Ceramic TiC/a:C protective nanocomposite coatings: Structure and composition versus mechanical properties and tribology

The relationship between the structure, elemental composition, mechanical and tribological properties of TiC/amorphous carbon (TiC/a:C) nanocomposite thin films was investigated. TiC/a:C thin film of different compositions were sputtered by DC magnetron sputtering at room temperature. In order to prepare the thin films with various morphology only the sputtering power of Ti source was modified besides constant power of C source. The elemental composition of the deposited films and structural investigations confirmed the inverse changes of the a:C and titanium carbide (TiC) phases. The thickness of the amorphous carbon matrix decreased from 10 nm to 1–2 nm simultaneously with the increasing Ti content from 6 at% to 47 at%. The highest hardness (H) of ~26 GPa and modulus of elasticity (E) of ~220 GPa with friction coefficient of 0.268 was observed in case of the film prepared at ~38 at% Ti content which consisted of 4–10 nm width TiC columns separated by 2–3 nm thin a:C layers. The H3/E2 ratio was ~0.4 GPa that predicts high resistance to plastic deformation of the TiC based nanocomposites beside excellent wear-resistant properties (H/E=0.12).     

Sputtered nanocrystalline ceramic TiC/amorphous C thin films as potential materials for medical applications

The relationship between structural behaviour of sputtered TiC/amorphous C (TiC/a:C) thin films and corrosion properties was measured in three various pH solutions (0.5 M NaCl (pH=6); 0.1 M HCl (pH=1); and 0.1 M NaOH (pH=13)). The ~400 nm thick nanocomposites were deposited by DC magnetron sputtering on different substrates (Ti6Al4V alloy and CoCrMo alloy) in argon at 25 °C and 0.25 Pa with 150 W input power of carbon target and 50 W input power of titanium target. The structure and composition of nanocomposites were investigated by Transmission and Scanning Electron Microscopy. In both samples the structural investigations confirmed columnar structure of TiC/a:C films with 25–50 nm sized cubic TiC. These columns were separated by 2–3 nm thin amorphous carbon layers. TiC/a:C /Ti6Al4V alloy implant material showed better corrosion resistance than the TiC/a:C/CoCrMo alloy in 0.5 M NaCl solution based on results of the Electrochemical Impedance Spectroscopy. For both samples, the 0.1 M NaOH solution was the most corrosive media.     

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,mechanical and biological comparison of TiC and TiCN nanocomposites films

The vacuum deposition provides great flexibility for manipulating material's chemistry and structure. A combination of metallic (Ti) and carbon phase can enhance certain physical properties of nanocomposite thin films.In this work, the comparison of nanocomposite films composed of TiC or TiCN grains embedded in amorphous carbon matrix is reported. The films were prepared by dc magnetron sputtering at 200 °C in argon and nitrogen. In the case of argon deposition, 4–5 nm TiC grains in carbon matrix were observed. The nitrogen deposition combined with low content of Ti (～1.2 at%) proved to be insufficient for the development of larger crystals. The carbon had carbide character in TiC film, whereas in TiCN film all the carbon had graphite type environment. TiC film deposited in argon exhibited better mechanical properties than TiCN films deposited in nitrogen. In both cases, the good biocompatibility was observed after 7 days osteoblast cells seeding.     

Mechanical and tribological properties of TiC/amorphous hydrogenated carbon composite coatings fabricated by DC magnetron sputtering with and without sample bias

TiC/amorphous hydrogenated carbon (a-C:H) composite films were deposited by Ti DC magnetron sputtering using argon and acetylene as the carrier gas and precursor, respectively. The working pressure was maintained at 4 × 10^− 1 Pa and the composition of the films was modulated by controlling the partial pressure of acetylene. The composition and structure of the films were evaluated by X-ray photoelectron spectroscopy and glancing angle X-rays diffraction, whereas the hardness and elastic modulus values of the films fabricated using different sample biases were measured by nano-indentation. Ball-on-disk tribometry was used to measure the tribological properties, and secondary electron microscopy was used to analyze the wear tracks. The results show that the friction coefficients and wear rates do not vary significantly with the Ti concentrations when the Ti concentration is above 39.7 at.% or below 20 at.% but increase with increasing titanium concentrations between 20 at.% and 39.7 at.%. The wear mechanism depends on the relative amounts of TiC and a-C:H. At high Ti concentrations, the mechanism resembles that of TiC due to the thin a-C:H matrix surrounding the TiC grains. At low Ti concentrations, the mechanism is similar to that of DLC as the effects of the a-C:H matrix dominates over those of the TiC grains.     

