Properties of the TiN coatings on previously Ti ion-implanted magnesium alloy substrate

To enhance the mechanical properties of TiN coating on magnesium alloy, metal vapor vacuum arc (MEVVA) ion implantation was performed to modify magnesium alloy substrate before TiN film deposition. Implantation energy was fixed at 45 keV and dose was at 9 × 10¹⁷ cm^− 2. TiN coatings were deposited by magnetically filtered vacuum-arc plasma source on unimplanted and implanted substrate. The microstructure composition distribution and phase structure were analyzed using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The chemical states of some typical elements of the TiN coating were analyzed by means of X-ray photoelectron spectroscopy (XPS). The properties of corrosion resistance of TiN coatings were studied by CS300P electrochemical-corrosion workstation, and the mechanism of the corrosion resistance was also discussed.     

Influence of substrate bias, deposition temperature and post-deposition annealing on the structure and properties of multi-principal-component (AlCrMoSiTi)N coatings

Nitride films are deposited from a single equiatomic AlCrMoSiTi target by reactive DC magnetron sputtering. The influence of the substrate bias and deposition temperature on the coating structure and properties are investigated. The bias is varied from 0 to − 200 V while maintaining a substrate temperature of 573 K. And the temperature is changed from 300 to 773 K whilst maintaining a substrate bias of − 100 V. From X-ray diffraction analysis, it is found that all the as-deposited coatings are of a single phase with NaCl-type FCC structure. This is attributed to the high mixing entropy of AlN, CrN, MoN, SiN, and TiN, and the limited diffusion kinetics during coating growth. Specific aspects of the coating, namely the grain size, lattice constant and compressive stress, are seen to be influenced more by substrate bias than deposition temperature. In fact, it is possible to classify the deposited films as large grained (~ 15 nm) with a reduced lattice constant (~ 4.15 Å) and low compressive residual stresses for lower applied substrate biases, and as small grained (~ 4 nm) with an increased lattice constant (~ 4.25 Å) and high compressive residual stresses for applied biases of − 100 V or more. A good correlation between the residual stress and lattice constant under various deposition conditions is found. For the coatings deposited at − 100 V, and at temperatures above 573 K, the hardness could attain to the range of 32 to 35 GPa.Even after annealing in vacuum at 1173 K for 5 h, there is no notable change in the as-deposited phase, grain size or lattice constant of the coatings but an increase in hardness. The thermal stability of microstructure is considered to be a result of the high mixing entropy and sluggish diffusion of these multi-component coatings. For the anneal hardening it is proposed that the overall bonding between target elements and nitrogen is enhanced by thermal energy during annealing.     

Deposition of nanolayered CrN/AlBN thin films by cathodic arc deposition: Influence of cathode arc current and bias voltage on the mechanical properties

Thin films of CrAlBN were deposited on SKD 11 tool steel substrate using Cr and AlB cathodes in a cathodic arc plasma deposition system. The influence of AlB cathode arc current and substrate bias voltage on the mechanical and the structural properties of the films was investigated. The CrAlBN thin films had a multilayered structure in which the nano-crystalline CrN layer alternated with the amorphous AlBN layer. The hardness of the films increased as the AlB cathode arc current was raised from 35 to 45 A, and then decreased with further increase of the current. The hardness of the films increased rapidly with the increase of the bias voltage from − 50 to − 150 V. Further increase in the bias voltage decreased the hardness. The maximum hardness of 48 GPa was obtained at the bias voltage of − 150 V. With the increase of bias voltage, a good correlation between the residual stress and the hardness of the films was observed.     

Study of adhesion of TiN grown on a polymer substrate

TiN films were deposited on polycarbonate substrates by cathodic vacuum arc using the plasma immersion ion implantation and deposition (PIII&D) method. The biaxial intrinsic stress in the film deposited using PIII&D with 3 kV applied bias was 0.3 GPa — much lower than that found in films deposited without the application of high-voltage pulsed bias. It was found that the dominant mechanism for generating stress in the TiN film was thermal stress arising from the large difference between the thermal expansion coefficient of TiN and that of the polymer. Tensile testing was used to ascertain film adhesion and a model was used to estimate the adhesion between the film and the substrate. It was found that PIII&D strongly reduced the stress in the TiN film and increased the adhesion to the polycarbonate. The ultimate shear strength of adhesion is of the same order of magnitude as that of TiN on stainless steel.     

