Substrate effect on wear resistant transition metal nitride hard coatings: Microstructure and tribo-mechanical properties

Four types of different hard transition metal nitrides (TMN:ZrN, CrN, WN and TiN) coatings were deposited on Si (100) and 316LN stainless steel substrates using DC magnetron sputtering. A comprehensive study of microstructure and substrate dependent tribo-mechanical properties of TMN coatings was carried out. Higher hardness (H) and elastic modulus (E) were obtained for WN (H=40 GPa and E=440 GPa) and TiN (H=30 GPa and E=399 GPa) coatings. This is related to the formation of (100) and (111) preferred orientations in WN and TiN coatings, respectively. However, the less hardness and elastic modulus were obtained for ZrN and CrN coatings where (200) orientation is preferred. Remarkably, low friction coefficient (0.06–0.57) and higher wear resistance in the coatings deposited on steel substrates are directly associated with the higher resistance to plastic deformation (H³/E²) and the presence of intrinsic compressive stress. Three body wear modes enhanced the friction coefficient (0.15–0.62) and the wear rate in the coatings deposited on Si substrates. This is primarily associated with low fracture toughness of brittle single crystalline Si (100) substrates. Steel-on-steel contact was dominated in ZrN/steel sliding system. This occurs due to the severe adhesive wear mode of steel ball, whereas, the abrasive wear modes were attained for the CrN, WN and TiN coatings sliding against steel balls.     

Syntheses of nano-multilayered TiN/TiSiN and CrN/CrSiN hard coatings

Nano-structured superhard coatings represent the state-of-the-art in the rapidly increasing worldwide market for protective coatings. In this study, the combination of nano-composite and nano-multilayered structures into the same coating was attempted. Nano-multilayered coatings of TiN/TiSiN and CrN/CrSiN were deposited on tool steel substrates by closed-magnetic-field unbalanced DC magnetron sputter ion plating. The coating structures were characterized using X-ray diffraction, atomic force microscopy, and scanning electron microscopy. Mechanical characterizations were performed including nano-hardness measurement, progressively-increasing-load scratch test, and wear test. TiN/TiSiN coatings have a nano-hardness of 40.2 GPa, whereas CrN/CrSiN coatings have a hardness of 30.9 GPa. TiN/TiSiN coatings also showed a higher critical failure force and scratch fracture toughness as well as better wear resistance and lower acoustic emission signal, indicating less total damage to the coatings.     

Microstructure evolution and wear resistance of nitride/aluminide coatings on the surface of Ti-coated 2024 Al alloy during plasma nitriding

A duplex surface treatment consisting in depositing a Ti film followed by plasma nitriding was adopted to improve the wear resistance of 2024 Al alloys. Nano-grained Ti films were firstly deposited on the substrate surface by using magnetron sputtering, then plasma nitrided for 8 h at 400 °C, 430 °C, 460 °C and 490 °C, in a gas mixture of 40% N₂+60% H₂. Duplex coatings composed of three sublayers (i.e. the outmost TiN_0.3 layer, the intermediate Al₃Ti layer and the inside Al₁₈Ti₂Mg₃ layer) were obtained at nitriding temperature higher than 460 °C. The coatings obtained at 400 °C and 430 °C consisted of mainly α-TiN_0.3 with (002) preferred orientation. The surface hardness of the coatings increased at higher nitriding temperature, reaching the maximum of 500 HV at 490 °C, which was about 8 times higher than that of the uncoated alloy. The friction coefficients of 2024 Al alloy decreased in the coatings prepared at higher nitriding temperature, reaching the lowest values of 0.31 at 490 °C. The wear rate of the coated samples decreased by 56% compared with the uncoated ones. The analysis of worn surface indicated that the nitrided samples exhibited severe adhesive wear at 400 °C that changed to predominant abrasive wear at increased nitriding temperature.     