Microstructure,hardness and toughness of boron carbide thin films deposited by pulse dc magnetron sputtering

Boron carbide thin films were deposited on (100) silicon substrates at ambient temperature via. pulse dc magnetron sputtering. Various frequency and duty cycles were applied to the hot-pressed B₄C target in order to understand their influence on the structure and mechanical properties of the B₄C films. X-ray Energy dispersive spectrum, Raman spectroscopy and Transmission electronic microscopy were used to characterize the composition and microstructure of the films. Nanoindenter was employed to measure the hardness and modulus. The film toughness was evaluated by a microindentation method. The results show that both pulse frequency and duty cycle significantly affect the B/C atomic ratio and then hardness and modulus in the boron carbide films. However, the amorphous structure of the films was maintained when the frequency and duty cycle changed. The maximum hardness of 29 GPa and modulus of 247 GPa combined with relative high toughness (3.3 MPa m^1/2) were achieved under 50 kHz frequency and 30% duty cycle. In addition, there was no evidence to prove that the graphite phase existed in the B₄C films although exceeded C concentration was detected.     

Cu3N films prepared by the low-pressure r.f. supersonic plasma jet reactor: Structure and optical properties

A low-pressure r.f. supersonic plasma jet reactor (RPJ) has been used for deposition of Cu₃N thin films. From a comparison of experimental values of composition weight per cent with the theoretically predicted values, it follows that if the r.f. power absorbed in the reactor does not exceed 75 W, stoichiometric Cu₃N films can be obtained. The typical value of the deposition growth rate was found to be in the order of 16 nm min⁻¹ for r.f. power P_w≈40 W. The optical energy gap, E_g, microhardness, H, and Young's modulus, E, of the deposited Cu₃N thin films increase with decreasing r.f. power. They are E_g=1.24 eV, H=8.8 GPa and E=146 GPa for the sample deposited with a r.f. power of 40 W. Deposition of Cu₃N thin films by means of the modificated RPJ reactor (with a multi-jet system) on to internal walls of cavities, holes and on the surface of complex shapes of hollow substrates can be useful for surface-treatment technology.     

The changes in structural and optical properties of (ZnO:AlN) thin films fabricated at different RF powers of ZnO target

AlN doped ZnO thin films were prepared on glass and Si (100) substrates by RF sputtering. The ratio of nitrogen (N₂) to Argon (Ar) used to prepare the films was 80:20. The films were deposited at different RF powers of 150 W, 175 W, 200 W, 225 W and 250 W for ZnO target and 200 W for AlN target. XRD results revealed the existence of (002) ZnO phase for RF power of ZnO target above 175 W. However, at the RF power of 150 W, the film exhibited amorphous properties. The prepared films showed transmission values above 70% in the visible range. The average calculated value of energy band gap and the refractive index were 3.43 eV and 2.29 respectively. The green and UV emission peaks were observed from PL spectra. Raman Peaks at 275.49 cm^?1 and 580.17 cm^?1 corresponding to ZnO:N and ZnO:AlN were also observed.     

Hard silicon carbonitride films obtained by RF-plasma-enhanced chemical vapour deposition using the single-source precursor bis(trimethylsilyl)carbodiimide

Amorphous silicon carbon nitride (Si/C/N) coatings were prepared on steel substrates by RF plasma-enhanced chemical vapour deposition (RF-PECVD) from the single-source precursor bis(trimethylsilyl)carbodiimide (BTSC). The films were characterised by X-ray diffraction (XRD), ellipsometry, FTIR, glow discharge optical emission spectroscopy (GDOES), optical microscopy, AFM, hardness measurements, scratch-, tribological- and corrosion-tests. The results of these studies show that the coatings obtained on the RF-powered electrode (cathode) were black, thick (>20 μm) and hard (21–29 GPa), while those grown on the grounded electrode (anode) were yellow, thin (<4 μm) and soft (∼5 GPa). Coatings on the anode contained around 19 at.% oxygen and exhibited silicon predominantly bonded to oxygen. In contrast, the oxygen content of the films deposited on the cathode was below 2 at.%. Silicon atoms in these coatings are co-ordinated predominantly to nitrogen and carbon. The surface of all coatings was very smooth with a maximum rms roughness between 2 nm and 5 nm for an area of 5 μm × 5 μm. Scratch and tribological tests reveal a brittle nature of the cathode-coatings and rather weak adhesion to the metal substrates. Salt-spray tests indicate an excellent corrosion resistance of the material.     

