TiCN Films Research Articles

Enhanced adhesion and corrosion resistance through the modulation of a metallic Ti underlayer thickness

In this investigation, TiCN/TiN thin solid film was selected as a protective coating and deposited onto AZ31 alloy through reactive magnetron sputtering. To mitigate the potential failure resulting from the significant physical disparity between the ceramic film and the metal substrate, a Ti thin film was employed as a base layer. Following the deposition process, an analysis was conducted on the structural features, residual stress, fracture morphology, adhesion strength, and corrosion characteristics of the film/substrate system utilizing X-ray diffraction, scanning electron microscopy, scratch testing, and electrochemical workstation. The findings indicate that the incorporation of a Ti metallic underlayer significantly improves the adhesion and corrosion resistance of the TiCN film. However, when the thickness of the Ti layer surpasses 0.37 μm (deposition of 15 min), it leads to the formation of a distinct columnar crystal microstructure, increased residual stress, and diminished adhesion and corrosion resistance. Additionally, this study delves into the corrosion failure mechanisms in a chloride environment and explains the principles of residual stress measurement through XRD.

Mechanical Characteristics of Al2O3, TiCN, and TiAlN Hard Coating Films Measured by Microcantilever Bending Test

Mechanical Characteristics of Al2O3, TiCN, and TiAlN Hard Coating Films Measured by Microcantilever Bending Test

Comparative assessment and experimental analysis of atomic coordination and mechanical properties of sputter deposited Ti-rich TiN, TiC, and TiCN thin films

In the present work, Titanium nitride (TiN)150 nm, Titanium on Titanium nitride (TiN75 nm/Ti75 nm), Titanium on Titanium carbonitride (TiCN75 nm/Ti75 nm), and Titanium on Titanium carbide (TiC75 nm/Ti75 nm) films were deposited on Si (100), quartz, and glass substrates through dc-magnetron sputtering. Vacuum annelation was carried at 600ºC for 1 hr to form TiN (m-TiN), Ti-rich TiN (b-TiN), Ti-rich TiC (b-TiC) and Ti-rich TiCN (b-TiCN) films. b-TiCN showed less optical absorbance and band gap compared to b-TiN and b-TiC films and more detrimental types of defects, which might lead to the degradation of mechanical properties in b-TiCN film. The shifting of the Ti-N core orbital towards higher binding energy showed the higher bond strength of the b-TiN film. The ITA/ITO ratio increased from 0.8 to 2.37 for b-TiC to b-TiN films, signifying the deterioration in medium-range order. The defect parameter, ID/IG, increased from 0.63 to 0.71, indicating that b-TiCN has higher defects than b-TiC films. The valence band spectra revealed that b-TiN and b-TiC valence bands are present above the Fermi level but below in the case of b-TiCN films. X-ray absorption spectroscopy confirmed that the Ti L, N K, and C K-edge were observed at 462.38, 404.53, and 287.33 eV, respectively. The highest Young’s modulus and hardness were 97.43 and 18.47 GPa, respectively, measured by a Berkovich nanoindenter for b-TiN thin films.

Sliding friction behaviors of TiCN/Cr3C2-NiCr and TiCN/WC-CoCr duplex coatings fabricated by combining HVOF and HT-CVD procedures

Hard films play essential roles in the wear protection of metal moving components. In this study, the TiCN/Cr3C2-NiCr and TiCN/WC-CoCr duplex coatings were designed and fabricated by utilizing the high-velocity oxygen fuel and the high-temperature chemical vapor deposition processes. The effects of two cermet interlayers on the microstructure, mechanical characteristics, stress distribution, and sliding wear behavior of the top TiCN films were thoroughly explored. Results evidenced that the TiCN/WC-CoCr duplex coating had a smoother surface than the TiCN/Cr3C2-NiCr duplex coating. The load-bearing capacity and fracture toughness of TiCN/WC-CoCr duplex coating were superior to TiCN/Cr3C2-NiCr duplex coating due to WC-CoCr coating possessing higher hardness, elastic modulus and high-temperature stability. The TiCN/WC-CoCr duplex coating also exhibited lower Von Mises stress compared to TiCN/Cr3C2-NiCr duplex coating, and the stress concentration zone was further away from the interface between the TiCN film and the cermet interlayer. The wear resistance of TiCN/WC-CoCr duplex coating was approximately 2 and 1.5 times that of the single TiCN film and TiCN/Cr3C2-NiCr duplex coating under 20 N load. Moreover, the wear mechanisms of the duplex coatings involved abrasive wear, adhesive wear and oxidative wear. This work significantly enhanced the wear resistance of TiCN films, which will broaden the application of TiCN film in non-load-bearing metal moving components.