Characterization of thick and soft DLC coatings deposited on plasma nitrided austenitic stainless steel

Thick and soft a-C:H:Si coatings containing more than 45% hydrogen (thickness: 25–27 μm, hardness: 6 GPa, Young's Modulus 38 GPa and low ratio of sp³ bonds) were deposited by PACVD with a DC pulsed discharge on nitrided (duplex sample) and non-nitrided austenitic stainless steel (coated sample). After deposition, the chemical, microstructural and tribological properties were studied. Finally, the adhesion and the atmospheric corrosion resistance of a-C:H:Si coatings were also investigated.In pin-on-disk tests, the friction coefficient using an alumina pin of 6 mm in diameter as counterpart, under 0.59 GPa Hertzian pressure was 0.05 for the coated samples and 0.076 for the duplex samples. These values were more than one order of magnitude smaller than the friction coefficient of the nitrided sample without coating, which was around 0.65. In the coated samples, the wear loss could not be measured. In ball-on-disk tests under dry sliding conditions, the coatings were tested under different Hertzian pressures (1.29, 1.44 and 1.57 GPa) using a steel ball with a diameter of 1.5 mm as counterpart. Using a normal load of 9 N, the a-C:H:Si coating of the coated samples was broken and detached thus leading to a coefficient of friction of around 0.429. However, in contrast to that, the friction coefficient of the duplex samples remained stable and reached as maximum a value of 0.208.In abrasive tests, mass loss was undetectable in both duplex and coated samples. Furthermore it could be seen that the a-C:H:Si film showed only some smaller grooves and no severe damage or deformation. On the contrary, severe damage was observed in the only nitrided sample. With respect to adhesion, the critical load to break the coating was higher in the duplex sample (27 N) than in the only coated sample (16.3 N). By chemical analysis using the salt spray fog test, the duplex sample remained clean, but the coated sample failed and presented film delamination as well as general corrosion.     

Effects of tailored nitriding layers on comprehensive properties of duplex plasma-treated AlTiN coatings

Duplex-treated AlTiN coatings were deposited by advanced plasma assisted arc (APA-Arc) technology on pre-plasma nitrided AISI-H13 steel substrates using different N₂/H₂ flow ratios. The microstructures and properties of the AlTiN coatings were comprehensively characterized and analyzed. The results show that the N₂/H₂ flow ratios can tailor the thickness of compound layer during plasma nitriding process and the bright nitriding layer without compound layer is achieved. The properties of duplex-treated AlTiN coatings are well improved compared with monolayer AlTiN coating. The adhesion of the AlTiN coating is well enhanced by duplex treatment process, and adhesion grade increases from HF3-4 for monolayer AlTiN coating to HF1 for composite coatings. Moreover, the composite coatings with various thickness compound layers show different load-bearing capacities, and the interfacial adhesion force of the composite coating without compound layer reaches 61 N. The hardness of AlTiN coating is also enhanced by duplex treatment with the highest hardness of 2935 HV_0.05. Meanwhile, tribological properties of AlTiN coatings are also slightly improved by duplex treatments.     

Influence of plasma nitriding treatment on the adhesion of DLC films deposited on AISI 4140 steel by PVD magnetron sputtering

Duplex surface treatments composed of diamond like carbon (DLC) coating followed by plasma nitriding have drawn attention for a while. In this study, AISI 4140 steel substrates were plasma nitrided at different treatment temperatures and times. Then, DLC films were deposited on both untreated and plasma nitrided samples using PVD magnetron sputtering. The effect of different plasma nitriding temperatures and times on the structural, mechanical and adhesion properties of DLC coatings was investigated by XRD, SEM, microhardness tester and scratch tester, respectively. It was found that surface hardness, intrinsic stresses, layer thickness values and phase distribution in modified layers and DLC coating were the main factors on adhesion properties of duplex coating system. The surface hardness and residual stress values of AISI 4140 steel substrates significantly increased with both DLC coating and duplex surface treatment (plasma nitriding + DLC coating). Increasing plasma nitriding temperature and time also increased the diffusion depth and the thickness of modified layers. Hard surface layers led to a significant improvement on load bearing capacity of the substrate material. However, it was also determined that the process parameters, which provided lower intrinsic stresses, improved the adhesion properties of the duplex coating system.     