Influence of negative bias voltage on structural and mechanical properties of nanocrystalline TiNx thin films treated in hot cathode arc discharge plasma system

Ti thin films were grown by DC sputtering on a glass substrate and then nitrided in a hot cathode arc discharge plasma system, which is an effective approach to independently monitoring the plasma and nitriding parameters. The hardness of pristine Ti thin film is found to be ~3.06 GPa, which increases upto ~16.08 GPa with an increase in negative bias voltage to −140 V and then decreases to ~15.05 GPa for higher of −240 V bias voltage. Similar kind of variation has been observed in crystallite size and surface roughness. Crystallite size is found to increase from 11.1 nm (pristine Ti) to 14.8 nm (for −140 V) and then reduces to 11.9 nm for –240 V. Surface roughness increases from 2.78 nm (pristine) to 6.84 nm (for –140 V), which is found to be 4.14 nm for –240 V. Optical and electrical measurements also reveal the strong impact of negative bias voltage on the bandgap and resistivity of the films. Above results are understood on the basis of diffusion of nitrogen ions for lower voltages and saturation of nitrogen ions in the host lattice for high voltages.     

Structural characterization of dual-metal containing diamond-like carbon nanocomposite films by pulsed laser deposition

Two metal dopants were simultaneously added into a diamond-like carbon (DLC) matrix using a KrF pulsed laser system at room temperature with no post-processing. The nanometer thin films were fabricated from carbon source targets containing the two metals of interest, Ti and Ni, in atomic percentages 2.5%, 5%, 7.5% and 10% each. Films from carbon targets containing only 5% Ni or 5% Ti were also deposited for comparison against the dual-metal containing films. Microstructure analysis shows that each individual metal reacted independently and uniquely with carbon as confirmed by XPS and surface analysis shows the presence of TiC bonds and Ni⁰. Therefore, there was no reaction between Ti and Ni as metals confirmed by XPS. Through this independent interaction, a superposition of microstructural properties was obtained as if the metals were doped separately into DLC. The separate interactions of the two metals with carbon were important as they were able to play separate and different roles in enhancing the properties of DLC. In addition, TEM analysis confirmed a unique self-assembly state where the nickel ions converge into nanosized clusters of ～ 5 nm in diameter and predominantly oriented in a (200) direction. The resultant films were also extremely smooth with RMS roughness of about 0.1 nm, thus retaining the inherent smoothness of DLC films. The combined Ti/Ni films could be used as substrates to grow carbon nanotubes with controlled density which could be used as cold electron emitters. Thus, it is interesting to study the growth mechanism and microstructure of the composite films.     

Mechanical and high pressure tribological properties of nanocrystalline Ti(N,C) and amorphous C:H nanocomposite coatings

This paper reports on the mechanical and high pressure tribological properties of nanocrystalline (nc-) Ti(N,C)/amorphous (a-) C:H deposited, using low temperature (～ 200 °C) DC reactive magnetron sputtering. The mechanical properties are affected by the nc-Ti(N,C)/a-C:H phase fraction ratio. For increasing C contents (from 31 to 47 at.%) an increase of the a-C:H phase content and a degradation of the nanocrystalline phase occurs leading to a reduction in nanoindentation hardness (H) values (from 15 to 9 GPa) and reduced modulus (Er) values (from 150 to 80 GPa). A strong correlation between H/E ratio and wear performance was exhibited by the coatings. The synthesized coatings survived up to 100 m sliding distance when tested using pin-on-disc sliding configuration at > 4.5 GPa contact pressures and the measured friction coefficient values were similar for all films (μ ～ 0.21–0.25).     