Effect of CH4 Flow Rate on the Tribological Behaviors of TiCN Films against Si3N4 Ceramic and Steel Ball

Control of the structural, mechanical and tribological properties of TiCN films play an important role in its numerous applications, including the cutting tools, mechanical components, aeronautical and biomedical engineering industries. Direct-current magnetron sputtering (DCMS) system was applied to deposit TiCN films onto n-type silicon (100) at room temperature. The Ti-TiN interlayer was used to enhance the adhesive strength between the coating and the substrate. The composition and microstructure of the TiCN films were studied using X-ray photoelectron spectroscopy (XPS) and field-emitted scanning electron microscopy (FESEM). The mechanical properties of the films as a function of methane (CH4) flow ratio were then characterized using nano-indentation measurements. The tribological behavior of TiCN films was investigated by UMT-2MT tribometer against a Si3N4 ceramic and AISI52100 steel ball. After the tribological tests, the wear rate of the films was obtained by the 3D surface profiler and the component content of wear debris was evaluated by energy dispersive X-ray spectroscopy (EDS). The results show that the tribological properties of TiCN films are a function of CH4 flow rates. The film obtained at a 10 sccm CH4 flow rate possesses a minimum average COF value of 0.1964 and reaches 72,000 cycles against a Si3N4 ball over the test duration. Furthermore, the wear rate was only 2.076 × 10−6 mm3/N·m. Furthermore, the TiCN films exhibited longer lifespan against the Si3N4 ball than against the steel ball under the normal load of 1 N, indicating that the TiCN films present better lubricative properties when against low-hardness counterparts than high-hardness counterparts.

Evaluation of Biocompatibility of 316 L Stainless Steels Coated with TiN, TiCN, and Ti-DLC Films

In this study, TiN, TiCN, and Ti-diamond-like carbon (Ti-DLC) films were coated on 316 L stainless steel (AISI 316 L) substrate surface by physical vapor deposition. The biocompatibility of the three films (TiN, TiCN, and Ti-DLC) and three metals (AISI 316 L, Ti, and Cu) was compared on the basis of the differences in the surface morphology, water contact angle measurements, CCK-8 experiment results, and flow cytometry test findings. The biocompatibility of the TiN and TiCN films is similar to that of AISI 316 L, which has good biocompatibility. However, the biocompatibility of the Ti-DLC films is relatively poor, which is mainly due to the inferior hydrophobicity and large amount of sp2 phases. The presence of TiC nanoclusters on the surface of the Ti-DLC film aggravates the inferior biocompatibility. Compared to the positive Cu control group, the Ti-DLC film had a higher cell proliferation rate and lower cell apoptosis rate. Although the Ti-DLC film inhibited cell survival to a certain extent, it did not show obvious cytotoxicity. TiN and TiCN displayed excellent performance in promoting cell proliferation and reducing cytotoxicity; thus, TiN and TiCN can be considered good orthodontic materials, whereas Ti-DLC films require further improvement.

Investigation of toxicity effect of TiCN coated on 304 SS and 410 SS substrates in rat fibroblasts and B-lymphocytes.

