Nano and Nanocomposite Superhard Coatings of Silicon Carbonitride and Titanium Diboride by Magnetron Sputtering

Superhard coatings (hardness >20 GPa) are being widely researched, driven by the need to use the components under different combinations of environments. Complex properties such as low friction and low wear, increased life time, and increased toughness are required in the same coating. Nanocomposite and nanocoatings are promising materials to achieve them. In the present communication, the author presents research findings on hard nanocomposite and nanocoatings of silicon carbonitride (SiCN) and titanium diborides by magnetron sputtering on Si and steel substrates. XPS, atomic force microscopy, and nanoindentation studies on both the films showed that they possessed high hardness, modulus, and significant elastic recoveries after unloading. These properties can be attributed to nanocrystalline dispersions of carbon nitride and silicon nitride phases in the amorphous SiCN matrix in nanocomposite SiCN thin films, whereas in the case of the TiB₂ film, nanosize grains led to higher hardness.     

电热爆炸定向喷涂NiCr/WC-Co复合涂层的特性

用电热爆炸定向喷涂技术在45钢基体上制备了NiCr／WC-17％Co复合涂层。用扫描电镜以及能谱仪对涂层显微组织和界面情况进行了观察分析。借助纳米硬度计测定了涂层的硬度和模量。结果表明：涂层颗粒细小且分布均匀,可分辨颗粒尺寸在200～300nm;涂层致密,孔隙率为1％;涂层与基体结合良好,界面附近存在元素扩散现象;弹性模量在涂层内最大为290GPa;涂层硬度达到17．7GPa。涂层硬度和弹性模量沿横截面平稳下降,体现出了复合涂层的特征。     

Mechanical properties of PECVD thin ceramic films

Silicon dioxide (thickness 350 nm and 969 nm) and silicon nitride (thickness 218 nm) films deposited on silicon substrate using plasma enhanced chemical vapor deposition process were investigated using a Berkovich nanoindenter. The load-depth measurements revealed that the oxide films have lower modulus and hardness compared to the silicon substrate, where as the nitride film has a higher hardness and slightly lower modulus than the substrate. To delineate the substrate effect, a phenomenological model, that captures most of the ‘continuous stiffness measurement’ data, was proposed and then extended on both sides to determine the film and substrate properties. The modulus and hardness of the oxide film were around 53 GPa and 4–8 GPa where as those of the nitride film were around 150 GPa and 19 GPa, respectively. These values compare well with the measurements reported elsewhere in the literature.     

Fabrication of Ceramic Hip Implant Composites: Influence of Silicon Nitride on Physical,Mechanical and Wear Properties

This study examined the effects of silicon nitride reinforcement on physical, mechanical and wear properties of different ceramic (zirconium oxide, magnesium oxide, chromium oxide and aluminum oxide) containing hip implant composites. The hip implant composites were produced using conventional mixing and spark plasma sintering methods by substituting aluminum oxide (68, 70.5, 73 and 75.5 wt.%) with silicon nitride (0, 2.5, 5 and 7.5 wt.%). Experimental results showed that silicon nitride content had significant effect on the evaluated physical, mechanical and wear properties. The density of the composites found to decrease whereas void content, Young’s modulus, hardness, wear resistance and fracture toughness first decreased (for 2.5 wt.%) and then increased with the increasing amount of silicon nitride content. The maximum hardness, Young’s modulus, wear resistance and fracture toughness values of 28.64 GPa, 280.18 GPa, 0.0076 mm³/million cycles and 11.84 MPa.m^1/2, respectively were registered for 2.5 wt.% silicon nitride additions that also had the lowest void content (0.38%).