Characterization of carbon/carbon composite/Ti6Al4V joints brazed with graphene nanosheets strengthened AgCuTi filler

Carbon/carbon (C/C) composite and Ti6Al4V alloy (wt%) were successfully brazed with graphene nanosheets strengthened AgCuTi filler (AgCuTiG). Graphene nanosheets (GNSs) with low CTE and high strength were dispersed into AgCuTi filler by ball milling. The interfacial microstructure was systematically characterized by varieties of analytical means including transmission electron microscopy (TEM). Results show that typical interfacial microstructure of the joint brazed at 880 °C for 10 min is a layer structure consisting of (Ti6Al4V/diffusion layer/Ti2Cu + TiCu + Ti3Cu4 + TiCu4/GNSs + TiCu + TiC + Ag(s,s) + Cu(s,s)/TiC/C/C composite). The interfacial microstructure and mechanical properties of brazed joints changed significantly as temperature increased. High temperature promoted the growth of TiCu and TiC phases, which were attached to GNSs. Meanwhile, the diffusion layer and primary reaction layers thickened as temperature increased, while the thickness of brazing seam decreased. The maximum shear strength of 30.2 MPa was obtained for the joint brazed at 900 °C for 10 min. GNSs decreased the thickness of brittle reaction layers and promoted the formation of TiCu and TiC phases in brazing seam, which caused the strengthening effect and decreased the CTE mismatch of brazed joints. The fracture modes are also discussed in this paper.     

Microstructure and mechanical properties of hot-pressed B4C/TiC/Mo ceramic composites

Boron carbide (B₄C)/TiC/Mo ceramic composites with different content of TiC were produced by hot pressing. The effect of TiC content on the microstructure and mechanical properties of the composites has been studied. Results showed that chemical reaction took place for this system during hot pressing sintering, and resulted in a B₄C/TiB₂/Mo composite with high density and improved mechanical properties compared to monolithic B₄C ceramic. Densification rates of the B₄C/TiC/Mo composites were found to be affected by additions of TiC. Increasing TiC content led to increase in the densification rates of the composites. The sintering temperature was lowered from 2150 °C for monolithic B₄C to 1950 °C for the B₄C/TiC/Mo composites. The fracture toughness, flexural strength, and hardness of the composites increased with increasing TiC content up to 10 wt.%. The maximum values of fracture toughness, flexural strength, and hardness are 4.3 MPa m^1/2, 695 MPa, and 25.0 GPa, respectively.     

Influence of substrate bias voltage on structure and properties of hard Si–B–C–N films prepared by reactive magnetron sputtering

We systematically investigated the effect of the rf induced negative substrate bias voltage, U_b, on characteristics of novel quaternary Si–B–C–N films. The films were deposited on Si(100) or glass substrates by reactive dc magnetron co-sputtering of silicon, boron and carbon from a single C–Si–B or B₄C–Si target in nitrogen–argon gas mixtures at substrate temperatures of 180–350 °C. Elemental compositions of the films, their surface bonding structure, and mechanical and electrical properties were primarily controlled by the U_b values, varied from a floating potential (being between − 30 and − 40 V) to U_b = − 700 V. The energy and flux of ions bombarding the target and the growing films were evaluated on the basis of the measured discharge characteristics. The films were found to be amorphous with thickness up to 5 μm and density around 2.4 g/cm³. They exhibited hardness up to 44 GPa, modified Young's modulus between 170 and 280 GPa, elastic recovery up to 82% and good adhesion to substrates at a low compressive stress (0.6–1.8 GPa). The results of stress measurements were compared with predictions of the model developed by Davis and a beneficial role of silicon in reducing the compressive stress in the films was proved. Electrical conductivity of the semiconductive Si–B–C–N films with a high (approximately 40 at.%) carbon content was controlled by the nitrogen–argon gas mixture composition and the U_b values.     

The preparation of high quality oriented diamond thin films via low temperature and hydrogen ion etched nucleation

A three-step process was used to prepare high quality [001]-oriented diamond films. First, diamond crystallites were nucleated for 20 min on Si(001) at a temperature around 740 °C by bias-enhance method, during this step the portion of [001]-oriented diamond nuclei was increased in comparison with the nuclei deposited by a two-step method. Then hydrogen ion etching was performed for 30 min by setting an electric potential of −140 V. After the etching step most of the crystallites were [001]-oriented and twinned crystallites disappeared. Finally, diamond thin films were deposited under conventional conditions for [001]-textured growth. SEM was used to analyse the morphology of diamond crystallites and films. The results indicate that large area, uniform and [001]-oriented diamond thin films can be prepared by three-step growth. The films show good Raman characteristics and higher thermal conductivity than those deposited by a two-step process.     