In the present study, TiCN thin films were coated on AISI 304 and AISI 410 stainless steel (SS) substrates by Cathodic Arc Physical Vapor Deposition method. TiCN-coated substrates were confirmed by the XRD analysis results. Dense morphology and fine-grained surface of TiCN film were established by SEM images. Cellular toxicity of the coated 304 SS and 410 SS substrates was investigated in the fibroblasts and B-lymphocyte. In respect to that, we have shown coated substrates cytotoxicity, oxidative stress as well as cell viability, reactive oxygen species (ROS), lipid peroxidation (MDA), protein carbonyl, glutathione oxidase (GSSG), and glutathione reductase (GSH) assessment, releasing cytochrome c (Cytc), lysosomal membrane destabilization (AO) may lead to cell death signaling. Our results showed that the coated 304 SS and 410 SS substrates induced cells dysfunction via a significant increase in ROS production, MDA (P<0.01 and P<0.001), protein carbonyl (P<0.05), and GSSG (P<0.05 and P<0.01) that correlated to cytochrome c release (P<0.01). In addition, increased disturbance in oxidative phosphorylation was also shown by the decrease in cell viability (P<0.001) and GSH (P<0.01 and P<0.001) in the coated 304 SS and 410 SS substrates-treated fibroblast and B-lymphocytes. The coated 304 SS and 410 SS substrates contacted cells and trafficked to the lysosomes and this is followed by lysosomal damage, leading to apoptosis/Necrosis. Our results indicated that these materials cause cellular dysfunction and subsequent oxidative stress leading to cognitive impairment in the rat fibroblasts and B-lymphocytes cells.

Comparative Investigation on Corrosion Resistance of Stainless Steels Coated with Titanium Nitride, Nitrogen Titanium Carbide and Titanium-Diamond-like Carbon Films

In this study, the corrosion resistance of titanium nitride (TiN), nitrogen titanium carbide (TiCN) and titanium-diamond-like carbon (Ti-DLC) films deposited on 316L stainless steel (SS) were compared via differences in the surface and section-cross morphologies, open circuit potential tests, electrochemical impedance spectroscopy and potentiometric tests. The corrosion resistance of the TiCN and Ti-DLC films significantly improved because of the titanium carbide (TiC) crystals that obstruct the corrosive species penetrating the as-deposited film in the electrolyte atmosphere. TiN exhibited the lowest corrosion resistance because of its low thickness and high volume of defects. The Ti-DLC film showed the lowest corrosion current density (approximately 4.577 μA/cm2) and thickness reduction (approximately 0.12 μm) in different electrolytes, particularly those with high Cl− and H+ concentrations, proving to be the most suitable corrosion protection material for 316L SS substrates.

Cellular Toxicity Mechanisms of TiCN-Cp-Ti Screw on Tooth Gum Cells in Rat

Cellular toxicity mechanism of TiCN film deposited on Cp-Ti substrate by Cathodic Arc Physical Vapor Deposition (CAPVD) method has yet to be clarified. The present study is aimed at finding out the possible effects of synthesized TiCN on the isolated tooth gum cells and realizing its cytotoxicity mechanism under experimental conditions compared to that of Au screws (standard in medicine). Results of the XRD analysis showed that TiCN film was formed in coating. The SEM image of TiCN film displayed a rough and irregular morphology and fine-grained surface. In addition, some other features such as cell viability, the level of Reactive Oxygen Species (ROS), lipid peroxidation (MDA), Glutathione Count (GSH and GSSG), Adenosine Triphosphate (ATP) were examined. On the other hand, activity of succinate dehydrogenase (complex II), NADH dehydrogenase (complex I), Coenzyme Q-cytochrome c reductase/Cytochrome b (complex III) and cytochrome c oxidase (complex IV) were also determined. Finally, it was also determined that level of Alkaline Phosphatase (ALP), Aspartate Amino Transferase (AST), Alanine Aminotransferase (ALP), Urea, Creatinine Clearance (CR) in rat (tooth gum cells) could also change. The results of the study revealed that TiCN coating did not incur an extremely change on cellular toxicity biomarker compared to Au standard screw in animal study. Our study provides the first evidence that TiCN coating is a biocompatible material in the cell. This paper suggests that the use of the TiCN in human dental applications need further examinations in a wide range of cellular-death signaling.

