TiN, TiN gradient and Ti/TiN multi-layer protective coatings on Uranium

Single-layer TiN, gradient TiN and multi-layer Ti/TiN coating were deposited on silicon and uranium substrates by means of arc ion plating technique. The main phase in the single-layer TiN coating was TiN with a (111) preferred orientation. Ti and TiN were observed in the TiN gradient coating and Ti/TiN multi-layer coatings. The single-layer TiN coating has demonstrated the best wear resistance among the three coatings. Compared with the bare U substrate, the corrosion potential E_corr of the multi-layer Ti/TiN coatings is increased by 580 mV, and the corrosion current density I_corr is decreased at least by two orders of magnitude. The multi-layer Ti/TiN coatings possessed the highest corrosion resistance among the three coating in a 0.5 μg/g Cl⁻ solution.     

钛合金表面百微米级Ti/TiN多层复合涂层性能研究

目的提高TiN硬质涂层的厚度及各项力学性能。方法采用等离子增强PVD技术在钛合金(TC4)基体表面制备多层复合Ti/TiN涂层,对涂层进行扫描电镜(SEM)分析,采用划痕法表征涂层的结合强度,用维氏显微硬度计测试涂层的显微硬度,利用销盘式摩擦磨损试验仪评价涂层的摩擦磨损性能。结果制备的多层复合Ti/TiN涂层厚度最高可达100μm,且未发生剥落等失效,结合强度相对于单层TiN提高了近3倍。由于Ti、TiN的多层复合调制作用,制备的Ti/TiN显微硬度测试表明复合涂层的显微硬度高达2700 HV0.025,同时,涂层在原有耐磨性能优良的基础上具备自润滑减摩作用,经过近20 000 m的磨损测试,复合涂层的摩擦系数低至0.25左右,且未完全失效。结论多层复合结构能够有效提高TiN硬质涂层的厚度,制备的Ti/TiN多层复合涂层的各项力学性能显著提高。     

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.     

气相沉积 Ti / TiN 多层薄膜的力学及耐腐蚀性能研究

目的研究多层薄膜的界面对薄膜性能的影响。方法通过直流磁控溅射法在45#钢表面制备Ti N及Ti/Ti N多层薄膜,采用扫描电镜和XRD衍射分析仪对薄膜表面形貌及相结构进行观察和分析,使用纳米压痕仪、电子薄膜应力分布测试仪对Ti N及Ti/Ti多层薄膜的力学性能以及残余应力大小进行研究,并运用电化学设备对Ti N及不同调制周期的Ti/Ti多层薄膜的耐腐蚀性能进行研究。结果制备的Ti N及Ti/Ti N多层薄膜表面光滑且结构致密,Ti N晶粒细小且为非晶相;薄膜力学性能良好,内部均存在残余压应力。随着调制周期的减小,弹性模量和硬度先减小后增大,内部残余应力逐渐减小且分布不均匀程度逐渐增大。薄膜在H_2SO_4中的腐蚀试验表明:当Ti/Ti N多层薄膜调制周期为1μm时,多层薄膜的耐腐蚀性能不如Ti N薄膜,随着Ti/Ti N多层薄膜随调制周期的减小,多层薄膜的耐腐蚀性能逐渐升高;当调制周期为0.5μm时,Ti/Ti N多层薄膜的耐蚀性能已超过Ti N薄膜。结论 Ti/Ti N多层薄膜界面的增多有助于减小薄膜的残余应力,并且可提高薄膜的耐蚀性能。     

多弧离子镀沉积Ti/TiN多层薄膜的摩擦磨损及电化学性能

软硬交替多层结构的薄膜因其优异的抗摩擦磨损性能和耐腐蚀特性使其在工程领域具有重要的应用价值。利用多弧离子镀在不锈钢和Si(100)表面沉积了Ti N单层薄膜和3种不同Ti/Ti N调制比的多层膜,利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、CSM摩擦磨损试验机和电化学工作站分别分析了薄膜的结构特征、耐磨损性能和电化学性能。结果表明:多层膜层状结构明显,Ti N相出现(111)面择优取向;Ti与Ti N沉积时间比为1∶5的样品具有较低的摩擦因数(0.26)和磨损率(6.6×10–7 mm3·N–1·m–1);在3.5%Na Cl溶液中,多层膜样品的腐蚀电流密度较不锈钢基体降低了两个数量级,腐蚀电位较不锈钢基体明显提高,表明多层膜可以提高不锈钢基体的耐腐蚀性。     

