Influence of Si content and growth condition on the microstructure and mechanical properties of Ti-Si-N nanocomposite films

Thin films of Ti-Si-N have been prepared by ion beam assisted deposition (IBAD) from two Ti and Si targets. The silicon concentration in the deposited coatings is varied between 0 and 23.7 at.%. The influence of Si content and growth conditions on the microstructure and mechanical properties were investigated using XPS, AFM, XRD and nanoindenter. These nanocomposite coatings exhibit improved mechanical properties in comparison with TiN deposited under the same condition. The hardness measured by nanoindentation reached 42 GPa in Ti-Si-N films containing 11.32 at.% of Si, whereas TiN films only had a value of about 18 GPa. AFM showed that the finest grain size of Ti-Si-N appeared to be 5 nm when Si content was 11.32 at.%. From XPS and XRD results, the microstructures of the high hardness samples were found to consist of nanocrystal TiN grains and amorphous Si₃N₄.     

工艺参数对离子束辅助沉积TiN薄膜性能的影响

为进一步提高牙科材料的生物相容性、耐磨性和耐腐蚀性能,将离子束辅助沉积制备TiN纳米薄膜技术引入到铁铬钼牙科材料的研究中,在Fe-Cr-Mo合金基体上制备了TiN薄膜.测定了表面膜层的显微硬度,在模拟口腔环境的溶液中,采用电化学方法,对经不同工艺参数沉积TiN薄膜的牙科用Fe-Cr-Mo合金的耐蚀性进行测试,并以未进行表面镀膜的Fe-Cr-Mo合金为对照.结果表明:经TiN镀膜处理的Fe-Cr-Mo软磁合金硬度明显增加,在口腔环境中的耐腐蚀性较未经表面镀膜处理的有明显提高.工艺参数不同,硬度增加的程度不同,耐蚀性差别也较大,当氮气流量为1.5mL/min,溅射时间为4h时,得到的膜厚为2μm,此时TiN膜硬度最高,在口腔溶液中耐腐蚀性最好.     

TiN Coatings Modified by an Interlayer of Electroplated Chromium on Mild Steel

TiN films on mild steel were deposited by reactive d.c. magnetron sputtering: electroplated chromium was incorporated as an interlayer. Surface hardness, measured by the Knoop indentation method under a load of 25 gf, phase analysis by the X-ray diffraction method and corrosion behaviour by the potentiodynamic measurement technique of these coatings have been evaluated. Surface hardness values were found to increase from about 1000–1100 for TiN coatings on mild steel to about 1800–1900 (HK₂₅) for TiN coatings with chromium as interlayer. Potentiodynamic corrosion tests, performed in IN H₂SO₄ solutions, have shown that with a chromium interlayer the corrosion resistance increases significantly as compared to TiN only sputtered coatings on mild steel samples. No spoiling of TiN coatings was observed during full sweep voltage of -1000 mV to +1000 mV when they were tested with a chromium interlayer.     

AZ91C镁合金表面Ti-TiN复合镀层的阴极多弧离子镀法制备与表征

采用阴极多弧离子镀膜技术,在AZ91C镁合金基底上首次成功镀制了结合力强的以Ti为过渡层的TiN复合膜层,并利用高分辨扫描电子显微镜(SEM)、X射线能谱仪(EDS)、显微划痕测试等技术对复合膜层的形貌、组织结构及性能进行分析研究。结果表明,采用多弧离子镀膜工艺,能在经过恰当预处理的镁合金基底上制备出性能良好的TiN膜,膜层均匀、致密,膜基结合力达130 mN以上,复合硬度达500 HV左右(AZ91镁合金基底为125 HV)。此外中性盐雾强化实验表明,经该方法处理后的镁合金在ASTM-B117标准测试条件下,腐蚀速率明显降低,经过200 h后,表面无明显腐蚀现象。真空多弧离子镀膜技术有望在镁合金表面防护领域得到应用。     

负偏压对多弧离子镀TiN薄膜的影响

采用不同偏压,在201不锈钢表面进行多弧离子镀TiN薄膜,研究了偏压对薄膜表面形貌、硬度、相结构及耐蚀性的影响.研究表明:薄膜表面存在着许多液滴颗粒,随着偏压的增加,液滴减少,但过大的偏压会使表面出现凹坑;薄膜的显微硬度随偏压的升高先增大后减小,偏压为-200 V时的本征硬度为2 195HV;在3.5％的NaCl溶液中...     