Tribological Behavior of Tool Steel Substrate and Solid Films against 304 BA Austenitic Stainless Steel under Dry Sliding

The objective of this work is to study the tribological behavior of the contacting surfaces of SKD11 grade hardened cold work tool steel against grade SUS304BA austenitic stainless steel. DLC, CrN, TiN, and TiCN films were coated on the surface of the tool material to test the tribological performance. Simulation testing with a pin-on-disk was used in this study. The study was done under dry conditions with sliding velocities at 50, 100, and 150 mm/s and contact pressures of 807, 1095, and 1280 MPa. The results show that the main problem is the adhesion of the workpiece material on the tool surface. The severity of the adhesion from the workpiece material is proportional to the sliding velocity and the contact pressure between the contacting surfaces. The coefficient of friction between the contacting surfaces has a positive relationship with the adhesion occurring on the tool surface. The hardness of the film coating is useful for preventing wear of the tool material, especially under high pressure between the contacting surfaces. However, it does not prevent the adhesion of workpiece material of low sliding velocity and low contact pressure conditions. Noncoated SKD11 tool steel has better effectiveness of adhesion performance than CrN, TiN, and TiCN film coatings.

Comparative Investigation on the Tribological Performances of TiN, TiCN, and Ti-DLC Film-Coated Stainless Steel

TiN, TiCN, and Ti-diamond-like carbon (DLC) films were coated on 316L stainless steel surfaces by physical vapor deposition. All films exhibited uniform and dense surfaces with good adhesion. The Ti-DLC film demonstrated the lowest surface roughness. TiC and free C were observed in both the TiCN and Ti-DLC films. Among the three films, the TiCN film demonstrated the highest hardness and elastic modulus, followed by the Ti-DLC film and finally the TiN film. Under dry conditions, all films exhibited significantly lower coefficients of friction than stainless steel. The Ti-DLC film showed the lowest coefficient of friction and is thus considered an ideal anti-wear material for orthodontic applications. The friction mechanisms of the three films were also compared. Therefore, this study provides experimental data and a theoretical basis that may guide the production and modification of dental braces.

20 Hz synchrotron X-ray diffraction analysis in laser-pulsed WC-Co hard metal reveals oscillatory stresses and reversible composite plastification

The lifetime of WC-Co inserts used in cutting processes, such as milling, is limited by millisecond temperature and mechanical pulses, which occur as a result of interrupted tool-workpiece contact, thermal fatigue and wear. In the current work, synchrotron X-ray diffraction (XRD) was used in conjunction with a pulsed laser heating set-up to characterise the time-dependent development of stresses and microstructure in locally irradiated WC-Co inserts coated by chemical vapour deposition with 6.5 and 3.5 μm thick TiCN and α-Al2O3 films, respectively. Diffraction data from the WC phase were used to evaluate the time and temperature-dependent evolution of in-plane stresses, thermal strains and integral breadths of WC diffraction peaks in experiments with a single and five successive laser shocks applied within 2.2 and 20 s, respectively, using a laser spot diameter of ~5.8 mm and an X-ray beam size of 1 × 1 mm2. The laser heating induces the formation of compressive stresses in the inserts' substrates. Above a temperature of ~750 °C, at the onset of WC-Co composite plastification, compressive stresses relax and then vanish in WC at the maximal applied temperature of ~1300 °C, followed by the build-up of tensile stresses. The applied cyclic heating up and cooling down led to the repetitive formation of compressive and tensile stresses, with temperature dependencies oscillating with the number of applied laser pulses. The observed relatively high tensile stress level of ~1100 MPa in WC was a consequence of the stabilising function of the coating, which hindered the initiation of surface hot cracks and stress relaxation. The stress evolution was coupled with changes in XRD peak broadening, which however strongly depended on the particular hkl reflections and showed oscillatory behaviour within a single temperature cycle. In summary, the unique diffraction set-up revealed stress levels and provides insight into the WC-Co composite plastification mechanism governing the stress build-up and relaxation in locally thermo-shocked WC-Co inserts at millisecond time resolution.