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 利用磁过滤阴极电弧镀分别在硬质合金和高速钢基体上沉积厚度约2～3μm的TiN薄膜,并用MEVVA源离子注入装置对TiN薄膜注入金属离子V+和Nb+。应用北京同步辐射装置（BSRF）的同步辐射光源,采用掠入射X射线衍射（GIXRD）的方法对TiN薄膜表面离子注入层的微观结构进行了分析研究。结果表明：未经过离子注入的TiN薄膜均存在特定方向的择优取向,而较小剂量(1×10ˇ17ions/cm2)的离子注入可以使晶粒细化、择优取向减弱或改变;当离子注入的剂量达到5×10ˇ17ions/cm2时,TiN薄膜表面离子注入层被非晶化。结合透射电镜的研究结果,观察到TiN薄膜表面非晶层的厚度约为50～100nm,并简要地讨论了离子注入过程对微观结构的影响机制。     

Cathodic arc plasma deposition of nano-multilayered ZrN/AlSiN thin films

Thin films of ZrN/AlSiN were deposited on SKD 11 tool steel substrate using Zr and AlSi cathodes in an Ar/N₂ gas mixture in a cathodic arc plasma deposition system. The influence of the AlSi cathode arc current and the substrate bias voltage on the mechanical and structural properties of the films was investigated. X-ray diffraction, electron probe micro-analysis, high resolution transmission electron microscopy, nanoindentation and profilometry were used to characterize the films. The ZrN/AlSiN thin films had a multilayered structure by rotating the substrate in which nano-crystalline ZrN layers alternated with amorphous AlSiN layers. The hardness of the films increased as the AlSi cathode arc current was raised from 35 to 40 A, and then decreased with a further increase of the current. The hardness of the films increased with the increase of the bias voltage from − 50 to − 100 V. Further increase in the bias voltage decreased the hardness. The films exhibited a maximum hardness of 38 GPa. With the increase of bias voltage, the residual stress of the films correlated well with the hardness.     

Effect of coating thickness on the deformation mechanisms in PVD TiN-coated steel

The deformation mechanisms of a range of TiN coatings with different thicknesses, deposited on a V820 steel substrate following nanoindentation were characterized using focused ion beam (FIB) cross-sectioning and imaging, as well as cross-sectional transmission electron microscopy (TEM) of the indented region. Four TiN coatings were examined, including a cathodic arc evaporation (CAE) coating with a thickness of ∼ 0.7 μm and low voltage electron beam (LVEB) evaporation coatings with thicknesses of ∼ 2.0, ∼ 3.7 and ∼ 4.0 μm. Based on a model developed by Xie et al., the intercolumnar shear stresses were calculated to be approximately 2.20, 3.05, 3.50 and 3.55 GPa in the ∼ 0.7, ∼ 2.0, ∼ 3.7 and ∼ 4.0 μm thick TiN coatings respectively, that is, increasing as the coating thickness increases. Columnar cracking and shear steps at the coating/substrate interface were observed more frequently in the thinner TiN coatings indicated that these coatings deformed predominantly by shear along the columnar grain boundaries. In contrast, inclined cracking was the more dominant fracture type in the thicker TiN coatings. It is suggested that increased grain boundary strength occurs together with a lack of direct crack path along the grain boundaries through the thicker coatings due to the more equiaxed grain structure. Clearly, the grain structure and/or thickness of the TiN coating play a highly significant role in the deformation mechanisms.     

Study on the role of PVD TiN coating in improving the performance of electroplated monolayer superabrasive wheel

The monolayer grinding wheels, coated with a physical vapour deposited (PVD) coating (viz. TiN, HfN, TiN + ZrN etc.), have been reported to outperform their uncoated counterparts as claimed in some patented literatures. The present work aims at exploring the mechanism how PVD TiN augments the performance of nickel electroplated monolayer superabrasive wheels. This study also includes the effect of negative substrate bias voltage on performance of TiN coated electroplated cBN wheels during grinding of hardened bearing steel. TiN was deposited by pulsed DC closed-field unbalanced magnetron sputtering (CFUBMS) technique in an in-house PVD coating system. The structure of the TiN coating and post-grinding condition of the wheels were observed using scanning electron microscopy (SEM). Energy dispersive X-ray (EDX) line scan, Electron probe micro analysis (EPMA) and secondary ion mass spectrometry (SIMS) depth profiling at the junction of TiN and nickel layer indicated the occurrence of inter-diffusion between them and grazing incidence X-ray diffraction (GIXRD) confirmed the formation of Ni-Ti intermetallic phases at their interface. The scratch test revealed a significant increase in cohesive and adhesive strengths of nickel layer when TiN was deposited at a bias voltage of −60 V or beyond that. The uncoated cBN wheel exhibited large number of grit fracture at the bond level and some grit pull-out. Such failures of grit were significantly arrested with TiN coating deposited at the bias voltages of −60 V and −90 V.     