     

Investigation of the mechanical properties of electrodeposited nickel and magnetron sputtered chromium nitride coatings deposited on mild steel substrate

Electrodeposition and magnetron sputtering techniques have been employed for the deposition of Ni and bilayer NiCrN coatings, respectively, on mild steel substrate. Ni electrodeposition was performed using sulfate Watt’s bath, while magnetron sputtering was performed on electrodeposited Ni using DC power 350 W and base pressure of 3 × 10^?5 Torr in order to prepare bilayer NiCrN coatings. Structural and mechanical properties of Ni and bilayer NiCrN coatings have been investigated using various characterization techniques such as SEM-EDX, XRD, hardness, adhesion testing, etc. SEM analysis reflects the formation of spherical/nodular particles of varying sizes in NiCrN coating whereas Ni coating shows irregular, agglomerated, and non-uniform distribution of particles. Formation of hard CrN phase in NiCrN coating has been confirmed by XRD and EDX. NiCrN coating exhibits better hardness in comparison with Ni coating due to the formation of nitride phase. Micro scratch testing of bilayer NiCrN coating shows better interlayer adhesion and adhesion with mild steel substrate. The combination of electrodeposition and magnetron sputtering can produce inexpensive NiCrN coating containing hard CrN phase with better mechanical properties for automotive applications.     

Multiple cohesive cracking during nanoindentation in a hard W-C coating/steel substrate system by FEM

Stress evolution and subsequent cohesive cracking in the hard and stiff W-C coating on steel substrate during nanoindentation have been investigated using finite element modelling (FEM) and eXtended FEM (XFEM). The FEM simulations showed that the maximum principal stresses in the studied system were tensile and always located in the coating. They evolved in several stages. At indentation depths below 15% of the relative indentation depth, the maximum principal tensile stresses of ∼3 GPa developed at the top surface of the coating along the indenter/coating interface. At relative depths range 15–60%, the maximum tensile stresses of ∼6–8 GPa concentrated under the indenter tip in the coating along the interface with the substrate. At relative depths exceeding 60%, the maximum stresses gradually increased up to 10 GPa and they were located in the sink-in zone outside the indent as well as below the indenter tip. The first and subsequent cohesive cracks developed when the maximum tensile stresses in the sink-in zone at the top surface of the coating (and at the coating/substrate interface under the indenter) repeatedly reached the ultimate tensile strength of the coating. The hardness profile as well as cohesive cracking is controlled by the deformation of the substrate defined by the ration of the yield stresses of the coating and substrate. Very good correlation between the experimentally obtained cracks and multiple cracks predicted by XFEM confirmed the ability of the applied modelling in the prediction of fracture behavior of the studied coating/substrate system.     

Microstructure and mechanical properties of pulsed laser deposited boron nitride films

Boron nitride films were prepared by pulsed laser ablation from a boron nitride target using a KrF-excimer laser, where the growing films were deposited in nitrogen atmosphere or bombarded by a nitrogen/argon ion beam. Films deposited without or at weak ion bombardment (such films will be called l-BN in this paper) are hexagonal with amorphous to turbostratic microstructure (l-BN) and show high adhesive strength to silicon and stainless steel substrates. By using them as intermediate layers, the adhesion of pure cubic boron nitride films (c-BN) can significantly be improved. l-BN films and l-BN/h-BN/c-BN layer systems have been investigated by in-situ ellipsometry, infrared spectroscopy and cross-section and plan-view high-resolution transmission electron microscopy, including diffraction. The mechanical properties, i.e. stress and hardness, of these films and layer systems are presented. l-BN films deposited at higher laser energy densities have compressive stresses as high as 11.5 GPa. Films deposited at lower laser energy densities have stresses in the range of 4.7 to 1.3 GPa and a Vickers hardness in the range of 18.6 to 7.5 GPa depending on substrate temperature and ion bombardment. The compressive stresses of 400 nm thick adherent c-BN films were estimated to be 4.5 GPa.     