Influence of C2H2 Flows on Microstructure and Corrosion Resistance of TiCN Films Doped with Carbon Atoms

Nanosized TiCN/TiN films were deposited on AZ31 by reactive magnetron sputtering under different acetylene flows. The microstructures of obtained films were characterized, and their corrosion behaviors were also investigated. The films doped with carbon atoms under different acetylene flows own different structures and grain sizes. The grain size decreased to some extent, and the film structure changed from polycrystalline to nanocrystalline, with an increase of C2H2 flow. The surface morphology also changed from rough to smooth, with an increase of C2H2 flow. The Tafel curves and electrochemical impedance spectroscopy (EIS) demonstrated that the composite films could greatly improve the corrosion resistance of bare substrates in a 3.5% NaCl solution, and the films’ corrosion resistance is different, owing to their different structures and grain sizes.

Corrosion Resistance of TiCN Films Prepared with Combining Multi-arc Ion Plating and Magnetron Sputtering Technique

TiCN films were deposited on AISI 304 stainless steel substrate by combining multi-arc ion plating and magnetron sputtering technique with ionizing titanium and graphite targets in an Ar+N2 mixture gas. The effect of duty ratio on the microstructure and corrosion resistance of TiCN films in a NaCl 3.5 wt% solution was investigated. The results show that the as-deposited films exhibit smooth, uniform and dense morphologies, mainly forming a fcc-TiN type structure with Ti-(C, N) bond as well a as few α-CNx, and present (111) preferred orientation with the increase of duty ratio. TiCN films display a better resistance to corrosion than the bare substrate; as the duty ratio increases, the corrosion resistance is enhanced gradually. When the duty ratio is 40%, the TiCN film shows the optimal corrosion resistance with a corrosion current density (icorr) of 3.262×10−7 A·cm−2 and a polarization resistance (Rp) of 238.4 kΩ·cm2. Electrochemical impedance spectroscopy (EIS) of the films also indicates that the penetration behavior of corrosive ions and the local corrosion process are two key factors affecting the electrode corrosion reaction kinetics process, which is consistent with the polarization curves analyses.

Influence of substrate bias on the structure and properties of TiCN films deposited by radio-frequency magnetron sputtering

The aim of this paper is to investigate the effects of the substrate bias on the structure and properties of the TiCN thin films. The TiCN films were grown onto silicon and steel substrates by rf reactive magnetron sputtering from a pure titanium target in Ar-CH4-N2 gas mixture. Various techniques (such as X-ray diffraction, Raman spectroscopy, energy dispersive X-ray spectroscopy, nanoindentation and potentiodynamic polarization) were used to analyze the structure, phase composition, mechanical properties, and corrosion-resistance of TiCN films. Additionally, the friction and wear properties of TiCN films were investigated by sliding them against alumina ball in the air. Experimental results of the deposition rate showed a decrease from 31nm/min to 9nm/min at biased substrate voltage from Vs=0 to −100V respectively. The refractive index for the TiCxNy films was between 2.10 and 2.26, while the roughness of the films ranged from 14.2nm and 4.2nm. The film deposited at 0V was amorphous, while films at other bias voltages have a face-centered cubic structure (like NaCl type) with a preferential growth orientation of (111). It was observed that Ti and C contents increase from 38 to 52at.% and 25 to 36at.% respectively, as a function of increasing bias voltage. The results also indicate that TiCN films deposited at a substrate bias voltage of −70V had a maximum hardness of 39GPa, and exhibited better wear resistance, with minimum wear rate and lower coefficient of friction of 0.13. The hardness significantly increased from 16 to 39GPa when the bias voltage was increased from 0 to −70V and then slightly decrease to 38GPa as further increased to −100V. The minimum corrosion current density of the film was 0.0205mA/cm2 for films deposited at −70V, which is about five times less than that of the uncoated steel (0.1140mA/cm2).

Effect of friction at chip–tool interface on chip geometry and chip snarling in tapping process

During tapping processes, the chip snarling problem must be resolved to improve manufacturing efficiency. In this study, we used an electroless plating method to develop a tapping tool coated with Ni−P/abrasive-particle composite film to solve the chip snarling problem. The tapping test was conducted at 10m/min (conventional cutting velocity) and 50m/min with a machining center. The cutting torque and thrust force were measured using a dynamometer. The results of the tapping test indicate that the developed tapping tool coated with the composite film prevented chip snarling at 10m/min and 50m/min. The dimensionless diameter for the developed tapping tool, which is the diameter of the chip curl divided by the width of the helical flute, was less than 1.0 for both cutting conditions, whereas that for steam-treatment and TiCN film is greater than 1.0. Furthermore, we estimated the coefficient of friction between the rake face of the cutting edge of the tapping tool and the chip from the thrust force and cutting torque. The estimated coefficient of friction for the tapping tool coated with the composite film (>1.23) was greater than that for the other methods (<1.23). These results indicate that a high coefficient of friction (>1.23) is necessary to prevent chip snarling, and due to the high coefficient of friction, the developed tapping tool can prevent chip snarling even at a speed of 50m/min.