Si-modified aluminide coatings deposited on Ti46Al7Nb alloy by slurry method

Ti46Al7Nb alloy has been used as the research substrate material for the deposition of water-based slurries containing Al and Si powders. The diffusion treatment has been carried out at 950 °C for 4 h in Ar atmosphere. The structure of the silicon-modified aluminide coatings 40 μm thick is as follows: (a) an outer zone consisting of TiAl₃ phase and titanium silicides formed on the matrix grain boundaries composed of TiAl₃–type Ti₅Si₃; (b) a middle zone containing the same phase components with the matrix TiAl₃ and the silicides Ti₅Si₃, which formed columnar grains; (c) an inner zone, 2 μm thick, consisting of TiAl₂ phase. Cyclic oxidation tests were conducted in 30 cycles (690 h at high temperature) and showed a remarkably higher oxidation resistance of the Ti46Al7Nb alloy with the protective coating in comparison with the uncoated sample.     

Development of nano-structured cyclic multilayer Zn-Ni alloy coatings using triangular current pulses

Cyclic multilayer alloy (CMA) deposits of Zn-Ni were developed on mild steel from sulphate bath having thiamine hydrochloride (THC) and citric acid (CA) as additives. CMA coatings were developed galvanostatically using triangular current pulses, under different conditions of cyclic cathode current density (CCCD’s) and number of layers. The corrosion behaviors of the coatings were evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy methods, and were compared with that of monolayer Zn-Ni alloy of same thickness. At optimal configuration, CMA coating represented as, (Zn-Ni)_2.0/5.0/300 was found to exhibit ∼40 times better corrosion resistance compared to monolayer alloy, (Zn-Ni)_3.0. Cyclic voltammetry study demonstrated that THC and CA have improved the appearance of the deposit by complexation with metal ions. The corrosion protection efficacy of CMA coatings was attributed to the difference in phase structure of the alloy in successive layers, evidenced by XRD analysis. The formation of multilayer and corrosion mechanism was analyzed by Scanning Electron Microscopy (SEM) study.     

Microstructure and properties of TiN/Ni composite coating prepared by plasma transferred arc scanning process

The TiN/Ni composite coatings were deposited on 7005 aluminium alloy by high speed jet electroplating and then processed with plasma transferred arc(PTA) scanning process. The microstructure, microhardness and friction coefficient of PTA scanning treated specimens were investigated. It is shown that the PTA scanning treated specimens have a rapidly solidified microstructure consisting of the uniformly distributed TiN phase and fine Al₃Ni₂ intermetallic phases. The composite coating has an average microhardness of approximately HV 800. The friction coefficient of PTA scanning treated specimens (oscillated at around 0.25) is considerably lower than that of TiN/Ni composite coating (oscillated at around 0.35). The corrosion behavior of the composite coating in 3.5% NaCl solution at room temperature was also determined using a potentiostat system. In comparison with the corrosion potential _corr of −0.753 V for 7005 aluminium alloy, the corrosion potentials for TiN/Ti composite coating and PTA scanning treated specimen are increased by 0.148 V and 0.305 V, respectively. The PTA scanning treated specimen has the lowest corrosion current densityJ_corr as well as the highest corrosion potential _corr, showing an improved corrosion resistance compared with 7005 aluminium alloy.     

Wear of PVD Ti/TiN multilayer coatings

The wear characteristics of PVD Ti/TiN multilayer coatings subjected to two-body abrasion and particle erosion have been studied using diamond slurry and silicon carbide particles as abrasive medium and erodant, respectively. The abrasive wear rate of the Ti/TiN multilayer coatings was found to increase with the relative amount of metallic Ti in the coatings. In erosion, the lowest wear rate was recorded for the homogeneous TiN coating. For the Ti/TiN multilayer coatings the erosion rate was found to decrease with an increasing relative amount of metallic Ti in the coatings. It is concluded that the concept of multilayered coatings offers a potent means to tailor the properties of tribological coatings. In particular, demands of different applications can be met by adjusting the relative thickness of metallic Ti in Ti/TiN coatings. The amount of metallic Ti can, for example, be used to control the coating residual stress state. Multilayered Ti/TiN coatings seem promising for combined wear and corrosion protection.     