Wear assessment of Cr2O3-/TiAlN-coated DAC-10 tool steel against steel and Al2O3 counterbodies

TiAlN film was deposited on Cr₂O₃-coated plasma-nitrided DAC-10 tool steel to obtained multilayer Cr₂O₃/TiAlN coating layer using cathodic arc deposition technique. The structural make-up of the coating was characterized using Atomic Force Microscopy (AFM) and X-ray diffraction methods, and the mechanical properties were evaluated using nanoindentation and nanoscratch test. The structural phases of the coating indicated the presence of crystalline CrO structure and cubic TiAlN phases. The coating showcased improved hardness (38 GPa), elastic modulus (387 GPa), and adhesion along with appreciable H/E (0.09) and H³/E² (0.366 GPa) attributes. Further, friction-induced wear behavior of the coating was investigated against steel and Al₂O₃ counterbodies under dry sliding conditions. The wear behavior of the coating was greatly influenced by its hardness and deformation properties and frictional behavior of the counterbodies. More spikes and fluctuation were observed in the frictional curve against Al₂O₃ counterbody attributed to the emanation of TiO₂, Cr₂O₃, and Al₂O₃ compounds due to dry sliding leading to the formation of flakes and delamination induced debris. Against the steel counterbody, the coating mainly formed a typical smooth glossy surface ascribed to the formation of Fe₂O₃ compound on the worn surface.     

Carbon and titanium diboride multilayer coatings

Titanium diboride (TiB₂) is a metal-based refractory ceramic material that has been investigated in industrial applications ranging from cutting tools to wear parts, and for use in the aerospace industry. The unique properties which make this material so fascinating are its high hardness, high melting point and its corrosion resistance. TiB₂ is prevented from wider mainstream use because of its inherent brittle nature. With a view to overcome this in coating form and with the aim of providing in addition inherent lubricity, in this study, 50-layer TiB₂/C multilayer stacks have been fabricated, with varying volume fractions of ceramic whereby the interfaces of the layers limit crack propagation in the TiB₂ ceramic.TiB₂ has been multilayered with carbon to make use of the unique and hybrid nature of the bonding in carbon coatings. DC magnetron sputtering with substrate bias was the preferred route for the fabrication of these coatings. AISI tool steel has been used as the substrate material. By varying the amount of TiB₂ ceramic from 50% to 95%, the hardness of the coating is seen to increase from 5 to 17 GPa. The hardness is observed to decrease as a function of increasing carbon content, agreeing with other studies that the carbon layers are not load bearing. The graphitic nature of the sp² bond, however, acts as a lubricant layer.     

脉冲电流密度对Ni-WC纳米复合镀层耐蚀性及硬度的影响

采用脉冲电沉积法在304不锈钢基体上制备出Ni-WC纳米复合镀层,并研究了脉冲电流密度对Ni-WC纳米复合镀层耐蚀性及硬度的影响。结果表明:随着脉冲电流密度的增大,Ni-WC纳米复合镀层的织构呈现规律性变化,晶粒尺寸先减小后增大,硬度先增大后减小。当脉冲电流密度为10A/dm2时,Ni-WC纳米复合镀层的耐蚀性最好,硬度最高。     

The effect of substrate temperature on microstructural evolution and hardenability of tungsten carbide coating in hot filament chemical vapor deposition

Effect of substrate temperature on microstructural evolution and hardenability of tungsten carbide coating produced by hot filament chemical vapor deposition (HFCVD) process was studied. Annealed sheets of 316L stainless steels were used as the substrate. HFCVD technique, with substrate temperatures of 400 and 500°C, was used to deposit tungsten carbide coating on these sheets. Field Emission Scanning Electron Microscope (FE‐SEM) was used to study the evolution of microstructure. X‐Ray Diffraction spectroscopy was used to analyze the phases formed and Raman spectroscopy was employed to differentiate molecular composition of the coatings. The amount of the porosity of the coatings was measured and Vickers hardness measurement was used for hardness assessment. Results show that the tungsten carbide coatings have a honeycomb structure and increasing the temperature of the substrate increases the amount of porosity of the coating. XRD results showed that 3 different crystalline structures containing W, WC, and W₂C were formed in the coating deposited on the 316L stainless steel. Increasing the temperature of the deposition has increased the intensity of the peaks in the XRD results. Raman spectroscopy results indicated the presence of a carbon in the tungsten carbide coatings. Finally, microhardness of the tungsten carbide coating increases with increasing the temperature of the substrate.     