Improvement of oxidation resistance of TiCN films prepared by laser alloying

In this paper, we report the structural and electronic properties of TiCxNy films prepared by laser treatment under controlled gas atmosphere. X-ray diffraction shows the formation of TiCxNy along with the solid solutions of Ti(CN). The TiCxNy phases have been formed and are stable up to 650 °C. Subsequent laser irradiation at different laser energy densities in Ar-atmosphere modifies the microstructure and becomes oxidation resistant. Due to the formation of nano-crystalline TiCxNy, the affinity of Ti toward oxygen has been reduced remarkably after the Ar-treatments. Surface structure analysis by valence band spectroscopy reveals that the hybridization between Ti 3d and C 2p is increasing after the subsequent Ar-treatment at the cost of Ti 3d and N 2p hybridization.

Properties of TiAl/TiAlN/TiAlCN Films Deposited by Arc Ion Plating on GCr15 Rings

Ring is one of the major textile spinning machine consumable part, it has an important influence on yarn quality and cost. Ring of domestic cotton spinning enterprises generally has poor hardness, bad accuracy, not durable and difficult to guarantee the quality of the yarn, foreign ring has excellent performance, but it is too expensive, so it is difficult to widely used in China[1]. Vacuum arc ion plating technology has a wide range of applications in the aerospace, automobile, mold, tool, electronics and other fields [2-3]. TiN film which is prepared by arc ion plating technology has been widely used because of the TiN film has poor oxidation resistance and wear resistance at high temperatures, so the ternary films are developed on TiN film, such as TiAlN [4], TiCN etc. Traveller circle in the ring on the slide to produce large amounts of heat, it makes the ring surface temperature reach 400°C. When higher than 400°C, the TiCN film failure, therefore, ring should not be plated on the TiCN films. While TiAlN film oxidation temperature reaches 800°C. In HSS twist drill, depositing of TiAlN film can improve the service life more than four times [5]. Studies [6-8] have found that using pulsed laser deposition and chemical vapor deposition technique to prepare TiAlCN film, its wear resistance, high temperature stability is better. Pulsed laser deposition is mainly used in laboratory research. It is difficult to deposit a large area uniform film. Chemical vapor deposition of deposition rate is less than the arc ion plating, and produces lots of waste gas, leading to the environment is polluted. Arc ion plating technology can deposit the uniform films of large area with high deposition rate and deposition with no environmental pollution, therefore, this study, by means of vacuum arc ion plating technology to prepare high-precision, long-life and low-cost domestic cotton spinning ring. In order to obtain the best film process parameters, the performance of film is investigated at different bias and arc current.

Influence of the C2H2 flow rate on gradient TiCN films deposited by multi-arc ion plating

Gradient TiCN films were deposited in the arc ion plating system with Cr and Ti targets under the mixed Ar, C2H2 and N2 gases at a temperature of 480°C. In this study, the effect of the C2H2 flow rate on composition, microstructure, bonding energy, hardness, modulus, elasticity, plasticity, adhesion and tribological behaviors of the deposited TiCN films were systematically investigated. The XRD result showed that all the films exhibited a highly textured growth with the (111) as the preferred orientation along the surface normal. By increasing the flow rate of C2H2, the contents of TiC and TiCN decreased and increased, respectively, which led to a significant decrease in hardness from 62GPa to 31GPa. The adhesion strength increased and wear rate decreased due to the decrease of the brittle TiC phase in the films.

Structural, mechanical and biological comparison of TiC and TiCN nanocomposites films

Abstract 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.