Effect of TiN/Ti multilayer on fretting fatigue resistance of Ti-811 alloy at elevated temperature

The TiN/Ti multilayer was deposited on Ti-811 alloy surface by magnetron sputtering(MS) technique for improving fretting fatigue(FF) resistance of the titanium alloy at elevated temperature. The element distribution, bonding strength, micro-hardness and ductility of the TiN/Ti multilayer were measured. The effects of the TiN/Ti multilayer on the tribological property and fretting fatigue resistance of the titanium alloy substrate at elevated temperature were compared. The results indicate that by MS technique a TiN/Ti multilayer with high hardness, good ductility and high bearing load capability can be prepared. The MS TiN/Ti multilayer, for its good toughness and tribological behavior, can significantly improve the wear resistance and FF resistance of the Ti-811 alloy at 350 ℃.     

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.     

Effects of Duplex Nitriding and TiN Coating Treatment on Wear Resistance,Corrosion Resistance and Biocompatibility of Ti6Al4V Alloy

Ti6Al4V alloy substrates were nitrided at 900 °C. TiN coatings were then deposited on the nitrided substrates using a closed-field unbalanced magnetron sputtering system. The microstructure, hardness and adhesion properties of the TiN-N-Ti6Al4V substrates were evaluated and compared with those of an untreated Ti6Al4V sample, a nitrided Ti6Al4V sample and a TiN-coated Ti6Al4V sample, respectively. The tribological properties of the various samples were investigated by means of reciprocating sliding wear tests performed in 0.9 wt.% NaCl solution against 316L, Si₃N₄ and Ti6Al4V balls, respectively. In addition, the corrosion resistance was evaluated using potentiodynamic polarization tests. Finally, the biocompatibility of the samples was investigated by observing the attachment and growth of purified mouse leukemic monocyte/macrophage cells (Raw 264.7) on the sample surface after culturing periods of 24, 72 and 120 h, respectively. Overall, the results showed that the duplex nitriding/TiN coating treatment significantly improved the tribological, anti-corrosion and biocompatibility properties of the original Ti6Al4V alloy.     

(Ti,Al)N单层和TiN/(Ti,Al)N复合涂层的切削性能研究

借助EDX、SEM、强度测试和切削实验研究了采用磁控溅射在硬质合金基体上沉积的(Ti,Al)N单层和TiN/(Ti,Al)N复合涂层的切削性能。研究表明,两种涂层均与基体结合紧密;TiN/(Ti,Al)N复合涂层则表现出更好的切削性能。     

Structural and tribological properties of DC reactive magnetron sputtered titanium/titanium nitride (Ti/TiN) multilayered coatings

Ti/TiN multilayered coatings of 200 layers with the thickness of 1.5 μm were deposited by a reactive DC magnetron sputtering technique using a mixture of Ar and N₂ gas. XRD technique was employed to elucidate the structural parameters. The presence of different phases like TiN, TiO_xN_y and TiO₂ were confirmed by XPS analyses. The observation of longitudinal optic (LO) phonon modes in the Raman spectra confirmed the highly crystalline nature of the deposited films. A microhardness value of 25.5 GPa was observed for Ti/TiN multilayers. The observed lower friction coefficient value for the Ti/TiN multilayers on mild steel (MS) indicated that the stack layers have better wear resistance property. Results from the electrochemical polarization and impedance studies showed the favorable behavior of the Ti/TiN multilayers, which have improved the corrosion resistance property of MS in 3.5% NaCl solution. The results of this study demonstrate that these multilayers can improve the corrosion resistance of mild steel substrates.     

Effect of hydroxyapatite‐titanium‐MWCNTs composite coating fabricated by electrophoretic deposition on corrosion and cellular behavior of NiTi alloy

In this study, the hydroxyapatite (HA)‐titanium (Ti, 20 wt.%) multiwalled carbon nanotubes (MWCNTs, 1 wt.%) composite coating was applied on the NiTi alloy by using the electrophoretic deposition (EPD) technique. The morphologies and the phase structures of the coatings were investigated by the FESEM and XRD analysis, respectively. The corrosion behaviors of the coated NiTi samples were investigated using the polarization and electrochemical impedance spectroscopy tests in a simulated body fluid (SBF). The amounts of the released Ni ions from the coated NiTi were studied in the SBF. The results of the electrochemical tests revealed the corrosion resistance of the NiTi coated with HA was further improved by the addition of the Ti and MWCNTs to the HA coating. The current density and corrosion resistance of the NiTi alloy changed from 2.52 μA.cm^?2 and 24.13 kΩ to 0.91 nA.cm^?2 and 5.92 MΩ after coated with the HA‐Ti‐MWCNTs composite coating. Also, the number of nickel ions released from the surface of the NiTi alloy to the SBF medium suppressed from 11.8 to 0.08 μgr.L^?1, after coating with HA‐Ti‐MWCNTs. Also, the cellular proliferation in the culture medium consisting of the NiTi alloy coated with the HA‐Ti‐MWCNTs improved significantly (compared with that of the NiTi alloy) as shown no toxicity in the cell culture medium.     