Effects of B/C ratio on the structural and mechanical properties of TiBCN coating deposited by PACVD

TiBCN coating is known as a hard, self-lubricant and wear resistant coating which can be applied on industrial tools to increase their working life time under severe wear conditions. In this paper, TiBCN coatings with different B/C ratios were applied on H13 steel using plasma-assisted chemical vapor deposition from BBr₃, TiCl₄, CH₄, N₂ and H₂ reactants at 500 °C. The results signified that the introduction of B and C elements to TiN changed its preferred crystalline orientation from (200) to (111) and decreased crystal size from 12 to 9 nm as a result of the formation of amorphous phases which constrain grain growth. The addition of B and C altered the coating's nucleation and growth mechanisms and generated a strong surface etching agent of HBr which significantly changed surface morphology and roughness. Increasing flow ratio of CH₄ to BBr₃ from 0.125 to 0.25 influenced the coating's mechanical properties and increased coating's hardness from 18.1 to 23.2 GPa and Young's modulus from 296 to 334.7 GPa. Rising coating's C content remarkably improved its nano-wear resistance and the coating with the highest C content exhibited a wear volume of 1*10⁻¹⁹ m³ which was about 63% lower than that of TiN coating.     

Preparation and investigation of pulse co-deposited duplex nanoparticles reinforced Ni-Mo coatings under different electrodeposition parameters

In this work, Ni–Mo–SiC–TiN nanocomposite coatings were deposited on aluminium alloy by pulse electrodeposition with various electrodeposition parameters. The influences of the pulse frequency and duty cycle on the phase structure, morphology, mechanical and corrosion performance of the coatings were systematically investigated. The results showed that with increasing pulse frequency and decreasing duty cycle, the content of embedded duplex nanoparticles increased, and the grains refined gradually. The nanocomposite coating that was prepared at 20% duty cycle and 1000 Hz pulse frequency exhibited compact, uniform, and fine microstructures with the maximum incorporation of nanoparticles (6.81 wt% TiN and 1.72 wt% SiC). The wear rate and average friction coefficient then declined to 4.812 × 10^?4 mm³/N·m and 0.13, respectively, with a maximum microhardness of 519 HV. Simultaneously, the corrosion current density was reduced to 3.11 μA/cm², and a maximum impedance of 34888 Ω cm² was exhibited. The uniformly distributed duplex nanoparticles acted as a hindrance, which consequently supported the enhancement of corrosion and wear resistance. By investigating the variation of the pulse diffusion layer with electrical parameters, it was discovered that when the crystallite size is equivalent to or smaller than the diffusion layer thickness, it would be easier to cross the diffusion layer to incorporate in the coating. Additionally, the effects of various duty cycles and pulse frequencies on the nucleation process of the grains were discussed.     

Microstructure and indentation damage resistance of ZrB2‐20 vol.%SiC ipo‐eutectic composites

Zirconium diboride with 20 vol.% silicon carbide bulk composites were fabricated using directionally solidification (DS) and also by spark plasma sintering (SPS) of crushed DS ingots. During the DS the cooling front aligned the c‐axis of ZrB₂ grains and its Lotgering factor of f_(00l) was high as 0.98. The Vickers hardness was anisotropic and it was high as 17.6 GPa along the c‐axis and 15.3 GPa when measured in an orthogonal direction. On both surfaces, even when using 100 N indentation load, no cracks were observed, suggesting a very high resistance to crack propagation. Such anomalous behavior was attributed to the hierarchical structure of DS sample where the ZrB₂ phase was under strong compression and the SiC phase was in tension. In the SPSed sample, the microstructure was isotropic respect to the direction of applied pressure. Indentation cracks appeared around the indent corners but not emanated from the diagonals, confirming high damage resistance.     