One-step CVD-diamond coating process on 3-D titanium substrates using reticulated vitreous carbon as a solid carbon source

Nanocrystalline diamond (NCD), formed on three-dimensional (3D) titanium (Ti) substrates, through the etching of reticulated vitreous carbon (RVC) was investigated. Porous Ti was prepared by powder metallurgy and the RVC was produced at 1300 and 2000 °C graphitization index. In this chemical vapor infiltration/deposition process, the RVC sample was used as the only carbon source that ensured the production of pertinent growth species directly on the Ti surfaces including its inner and bottom (the opposite side of the sample). The films were deposited at 630 °C substrate temperature. NCD scanning electron microscopy images showed agglomerates of nanometer crystallites with a uniform surface texture covering all sample. Raman measurements showed the typical two shoulders at 1150 and 1490 cm^? 1 attributed to NCD formation. Electrochemical response by cyclic voltammetry measurements confirmed a wide potential window for such electrodes in addition to its exceptional reversibility response.     

Preparation and characterization of Si3N4-based composite ceramic tool materials by microwave sintering

Si₃N₄-based composite ceramic tool materials with (W,Ti)C as particle reinforced phase were fabricated by microwave sintering. The effects of the fraction of (W,Ti)C and sintering temperature on the mechanical properties, phase transformation and microstructure of Si₃N₄-based ceramics were investigated. The frictional characteristics of the microwave sintered Si₃N₄-based ceramics were also studied. The results showed that the (W,Ti)C would hinder the densification and phase transformation of Si₃N₄ ceramics, while it enhanced the aspect-ratio of β-Si₃N₄ which promoted the mechanical properties. The Si₃N₄-based composite ceramics reinforced by 15 wt% (W,Ti)C sintered at 1600 °C for 10 min by microwave sintering exhibited the optimum mechanical properties. Its relative density, Vickers hardness and fracture toughness were 95.73 ± 0.21%, 15.92 ± 0.09 GPa and 7.01 ± 0.14 MPa m^1/2, respectively. Compared to the monolithic Si₃N₄ ceramics by microwave sintering, the sintering temperature decreased 100 °C,the Vickers hardness and fracture toughness were enhanced by 6.7% and 8.9%, respectively. The friction coefficient and wear rate of the Si₃N₄/(W,Ti)C sliding against the bearing steel increased initially and then decreased with the increase of the mass fraction of (W,Ti)C., and the friction coefficient and wear rate reached the minimum value while the fraction of (W,Ti)C was 15 wt%.     

Mechanical properties of free-standing graphene oxide

The mechanical properties of free-standing graphene oxide (GO) films were investigated using nanoindentation on a dynamic contact module (DCM) system. The Young's modulus, stiffness, and ultimate strength of thin films were evaluated. Nanoindentation measurements were combined with the DCM to evaluate the mechanical properties of thin films and to predict the crack length and critical energy. Electrophoretically deposited GO film, 50 ~ 60 nm in thickness, was found to have a Young's modulus of 695 ± 53 ~ 697 ± 15 GPa. The critical energy values for 50- and 60-nm-thick films were 0.142 ~ 0.201 and 0.479 ~ 0.596 J/m², respectively. Nanoindentation combined with the DCM can thus be used to obtain the mechanical properties and critical energy of thin films.     

Preparation and characterization of freestanding SiC(Ti,B) films derived from polycarbosilane with TiN and B as additives

Freestanding SiC(Ti, B) films with high temperature resistance were fabricated from polymer precursor of polycarbosilane (PCS) blended with 0.26 wt% TiN and 0.74 wt% B powders. Results reveal that SiC(Ti, B) films with good mechanical properties are uniform and dense. After high temperature annealing at 1500 °C in argon, SiC(Ti, B) films exhibit better high temperature resistance as compared to SiC films without additives, which implies their potential applications in ultra-high temperatures (exceeding 1500 °C) microelectromechanical systems (MEMS). Sintering additives are effective in suppressing the growth of SiC crystals and decreasing the content of oxygen and free carbon, which is normally beneficial to enhance high temperature resistance of films.