Electrochemical studies of stainless steel implanted with nitrogen and oxygen by plasma immersion ion implantation

Plasma Immersion Ion Implantation (PIII) of stainless steel with nitrogen at temperatures lower than 400 °C has been reported to increase the hardness of the material by several times. However, expectations that the corrosion resistance will remain unaffected after implantation were not found to be so. In the present study the influence of post-oxygen implantation on the corrosion resistance of nitrogen implanted stainless steel is presented. Stainless steel samples were subjected to oxygen, nitrogen and post-oxygen ion implantation at different temperatures. GIXRD and microRaman studies of the implanted samples showed that oxygen implantation leads to the formation of an oxide layer consisting of corundum and spinel structures. The corrosion properties of the implanted samples were studied by potentiodynamic polarization and electrochemical impedance techniques in 3.5% NaCl solution. After nitrogen implantation the corrosion current increased and the corrosion potential shifted to the less noble side to − 0.486 V as compared to − 0.284 V for the substrate. Oxygen implantation at 400 °C shifted the corrosion potential to the nobler side to − 0.2 V with decrease of corrosion current. For post-oxygen ion implantation at temperatures lower than 400 °C, the corrosion current was higher than the substrate and the corrosion potential was also on the less noble side. However, post-oxygen ion implantation at 400 °C after nitrogen ion implantation resulted in improved corrosion resistance as the corrosion potential shifted to nobler side and the corrosion current was lower than that of substrate.     

Effects of Ti/TiN multilayer on corrosion resistance of nickel-titanium orthodontic brackets in artificial saliva

The effects of multilayered Ti/TiN or single-layered TiN films deposited by pulse-biased arc ion plating (PBAIP) on the corrosion behavior of NiTi orthodontic brackets in artificial saliva are investigated. The multilayered Ti/TiN coating is found to exhibit a greater free corrosion potential, much lower passive current density, and no breakdown up to 1.5 V. Moreover, electrochemical impedance spectroscopy (EIS) results indicate that the multilayered Ti/TiN coating has a larger impedance and lower porosity which is believed to be responsible for the exceedingly low metal ion release rate during 720 h exposure in the test solution. Visual inspection of the surfaces reveals different corrosion processes for the TiN and multilayered Ti/TiN coatings.     

Characteristics of copper oxide films deposited by PBII&D

Copper oxide films were deposited by plasma based ion implantation and deposition using a copper antenna as rf sputtering ion source. A gas mixture of Ar + O₂ was used as working gas. During the process, copper that was sputtered from the rf antenna reacted with oxygen and was deposited on a silicon substrate. The composition and the chemical state of the deposited films were analyzed by XPS. The structure of the films was detected by XRD. It is observed that Cu₂O film has been prepared on the Si substrate. It is found that the microstructure of the deposited film is amorphous for the applied voltage of − 5 kV. The surface layer of the deposited films is CuO. This is because the surface layer absorbs the oxygen from ambient air after the treated sample was removed from the vacuum chamber. An appropriate applied voltage, 2 kV under the present conditions, brings the lowest resistance. It is also seen that the maximum absorbance of the deposited films moves to a lower wavelength with increased applied voltage.     

Characteristics and machining applications of Ti(Y)N coatings

The Ti(Y)N coatings were successfully deposited onto 18-8 stainless steel substrates by the hollow cathode discharge ion-plating method. The influence of the rare-earth element yttrium on the TiN coating properties was studied. The results show that the adhesion of the coating to the substrate were evidently enhanced by adding a small amount (0.2 wt.%) of the rare-earth element yttrium, showing a critical load of about 390 g which is much higher than that (230 g) of the TiN coating/substrate. Investigation on the corrosion resistance of the Ti(Y)N coating and the TiN coating was performed in 0.5 N Na₂SO₄ + 0.1 N H₂SO₄ + 0.1 N NaCl corrosion media by means of an electrochemical potentiodynamic polarization. The Ti(Y)N coating exhibited much better corrosion resistance than the TiN coating, whose passivity maintaining current is about one order in magnitude smaller than that of the TiN coating.The Ti(Y)N coatings deposited on some HSS-based tools were presented and compared with the TiN coating. The service lifetime of Ti(Y)N coated tools is approximately 36% higher (on the pinion shape cutters) and about 50% higher (on punch side pin) compared to that of TiN coated. The Ti(Y)N coatings showed such excellent performance. It is attributed to that the transition area of Ti(Y)N/substrate consisted of three sublayers which revealed a gradual change of phase structure and composition, so that the adhesion of the coating/substrate was evidently enhanced. Moreover, Ti(Y)N coating showed a preferred orientation with (111) plane which is favorable to improve wear resistance and corrosion resistance of the coating.     