盐浴复合热处理技术耐磨涂层组织与性能

为寻求环保型耐磨表面改性技术,以Q235为基体进行盐浴复合热处理(QPQ),对其形貌、硬度、摩擦磨损与耐腐蚀性能进行了测试。结果表明,QPQ处理层硬度约为739 HV,摩擦磨损性能与镀铬层相当,耐蚀性能优于渗氮处理。     

Microstructure and nanoindentation creep behavior of TiC reinforced steel matrix composite after stabilizing heat treatments

The microstructure and nanoindentation creep behavior of characteristic phases in TiC reinforced steel matrix composite after stabilizing heat treatments were investigated. The results showed that the microhardness of matrix increased from 4.85 ± 0.30 GPa in the annealed sample to 13.45 ± 0.71～ 16.06 ± 0.88 GPa after stabilizing heat treatments, and the apparent hardness of TiC particle was also improved due to the martensitic strengthening of matrix. The dominant creep mechanism of the composite was dislocation movement, the primary micro creep stage dominated the micro creep behavior of annealed composite and the steady state creep dominated the micro creep behavior of stabilized composites. The micromechanical properties of the characteristic phases in the composite after TCC treatment were well matched, and the overall creep resistance of that was excellent, which provided theoretical support in achieving the consistency of micromechanical properties of the composite during the stabilizing heat treatments.     

Fabrication and characterization of in-situ duplex plasma-treated nanocrystalline Ti/AlTiN coatings

Plasma nitriding and plasma-assisted PVD duplex treatment was adopted to improve the load-bearing capacity, fatigue resistance and adhesion of the AlTiN coating. Ion etch-cleaning was applied for better adhesion before plasma nitriding. After plasma nitriding Ti interlayer was in-situ deposited by high power impulse magnetron sputtering (HIPIMS), followed by the AlTiN coating through in-situ deposition by advanced plasma-assisted arc (APA-Arc). The microstructure and properties of the duplex-treated coating were carefully characterized and analyzed. The results show that the thicknesses of the nitriding zone, the γ′-Fe₄N compound layer, the Ti interlayer and the AlTiN top layer with nanocrystalline microstructures are about 60 μm, 2–3 μm, 100 nm and 6.1 μm, respectively. The nitriding rate is about 30 μm/h and the AlTiN coating deposition rate reaches 6.1 μm/h. The interfacial adhesion of the Ti/AlTiN coating is well enhanced by ion etch-cleaning and a Ti interlayer, and the load-bearing capacity is also improved by duplex treatment. In addition, the instinct hardness of the Ti/AlTiN coating reaches 3368HV_0.05 while the wear rate coefficient of 5.394×10⁻⁸ mm⁻³/Nm is sufficiently low. The Ti/AlTiN coating, which possesses a high corrosion potential (E_corr=−104.6 mV) and a low corrosion current density (i_corr=4.769 μA/cm²), shows highly protective efficiency to the substrate.     

A comparative study of duty cycle and argon / methane flow ratio effect on the tribological behavior of DLC coatings over nitrided Astaloy Mo-based steel

Surface properties of Astaloy Mo-based steel were enhanced by using DLC deposition. The specimens were formed by double-sided compaction and heated for 30 min at 1393 K, in the NH₃ atmosphere. Following this, the plasma nitriding process was applied to improve the adhesion of the DLC coating. Afterward, the DLC coating was performed by Pulsed DC PACVD. Surface characteristics were studied by changing the duty cycle and the Argon/Methane flow ratio. The reciprocating method was carried out to evaluate wear behavior. Field emission scanning electron microscopy equipped with EDS and Raman spectroscopy, hardness tester, nanoindentation test and surface roughness tester were used to evaluate the chemical structure, wear mechanisms of DLC coatings. This study proved that hardness reached up to 12.2 ± 1.11 GPa and the wear behavior was enhanced significantly by the DLC coating deposition. The mass loss increased with a rise in the duty cycle. Increasing the Argon/Methane ratio from 4:1 to 6:1 caused a decrease in the mass loss of DLC coatings. Burnishing, pulling out and adhesive wear were the dominant mechanisms.     