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.     

A comparative study of the properties of TiN films deposited by MAIP and FCAP

In this study two types of TiN films were prepared, one using the filtered cathodic arc plasma (FCAP) technique with an in-plane “S” filter, and the other using the multi-arc ion-plating (MAIP), and both deposited under the same parameters. Comparisons of the texture, hardness, roughness, tribological and electrochemical corrosion behaviors of the two types of TiN films were given. The TiN films obtained by the FCAP technology were found to be highly uniform, smooth and macroparticle-free. The TiN films deposited by FCAP had a (111) preferred orientation, while there was no texture in the films deposited by MAIP. Under low load the two kinds of TiN coatings had very different wear mechanisms; the films of FCAP had a lower wear rate and friction coefficient compared with the TiN films deposited by the MAIP technique. The dense and hole-free structure of TiN films of FCAP could effectively avoid the avalanche of TiN films from the substrate during corrosion tests.     

Al含量对TiAlN涂层结构及性能的影响

目的 系统研究Al含量对TiAlN涂层结构以及硬度、热稳定性、抗氧化性能和耐腐蚀性能的影响.方法 利用阴极弧蒸发技术,采用Ti、Ti50Al50、Ti40Al60和Ti33Al67靶材制备出4种Ti1–xAlxN涂层.分别利用能量色散X射线光谱仪(EDX)、X射线衍射仪(XRD)、扫描电镜(SEM)、纳米压痕仪、热重分...     

Tarnishing resistance of silver–palladium thin films

Ag–Pd decorative coatings are supposed to provide better tarnishing resistance as compared to pure Ag, while keeping good optical (brightness) and mechanical properties (ductility). Palladium has a similar optical appearance as silver, and forms a thin protective oxide surface layer. Thus, a small incorporation of Pd in Ag could improve its tarnishing resistance.

Thin Ag–Pd films were deposited by magnetron co-sputtering from Pd and Ag targets. The Ar gas pressure, target power and substrate temperature were varied to modify the chemical composition of the films and optimise their properties.

The optical properties of the films were evaluated by spectroscopic ellipsometry and colorimetry. Increasing Ar gas pressure and substrate temperature results in a drastic decrease of the specular reflectivity of the films. At constant deposition conditions the reflectivity of the Ag–Pd films decreases with increasing Pd content.

The film hardness, evaluated by nanoindentation, increases with Pd content.

The tarnishing resistance of the films was evaluated by sulphidation tests. The colour change of the films due to the sulphidation was measured by colorimetry. The nature of chemical bonds of the tarnished products was evidenced by XPS. The results suggest an improvement of tarnishing resistance of the Ag–Pd films with increasing Pd content.     

Corrosion Behaviour of TiN/a-C Superhard Nanocomposite Coatings Prepared by a Reactive DC Magnetron Sputtering Process

Nanocomposite coatings of TiN/a-C were prepared on tool steel substrates using a multitarget reactive DC magnetron sputtering process at various TiN layer thicknesses (0.6-2.8 nm). The a-C layer thickness was approximately 0.45 nm. Structural characterisation of the coatings was done by X-ray diffraction (XRD). Incorporation of an a-C phase in TiN matrix reduced crystallite size of the coatings, as revealed by XRD and atomic force microscopy. XRD data showed that the nanocomposite coatings exhibited {111} texture and the average crystallite size was ca. 7.5-9.0 nm. Nanoindentation data showed that 1.5 μm thick nanocomposite coatings exhibited a maximum hardness of 5100 kg mm^?2. The potentiody-namic polarisation of 1.5 μm thick coatings in 0.5 M HCl solution indicated that the nanocomposite coalings exhibited superior corrosion protection of the tool steel substrate as compared to the single layer TiN coatings of similar thicknesses. Enhancement in the corrosion behaviour of the nanocomposite coatings has been attributed to small crystallite size and dense microstructure. Potentiodynamic polarisation studies conducted on ca. 100 nm thick nanocomposite coatings revealed that for a given a-C layer thickness the corrosion current decreased with a decrease in TiN layer thickness. This was supported by scanning electron microscopy (SEM) studies on the corroded samples. The SEM micrographs showed that density and diameter of the corrosion pits were smaller for nanocomposite coatings as compared to single layer TiN coatings of similar thicknesses.     