Cathodic arc plasma deposition of nano-multilayered Zr-O/Al-O thin films

Thin films of Zr-O/Al-O were deposited on SKD 11 tool steel substrate using Zr and Al cathodes in a cathodic arc plasma deposition system. The substrates were mounted on a rotating holder which alternatively exposed them to plasma from the two cathodes. The influence of the Zr and Al cathode arc currents and the substrate bias on the mechanical and the structural properties of the films were investigated. Films with a nano-layered structure of alternating Al-rich and Zr-rich layers were obtained. The Zr layers contained nano-crystallites of (101) oriented t-ZrO structure. Crystallites with α-Al₂O₃ structure were observed only when the substrate was negatively biased in the 100-150 V range. The hardness of the film decreased with the increase of Zr cathode current from 60 to 80 A, increased when the Al cathode current increased from 25 to 30 A, and decreased when the Al cathode current increased from 30 to 35 A. The hardness of the film increased with the increase of bias voltage up to − 150 V and then decreased with further increase of the negative bias. The film structure was elucidated by HRTEM microscopy. Good correlation between the residual stress and the hardness enhancement of the films was observed.     

Microstructure and residual stress of TiN films deposited at low temperature by arc ion plating

The TiN films were deposited on 316L stainless steel substrates at low temperature by arc ion plating. The influences of substrate bias voltage and temperature on microstructure, residual stress and mechanical properties of the films were investigated by EDS, SEM, XRD and nanoindenter tester, respectively. The results showed that the TiN films were highly oriented in (111) orientation with a face-centered cubic structure. With the increase of substrate bias voltage and temperature, the diffraction peak intensity increased sharply with simultaneous peak narrowing, and the small grain sizes increased from 6.2 to 13.8 nm. As the substrate temperature increased from 10 to 300 °C, the residual compressive stress decreased sharply from 10.2 to 7.7 GPa, which caused the hardness to decrease from 33.1 to 30.6 GPa, while the adhesion strength increased sharply from 9.6 to 21 N.     

离子注入对TC4钛合金TiN/Ti涂层结合力和抗砂尘冲蚀性能的影响

目的通过离子注入提高TiN/Ti涂层的结合力和抗冲蚀性能。方法先采用金属蒸气真空弧(MEVVA)离子源在TC4基体上分别注入四种离子(Mo、Ti、Nb、Co),再用磁过滤真空阴极弧(FCVA)技术制备TiN/Ti涂层。采用非球面测量仪、AFM、XRD和纳米压痕仪,对四种离子注入的TC4基体表面粗糙度、表面形貌、物相结构、纳米硬度和弹性模量进行表征,采用划痕仪测量涂层的结合力,采用涂层冲蚀考核平台对不同试样进行砂尘冲蚀性能试验。结果经过Mo、Ti、Nb离子注入的TiN/Ti涂层的结合力和抗冲蚀性能都有提高,其中Mo离子注入的TiN/Ti涂层的结合力达71 N、耐冲蚀时间为80 min,与未离子注入涂层相比,分别增加31.5%和77.8%,而平均冲蚀率降低39.5%,仅为0.0078mg/g。Co离子注入的TiN/Ti涂层的结合力仅为40 N,平均冲蚀率增大了19.0%,达0.0433 mg/g,其抗砂尘冲蚀性能明显下降。结论离子注入涂层的抗砂尘冲蚀性能与结合力密切相关,随着结合力的增大,TiN/Ti涂层的平均冲蚀率减小,其耐冲蚀时间增加,选择合适的离子注入可提高TiN/Ti涂层的抗冲蚀性能。     

基板温度对EB-PVD ZrO2涂层微观组织及残余应力的影响

采用电子束物理气相沉积(EB-PVD)技术在不锈钢基板上沉积ZrO2涂层.研究基板温度对涂层微观组织和残余应力的影响.结果表明:沉积的涂层均为t-ZrO2结构,涂层表面平整致密;随着基板温度的升高,涂层表面颗粒逐渐长大,表面粗糙度增大;涂层残余应力也随着基板温度的升高而增加,当基板温度为1000 ℃时,涂层残余应力的增量最大,ZrO2涂层的残余应力主要是由于涂层与基板热膨胀系数差别而产生的热应力引起.     