Effect of Na2SiO3 concentration on corrosion resistance and wear resistance of MAO ceramic film on the Al-Mg-Sc alloy

Although Al-Mg-Sc alloy was widely applied to aviation aerospace field, they were vulnerable to local corrosion and wear in the process of long-term service in severe environmental conditions. In this paper, micro-arc oxidation (MAO) ceramic films on Al-Mg-Sc alloy substrate were prepared in electrolyte solutions with different Na₂SiO₃ concentrations, and the corrosion resistance and wear resistance of the MAO samples were studied. The experimental results of potentiodynamic polarization (PDS) and long-term immersion tests indicated that the MAO ceramic film prepared in 10 g/L Na₂SiO₃ electrolyte solution had the best corrosion resistance, as manifested by no obvious cracks, serious collapse and corrosion products on the sample surface and no deep cracks and corrosion paths in the cross-sectional area. The increase of Na₂SiO₃ concentration in electrolyte solution also improved the wear resistance of MAO ceramic film, as manifested by low wear depth (10 μm)and width (1 mm) of the MAO ceramic film prepared in 10 g/L Na₂SiO₃ electrolyte solution against GCr15 steel ball. Studies in mechanisms suggested that as the Na₂SiO₃ concentration in the electrolyte increased, the MAO ceramic film became denser, which could prevent the penetration of corrosive medium, promote the generation of the anti-wear layer with SiO₂ as the main component to enhance the wear resistance. MAO ceramic film formed in Na₂SiO₃ electrolyte solution provided good protective performance for Al-Mg-Sc alloy in the corrosion and wear conditions, which had a broader application prospect.     

Thermal treatment effect on the surface and in vitro corrosion characteristics of arc deposited TiN coating on Ti alloy for orthopedic applications

The influence of post thermal treatment at (500,600,700, and 800 °C) of cathodic arc physical vapor deposited TiN coated Ti6Al4V (Ti64) alloy was studied for orthopedic uses. The structure, surface characteristics, mechanical properties of coated and treated samples was investigated using XRD, FESEM/EDX, XPS, AFM, and micro indentation. The influence of post heat treatment on the in vitro corrosion-resistant behavior in a physiological medium was assessed by linear polarization, electrochemical frequency modulation, and impedance spectroscopic measurements. The results showed that a TiN layer of 5 ± 0.15 μm was formed over Ti64 alloy with higher microhardness and modulus compared to the bare substrate. The rutile TiO₂ oxide phase begins to form with the TiN at 500 °C, the TiO₂ phase intensity increased with the temperature, and the TiO₂ upper layer over the TiN film was formed at 700 and 800 °C. The microhardness and modulus were increased at 500 °C due to enhanced crystallinity of TiN, then decreased with increasing the temperature due to the internal stress relaxation of TiN and formation of the TiO₂ phase. The treated samples showed higher resistance to plastic deformation compared to the TiN coated and uncoated alloy. The sample treated at 500 °C showed the highest hardness, modulus, and resistance to plastic deformation. The obtained in vitro corrosion results indicated that post thermal treatment improves the corrosion resistance of TiN coated.     

CD-4MCu双相不锈钢在稀硫酸介质中的腐蚀磨损行为

用失重法测定了固溶处理态和固溶+时效处理态CD-4MCu双相不锈钢在稀硫酸介质中的腐蚀磨损速率。结果表明,CD-4MCu在固溶态时硬度低,耐腐蚀磨损性能差;在固溶+时效处理态时硬度高,耐腐蚀磨损性能好。介质温度和浓度升高,CD-4MCu双相不锈钢腐蚀及磨蚀增加,腐蚀磨损交互作用增大。     

Mechanical,biocorrosion, and antibacterial properties of nanocrystalline TiN coating for orthopedic applications