Effect of Al additions in WC-(Cr1−xAlx)N coatings on the corrosion resistance of coated AISI D2 steel in a deaerated 3.5 wt.% NaCl solution

Multilayered WC-(Cr_1−xAl_x)N coatings were deposited on AISI D2 steel using cathodic arc ion plating (CAIP) process. Five kinds of WC-(Cr_1−xAl_x)N coatings were prepared: WC-Cr_0.6Al_0.4N, WC-Cr_0.57Al_0.43N, WC-Cr_0.53Al_0.47N, WC-Cr_0.48Al_0.52N and WC-Cr_0.45Al_0.55N. The Al concentration could be controlled by using evaporation source for Al targets and fixing the evaporation rate of the other metals (WC alloy and Cr). In this study, the corrosion behavior in deaerated 3.5 wt.% NaCl solution was investigated by electrochemical corrosion tests (potentiodynamic polarization test, galvanic corrosion test, electrochemical impedance spectroscopy (EIS)) and surface analyses (glow discharge optical emission spectroscopy, X-ray diffractometry, scratch adhesion test, scanning electron microscopy, electron probe micro-analyzer).

The results of potentiodynamic polarization test showed that the WC-Cr_0.48Al_0.52N coating with lower porosity exhibited the lower corrosion current density. The galvanic corrosion current between the coating and the substrate showed low values. In EIS measurements, the charge transfer resistance (R_ct) value of WC-Cr_0.48Al_0.52N coating only increased with the immersion time, when compared to the other coatings. It can be due to the corrosion products plugging the pores and increasing the pathway resistance.     

Structure and wear resistance of TiN and TiAlN coatings on AZ91 alloy deposited by multi-arc ion plating

In order to investigate the microstructure of TiN and TiAlN coatings and their effect on the wear resistance of Mg alloy, TiN and TiAlN coatings were deposited on AZ91 magnesium alloy by multi-arc ion plating technology. TiN and Ti70Al30N coatings were prepared on the substrate, respectively, which exhibited dark golden color and compact microstructure. The microstructures of TiN and Ti70Al30N coatings were investigated by X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The micro-hardness and wear resistance of TiN and Ti70Al30N coatings were investigated in comparison with the uncoated AZ91 alloy. The XRD peaks assigned to TiN and TiAlN phases are found. The hardness of TiN coatings is two times as high as that of AZ91 alloy, and Ti70Al30N coating exhibits the highest hardness. The wear resistance of the hard coatings increases obviously as result of their high hardness.     

W、Mo离子注入对离子镀TiN薄膜表面结构和性能的影响

目的进一步改善氮化钛薄膜的摩擦学性能。方法利用金属蒸汽真空弧源(MEVVA)在离子镀TiN薄膜表面进行等剂量W、Mo离子注入。采用扫描俄歇系统、光学三维形貌仪、X射线衍射仪和纳米压痕仪,分别分析了TiN薄膜的离子注入深度、表面形貌及粗糙度、相结构和不同压入深度的薄膜硬度。在球盘滑动摩擦磨损试验机上考察了TiN薄膜的摩擦学性能,并利用扫描电子显微镜和三维形貌仪对其磨损形貌进行分析。结果等剂量离子注入后,TiN表面注入层中W离子的含量明显大于Mo离子,两种离子注入对TiN薄膜的表面形貌和硬度的影响较小。XRD结果表明,W离子和Mo离子注入后均发现了Ti_2N硬质相。两种离子注入均可以不同程度地降低TiN薄膜的摩擦系数和磨损率。结论 W、Mo离子注入均可显著改善TiN薄膜的摩擦学性能,但Mo离子更有利于其摩擦系数的降低,而W离子注入更有利于TiN薄膜磨损率的降低。     

Corrosion Resistance of PAPVD TiN Coating on AISI 304 Stainless Steel

In this work the corrosion resistance of PAPVD TiN hard coatings on AISI 304 stainless steel with a titanium interlayer has been addressed. Cyclic voltammetry corrosion tests in NaCl 3.5% solutions were performed for samples prepared by depositing TiN/Ti onto steel using different deposition parameters. The surface morphology of the samples was examined by using a scanning electron microscope (SEM) and phase analysis was performed by X-ray diffraction (XRD). The cyclic voltammetry curves showed two distinct behaviours. Firstly, a reduction in corrosion resistance was observed when current density was increased for the whole potential range studied. The second observation, no less important, was the increase in corrosion resistance compared to the uncoated steel. The TiN films deposited showing (III) preferred orientation showed better corrosion resistance than films presenting other orientations.     

