphous silica-based powder with TiN nanocrystals precipitated by ammonolysis of Ti–Si–O ternary glass

Coloration of amorphous silica powder containing titania was investigated by nitridation in an ammonia flow. The oxide precursors were obtained by the hydrolysis of a mixture of tetraethyl orthosilicate (TEOS) and tetrabutoxy titanium (TBT). The color changed with the amount of TBT in the mixture, the hydrolysis pH and the ammonolysis temperature. The original white color of the 8 mol% TBT powder hydrolyzed under basic pH conditions changed to pale goldenrod at 700°C, then to dark olive green at 800°C, and further darkened with increasing ammonolysis temperature. A steel-blue color appeared at 900°C for the powder obtained with 3 mol% TBT, and increased in darkness at 1000°C. A similar bluish color was observed for powders obtained by acidic hydrolysis after ammonolysis above 900°C, and this was independent of the amount of titania, although the chroma decreased with increasing firing temperature for the powder with 3 mol% TBT. The ammonolysis powder products were characterized using X-ray diffraction (XRD), electron probe micro analysis (EPMA), transmission electron microscopy-electron energy-loss spectroscopy (TEM-EELS), scanning transmission electron microscopy-high-angle annular dark-field imaging (STEM-HAADF) and Ti–K edge X-ray absorption fine structure (XAFS). The color change was related to both precipitated TiN nanocrystals and residual titanium in the amorphous silica matrix. The TiN exhibited a goldish reflection and also plasmonic absorption from light blue to gray depending on the TiN crystallite size. The plasmonic absorption and resonance of nanocrystalline TiN will be useful similarly to that of gold in nanotechnology for various kinds of energy application.     

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 of Si–diamond–SiC composites by in-situ reactive sintering and their thermal properties

This article described a novel method of preparation of Si–diamond–SiC composites by in-situ reactive spark plasma sintering (SPS) process. The relative packing density of Si–diamond–SiC composite was 98.5% or higher in a volume fraction range of diamond between 20% and 60%. Si–diamond–SiC composites containing 60 vol% diamond particles yielded a thermal conductivity of 392 W/m K, higher than 95% the theoretical thermal conductivity calculated by Maxwell–Eucken's equation. Coefficients of thermal expansion (CTEs) of the composites are lower than the values of theoretical models, indicating strong bonding between the diamond particle and the Si matrix in the composite. The microstructures of these materials were studied by field emission scanning electron microscope (FE-SEM) and X-ray diffraction (XRD). As a result of reaction between diamond and silicon, SiC phase formed.     

Preparation of Ni–Mo–C/Ti(C,N) coated powders and its influence on the microstructure and mechanical properties of Ti(C,N)-based cermets

Ni–Mo–C/Ti(C,N) coated powders, namely Ni–Mo alloy and Mo₂C coated Ti(C,N) composite powders, were synthesized by using a heterogeneous precipitation and thermal reduction method, then pressed and vacuum sintered to fabricate cermets. The chemical composition, microstructure and phases of the composite powders and the microstructure and properties of sintered cermets were experimentally investigated. The results show that a fine and uniform microstructure of (Ti,Mo)(C,N)-Ni cermets without the conventional core-rim structure is obtained. The phases formed during the preparation of the coated powders as well as the cermets were analyzed by means of a X-ray diffraction (XRD) technique. The XRD result confirms the formation of the Ni₃Ti phase in the cermets. Due to the formation of the non-magnetic Ni₃Ti and the dissolution of Mo in Ni binder phase, the magnetic properties are strongly retarded. The fracture of the cermets is mainly characterized by inter-granular and dimple fractures. Better mechanical properties can be obtained in comparison with conventionally fabricated ones.     

Reactive sintering behavior and enhanced densification of (Ti,Zr)B2–(Zr,Ti)C composites

Reactive hot pressing was used to prepare (Ti,Zr)B₂–(Zr,Ti)C composites from equimolar ZrB₂ and TiC powders. The reaction and solid-solution coupling effect and enhanced densification in ZrB₂-50 mol.% TiC were proposed as contrasted to conventional consolidation of TiB₂-50 mol.% ZrC. The (Ti,Zr)B₂–(Zr,Ti)C composite sintered at a temperature as low as 1750 °C exhibited negligible porosity and average grain sizes of 0.30 μm for (Ti,Zr)B₂ and 0.36 μm for (Zr,Ti)C. Complete reaction and rapid densification of ZrB₂-50 mol.% TiC was achieved at 1800 °C for only 10 min. The densification mechanism was mainly attributed to material transport through lattice diffusion of Ti and Zr atoms with an activation energy of 531 ± 16 kJ/mol. This study revealed for the first time novel insights into rapid densification of refractory fine-grained diboride–carbide composites by reactive hot pressing at relatively low temperatures.