Microstructure and physical properties of PVD TiN/（Ti, Al）N multilayer coatings

Magnetron sputtered （Ti, Al） N monolayer and TiN/（Ti, Al） N multilayer coatings grown on cemented carbide substrates were studied by using energy dispersive X-ray spectroscopy （EDX）, scanning electron microscopy （SEM）, nanoindentation, Rockwell A indentation test, strength measurements and cutting tests. The results show that the （Ti, Al）N monolayer and TiN/（Ti, Al）N multilayer coatings perform good affinity to substrate, and the TiN/（Ti, Al）N multilayer coating exhibits higher hardness, higher toughness and better cutting performance compared with the （Ti, Al）N monolayer coating. Moreover, the strength measurement indicates that the physical vapour deposition （PVD） coating has no effect on the substrate strength.     

An investigation on oxidation,hot corrosion and mechanical properties of plasma-sprayed conventional and nanostructured YSZ coatings

Conventional and nanostructured YSZ coatings were deposited on IN-738 Ni super alloy by atmospheric plasma spray technique. The oxidation was measured at 1100 °C and hot corrosion resistance of the coating was measured in a mixed salt of V₂O₅ and Na₂SO₄ at 1050 °C using an atmospheric electrical furnace. According to the experimental results, nanostructured coatings showed a better oxidation and hot corrosion resistance than conventional one. The improved oxidation resistance of the nanocoating could be explained by the change of structure to a dense and more packed structure in this coating. The improvement in hot corrosion resistance was not as good as the oxidation but much better than conventional coating. The thermo-mechanical properties of the coating were tested using thermal cycles, nanoindentation, and bond strength tests during which nanostructured YSZ coating again showed a better performance by structural stability.     

Microstructure and properties of CVD coated Ti(C,N)-based cermets with varying WC additions

In this paper, multilayer coatings of TiN/TiCN/Al₂O₃/TiN are deposited on the Ti(C, N)-based cermets containing WC, and the effect of WC on the growth and adhesion strength as well as the mechanical properties of the coating are investigated. The multilayer coatings deposited by chemical vapor deposition (CVD) are uniform and dense. TiN coating exhibits a dense fine-grained structures and the Ti (C,N) on TiN coating shows dense columnar structure. The α-Al₂O₃ layer deposited on transition coating presents coarse grains with limited voids. The grain size of the columnar crystals deposited on the substrates gradually decreases with WC addition. The Al₂O₃ layer shows a preferred growth orientation of (104) plane. For TiN/TiCN phase, a change in orientation from (111) to (200) is observed. Generally, the (200) preferred orientation enhances and (111) preferred orientation diminishes with increasing WC addition. Strong adhesion of the CVD coating is obtained due to a sufficient amount of chemical elements, especially tungsten, diffusing from the substrate to the interfacial layer. Scratch tests show that the adhesion strength of TiN/TiCN/Al₂O₃/TiN films gradually increases firstly, and then decreases. With the addition of WC, the hardness, elastic modulus and plasticity index increase at the beginning, and then decrease. The change in nanohardness and elastic modulus is related to the grain size, elemental diffusion, and preferred orientation of the coating.     

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.     

Effect of TiN/Ti composite coating and shot peening on fretting fatigue behavior of TC17 alloy at 350 °C

A TiN/Ti composite coating has been prepared on a TC17 titanium alloy substrate by an ion-assisted arc deposition (IAAD) technique with a view to improving the fretting fatigue resistance of the titanium alloy at 350 °C. The composition distribution, bonding strength, micro-hardness, ductility, tribological properties, and fretting fatigue resistance at elevated temperature of the coating have been investigated. The results indicate that the IAAD technique can be used to prepare a TiN/Ti composite coating with high hardness, good ductility, excellent bonding strength, and high load-bearing capability. The TiN/Ti composite coatings can improve the resistance to wear and fretting fatigue of the Ti alloy, as manifested in its excellent tribological behavior at 350 °C. However, the fretting fatigue resistance of the titanium alloy treated by shot peening (SP) combined with IAAD TiN/Ti coating post-treatment was lower than that by IAAD TiN/Ti coating or SP alone, because the compressive residual stress induced by SP was significantly relaxed during coating process and the coating easily cracked and broke off.