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.     

Excellent corrosion protection performance of epoxy composite coatings filled with silane functionalized silicon nitride

Silicon nitride was firstly used as anticorrosive pigment in organic coatings. An effective strategy by combining inorganic fillers and organosilanes was used to enhance the dispersibility of silicon nitride in epoxy resin. The formed nanocomposites were applied to protect Q235 carbon steel from corrosion. The anticorrosive performance of modified silicon nitride with silane (KH-570) was investigated by electrochemical impedance spectroscopy (EIS), water absorption and pull-off adhesion methods. With the increase of immersion time, the corrosion resistance as well as adhesion strength of epoxy resin coating and unmodified silicon nitride coating decreased significantly. However, for the modified silicon nitride coating, the corrosion resistance and adhesion strength still maintained 5.7×10¹⁰ Ω cm² and 7.6 MPa after 2400-h and 1200-h immersion, respectively. The excellent corrosion resistance performance could be attributed to the chemical interactions between KH-570 functional groups and silicon nitride powders, which mainly came from the easy formation of Si-O-Si bonds. Furthermore, the modified silicon nitride coating formed a strong barrier to corrosive electrolyte due to the hydrophobic of modified silicon nitride powder and increased bonds.     

Influence of radio frequency magnetron sputtering parameters on the structure and performance of SiC films

Amorphous SiC films fabricated by Radio frequency (RF) magnetron sputtering have been widely used due to their excellent properties including high strength, good hardness and outstanding abrasion resistance. However, most researches set a lower target-substrate distance, which limits its large-scale coating for practical industrial application. In this work, the distance between the target and substrate was enlarged to 120 mm, and the effective coating area was about four to ten times than other researches. Furthermore, the effects of sputtering power, deposition pressure, substrate temperature and bias voltage on the structure and performance of SiC films were also investigated. Finally, SiC films with high elasticity modulus (310.8 GPa) and hardness (35.6 GPa) are obtained by RF magnetron sputtering.     

WC的质量浓度对Ni-WC纳米复合镀层耐蚀性及硬度的影响

采用脉冲电沉积方法在304不锈钢基体上制备出Ni-WC纳米复合镀层。研究了WC的质量浓度对Ni-WC纳米复合镀层性能的影响。结果表明:随着WC的质量浓度的增加,Ni-WC纳米复合镀层的耐蚀性先增强后减弱,硬度先增大后减小;当WC的质量浓度为30g/L时,Ni-WC纳米复合镀层的耐蚀性最好,硬度最大。     

On the evaluation of adhesion of coatings by automatic scratch testing

Automatic scratch testing is an expedient technique for comparatively evaluating the cohesive failure load and adhesion failure load of thin coatings on various substrates. In combination with SEM examination of the scratch track, this technique has been used herein to detect and evaluate various effects on coating strength and adhesion. For soft Triballoy T-800 and Stellite SF-6 cobalt-base coatings on 4340 low alloy steel, adhesion was found to be strong and failure was found to be cohesive in the coating. In the presence of a plated chromium interlayer, pre-existing cracks lowered substantially the cohesive failure load, which was also lowered by an increase in the coating deposition pressure. The spacing of transverse cracks within the coating was found in all cases to decrease with increasing applied normal load. In soft aluminum coatings on depleted uranium (DU)-0.75% Ti alloy specimens, alloying aluminum with magnesium or zinc enhanced the coating strength and adhesion. In (Al-Mg) coatings on this substrate, a smoother surface led to a lower friction coefficient and a higher adhesion failure load. In hard, thin TiN coatings on 17-4 PH steel, a lower bias voltage applied to the substrate yielded higher cohesive and adhesion failure loads. In hydrogenated amorphous SiC thin coatings on 4340 steel, loss of hydrogen by annealing converted the residual compressive stresses into tensile stresses and lowered both the cohesive and the adhesion failure loads. Finally, automatic scratch testing proved helpful in determining delamination loads in multilayer TiN/Ti/TiN coatings on DU-0.75% Ti alloy.     