CrAlYN/CrN superlattice coatings deposited by the combined high power impulse magnetron sputtering/unbalanced magnetron sputtering technique

CrAlYN/CrN coatings represent a new generation Ti-free PVD coatings tailored to serve high temperature applications such as dry high speed machining and protection of special grades aerospace and automotive alloys against environmental attack. The novel High Power Impulse Magnetron Sputtering (HIPIMS) technique was used for substrate pre-treatment (etching) followed by coating deposition utilising Unbalanced Magnetron Sputtering (UBM). The employment of HIPIMS resulted in smooth (R_a = 0.036 μm) and well adherent films with typical scratch adhesion critical load values on M2 high speed steel of L_C = 65 N. Low-angle XRD analysis showed that the coating has a nanoscale multilayer (superlattice) structure with a typical bi-layer thickness of 4 nm. XTEM observations confirmed this result and further revealed the dense, growth defect free structure of the coating due to the HIPIMS etching. CrAlYN/CrN combines high hardness of HK_0.025 = 3320 with a low coefficient of friction of 0.5 and an exceptionally low sliding wear coefficient of 3.7 × 10^− 17 m³ N^− 1 m^− 2, which is comparable to that of TiAlN/VN and Me-Carbon films. In dry high speed milling (V_cutting = 385 m min^− 1) of hardened A2 tool steel (HRC = 58), 8 mm cemented carbide ball nosed end mills coated with CrAlYN/CrN outperformed TiAlCrYN, which is one of the market leading coatings dedicated to this application. When the test is carried out at the higher end of the cutting speed range of 500 m min^− 1 this difference in performance becomes even more pronounced (factor of 8 longer life time), which demonstrates the excellent quality of CrAlYN/CrN.     

The effect of pulsed magnetron sputtering on the structure and mechanical properties of CrB2 coatings

CrB₂ thin films possess desirable combinations of properties (high hardness, wear resistance, chemical inertness, high thermal and electrical conductivity), which are attractive for a wide range of potential applications. Pulsed magnetron sputtering (PMS) of loosely-packed blended powder targets has allowed the deposition of stoichiometric chromium diboride coatings. The structure and properties of these coatings were found to be strongly dependent on the deposition process parameters; therefore investigation of the coating structures could explain certain differences between them and provide important information about the characteristics of the deposition process. In this study, characterization of the CrB₂ films was performed by scanning and transmission electron microscopy (SEM and TEM) techniques. The microstructures and properties of coatings deposited with different parameters are compared and changes that resulted from the variation of these parameters (particularly the pulsing duty cycle and the substrate biasing conditions) are discussed. The results show that besides the pulsing frequency, the target pulsing duty cycle is an important parameter of the PMS process, which is able to affect such coating properties as hardness, thickness and stress. Coating thickness measurement results suggest more intense bombardment of a growing film by energetic ions at lower values of duty cycle. Structural TEM analysis revealed two extremely different types of coating microstructures, obtained at quite similar substrate biasing conditions, i.e. floating (∼ − 15 V) and negatively biased (− 30 V). It appears that the structures of the coatings deposited at the negatively biased substrate are significantly affected by high-energy ion bombardment, which is a peculiarity of PMS that can modify film growth conditions. These conditions are not present when the substrate is allowed to float.     

Ion beam assisted deposition of TiN-Ni nanocomposite coatings

Hard and tough nanocomposite coatings consisting of hard TiN nanograins embedded in a soft metallic intergranular phase of Ni have been produced using ion beam assisted deposition. The chemical composition has been obtained by Rutherford Backscattering and the microstructural properties: phases, grain size, and texture of the coatings have been investigated by X-Ray Diffraction. In the composition range 0-22.5 at.% Ni, δ-TiN is the only crystalline phase and Ni appears as an X Ray amorphous phase. The hardness increases up to a maximum of 41 GPa at ~ 7 at.% Ni which corresponds to a TiN crystallite size of ~ 8 nm and a Ni intergranular phase thickness of roughly 1 monolayer. It is shown that the hardness enhancement in TiN-Ni nanocomposite coatings is not correlated with residual stresses, but rather with the intrinsic properties of the nanostructure. An important improvement in wear resistance is obtained for the coatings exhibiting the highest toughness and not the highest hardness. These results show that ion assisted processing is an effective tool for producing dense TiN-Ni nanocomposite coatings and tailoring their structure and mechanical properties.