The current study analyzes the surface, mechanical, biocorrosion, and antibacterial performances of a nanocrystalline TiN ceramic coating synthesized using cathodic arc-physical vapor deposition (PVD) on biomedical Ti6Al4V substrates. The surface hardness and modulus of elasticity were assessed using the microindentation method. The adhesion, friction coefficient, and antibacterial properties of the coating were evaluated. The in vitro corrosion of the prepared coated Ti alloy substrate was analyzed in simulated body fluid (SBF) via cyclic potentiodynamic polarization (CPP), dynamic electrochemical impedance spectroscopy (DEIS), and scanning vibrating electrochemical technique (SVET). The results demonstrated that a nanocrystalline TiN coating with a crystallite size of 10.33 nm and a thickness of 5 μm was formed with good adhesion on the alloy surface. The coating had an enhanced surface hardness of 38.63 GPa and a modulus elasticity of 358 GPa, and exhibited enhanced resistance to plastic deformation compared with the substrate – features that can enhance the service life of an implant. The antibacterial experiments indicated an upgraded antibacterial performance of the TiN coating compared to the bare alloy. The in vitro corrosion-resistance analyses confirmed the enhanced surface protective performance of TiN ceramic coatings against biocorrosion in SBF. The results showed higher impedance values in DEIS, a higher passive region in the CPP analysis, and a lower anodic current density in the SVET analysis compared with the bare substrate.     

Wear behaviors and high-temperature oxidation resistance properties of tantalum carbide layer

A TaC/Ta₂C bilayer is obtained by vacuum carburizing technology and characterized by scanning electron microscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction, the nano-indentation, friction and wear test, high-temperature oxidation experiment. XPS analyses indicate that the carburized layer is composed of intermediate layer Ta₂C and outer-layer TaC. The total thickness of the carburized layer is approximately 20 μm. The nano-indentation hardness of the carburized layer along the depth direction varies from 14.632 to 35.832 GPa. The formation of the hard phase in carbide considerably improves the wear resistance of pure Ta. The high-melting-point ceramic phase in carbide improves the high-temperature oxidation resistance of pure Ta, thereby making it serve in high-temperature air environment for a short time.     

AlN and intermetallic compound layers formed between aluminum and austenitic stainless steel using barrel nitriding

Recently, a new nitriding process was proposed to produce the aluminum nitride on an aluminum surface using a barrel. After barrel nitriding, AlN nitride layer is formed on the aluminum surface and the surface hardness can be improved remarkably. In this study, barrel nitriding was performed to investigate the interface between aluminum substrate, with SUS304 austenitic stainless steel used for a physical catalyst. The barrel nitriding was carried out at 893 K for 18 ks, 25.2 ks and 36 ks, respectively with aluminum and aluminum–magnesium alloy powder. After barrel nitriding, aluminum nitride layer and Fe–Al intermetallic compound layers were formed at the interface between pure aluminum and austenitic stainless steel at the same time. The thickness of the aluminum nitride layer and intermetallic layer was increased by increasing the treatment time.     

Wear and corrosion properties of a B–Al composite layer on pure titanium

A boriding and aluminizing two-step method was used to fabricate a B–Al composite layer on the surface of pure titanium. The composite layer was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), nanoindentation, wear tests, and electrochemical experiments. For comparison, single boriding and single aluminizing treatments were performed on pure titanium. The results show that the surface morphology characteristics from the single boriding and single aluminizing treatments were transferred to the composite sample. The XRD pattern reveals that the B–Al composite layer also has XRD peaks of Al₃Ti+TiB₂+TiB. The SEM results revealed that the B–Al composite layer is composed of an outermost TiB₂ layer, a TiB+Al₃Ti sublayer, an Al₃Ti layer, and an internal diffusion layer. The corrosion resistance of the composite sample is slightly better than that of the matrix, and the hardness is approximately 3 times higher than that of the matrix. The wear type is mainly abrasive wear, and the wear resistance is improved; with increasing temperature, the wear on the surface of the sample is intensified, and the wear resistance is reduced.