Evolution mechanism of the microstructure and mechanical properties of plasma-sprayed yttria-stabilized hafnia thermal barrier coating at 1400 °C

Yttria stabilized hafnia (Hf_0.84Y_0.16O_1.92, YSH16) coatings were sprayed by atmospheric plasma spraying (APS). The effects of thermal aging at 1400 °C on the microstructures, mechanical properties and thermal conductivity of the coatings were studied. The results show that the as-sprayed coating was composed of the cubic phase, and the nano-sized monoclinic (M) phase was precipitated in the annealed coating. The presence of M phase effectively constrained the sintering of the coating due to its superior sintering-resistance. The Young's modulus kept at a nearly same level of ~78 GPa even after annealing, and the coating annealed for 6 h yielded a maximum value of hardness but revealed a declining tendency in the Vicker's hardness with prolonged sintering time. The thermal conductivity increased from 0.8-0.95 W m^-1 K^-1 at as-sprayed state to 1.6 W m^-1 K^-1 after annealing at 1400 °C for 96 h. The dual-phase coating is promising to serve at temperatures above 1400 °C due to its excellent thermal stability and mechanical properties.     

Structural and tribological characterization of amorphous and crystalline titanium-nickel coatings

The interest in titanium-nickel (TiNi) alloys has increased with the discovery of the versatile properties of these alloys. In this study, the structural, mechanical and tribological properties of amorphous and crystalline TiNi coatings were investigated. The TiNi coatings were deposited with magnetron sputtering system. The crystallization process was conducted in a vacuum heat treatment furnace. The structural properties of the coatings were investigated with XRD, SEM and EDS analyses. Micro-hardness and pin-on-disc wear tests were used to obtain the mechanical and tribological properties of the coatings. AISI D2 steel, AISI 52100 steel, Aluminum 2024 alloy and copper were used as substrate materials, hence the effects of different substrates were also investigated. The highest coating hardness was obtained as 8.5?GPa and the lowest coefficient of friction value was obtained as 0.18. The tribological tests showed that the amorphous and crystalline TiNi coatings have different coefficient of friction and wear rate and using different substrate affects these properties.     

Investigation of the adhesion of NbN coatings deposited by pulsed dc reactive magnetron sputtering using scratch tests

Scratch tests have been used to investigate the adhesion of niobium nitride (NbN) coatings that were deposited by pulsed dc reactive magnetron sputtering at target currents of 1.5, 2.5, and 3.5 A onto M2 tool steel and silicon wafer. The coating adhesion on each material substrate was investigated using a progressive load scratch tester (PLST) and a multi-pass scratch tester (MPST). Microhardness tests and scanning electron microscopy (SEM) were also used to examine the hardness and microstructure of the NbN coatings. These results have indicated that the structural, mechanical, and adhesion properties of the NbN coatings improve with increasing target currents. While performing PLST and MPST tests, the highest adhesion and lowest friction force were obtained for the coatings deposited at a target current of 3.5 A. In addition, the triboscobic behaviors that were observed from the MPST of the coatings indicated that the target currents affect the friction behavior of the coatings.     

碳钢表面燃烧合成网络结构Cr_3C_2-WC陶瓷复合涂层的相组成与性能

利用燃烧合成技术,在普通碳钢表面原位自生Cr3C2-WC网络结构陶瓷复合涂层。通过X射线衍射仪、扫描电子显微镜、能谱仪和显微硬度计等测试手段对涂层中的网络结构陶瓷增强相的组织形貌、物相组成、化学成分及力学性能等进行了表征。结果表明:涂层由Cr3C2,WC,FeNi3,σ-FeCr和δ-CrNi等组成,Cr3C2-WC网络结构增强相由过饱和固溶体共晶析出。涂层与基体间的结合为冶金结合;表面涂层厚度约为2.0mm,显微硬度约为7.2GPa。制备的表面复合材料的硬度高于基体,改性效果明显。