Characterization of TiBN films grown by ion beam assisted deposition

This paper presents one of the first attempts to measure and model the ellipsometric data for ternary nitride coatings in general and TiBN coatings in particular. TiBN coatings with a functionally graded underlayer of Ti/TiN have been deposited at low temperatures (<200 °C) on a silicon substrate using ion beam assisted deposition (IBAD). The coating selected for detailed analysis had a total thickness of 1.5±0.2 μm. The deposited structure was characterized post-deposition using X-ray diffraction (XRD), atomic force microscopy (AFM), Rutherford backscattering (RBS), X-ray photoelectron spectroscopy (XPS), infrared spectroscopic ellipsometry (IR-SE), and visible-light spectroscopic ellipsometry (VIS-SE). The primary phases (TiB₂, TiN, and BN) in the film were identified using XRD. The surface morphology and nanocrystalline nature of the coating (grain size of 5–7 nm) were deduced using AFM. The chemical composition and phase composition of the sample was determined from RBS and XPS measurements and was subsequently deduced from the analysis of the VIS-SE data. The refractive indices for the constituent phases were deduced from the investigation of TiB_2, TiN and BN single layers with SE. Good correlation was observed between RBS, XPS and VIS-SE for the data on the TiBN sample. XPS and IR-SE suggested that BN formed in the amorphous form. The chemical composition study using these various techniques shows that in-situ SE is a potential technique to control the growth of ternary nitride coatings. Finally, the mechanical properties of the coating were evaluated using a nanoindenter. The hardness and elastic modulus were measured to be 42 GPa and 325 GPa, respectively.     

离子束辅助沉积TiN薄膜在模拟口腔溶液中的耐蚀性

应用离子束辅助沉积技术(IBAD)在Fe-Cr-Mo合金基体上制备了TiN薄膜,在模拟口腔环境溶液中测定了其自腐蚀电位、腐蚀电流密度、极化电阻、极化曲线,并用未经表面镀膜的铁铬钼合金进行了对比。结果表明:经TiN薄膜处理的Fe-Cr-Mo软磁合金在口腔环境中的耐腐蚀性较未经表面镀膜处理的有明显提高;当氮气流量为1.5cm3/min,溅射时间为4 h,得到的膜厚为2μm,此时TiN膜在口腔溶液中的耐腐蚀性能最好。     

TiN及TiSiN涂层在海水环境下的摩擦学行为研究

目的对比研究海水环境下Ti N及Ti Si N涂层与Al2O3对磨的摩擦磨损行为。方法采用多弧离子镀技术在316L不锈钢及单晶硅片上制备Ti N及Ti Si N涂层。利用场发射扫描电子显微镜(SEM)、X射线衍射仪(XRD)及X射线光电子能谱仪(XPS)分析了涂层的截面形貌及化学组织成分。选择纳米压痕仪测量了Ti N及Ti Si N涂层的硬度及弹性模量,使用UMT-3往复式摩擦试验机研究了人工模拟海水环境下Al2O3与Ti N及Ti Si N涂层对磨后的摩擦磨损行为,并采用扫描电镜(SEM)、电子能谱(EDS)及表面轮廓仪来深入分析了磨痕的摩擦磨损情况。结果研究表明,Ti N涂层的硬度为32.5 GPa,当Si元素掺入涂层以后,Ti Si N涂层的硬度提高到了37 GPa。同时,较之于Ti N涂层,Ti Si N涂层的腐蚀电流密度下降了一个数量级。在摩擦实验中,Ti N涂层的摩擦系数和磨损率分别为0.35和5.21×10-6 mm3/(N·m),而Ti Si N涂层的摩擦系数和磨损率均有明显下降,分别为0.24和1.96×10-6 mm3/(N·m)。结论 Si元素掺杂后能显著提高Ti N涂层在海水环境下的摩擦学性能,主要归因于结构的致密,硬度、韧性、抗腐蚀性的提高及润滑相的形成。     

TiN颗粒对镁合金微弧氧化过程及膜层性能的影响

目的分析Ti N颗粒在镁合金微弧氧化过程中的作用,并研究其在膜层中对镁合金硬度、耐磨和耐蚀等性能的影响。方法通过在微弧氧化电解液中添加2.7μm Ti N颗粒,并使其充分分散于电解液中,使电解液中Ti N颗粒的质量浓度分别为0、2、4、6 g/L,并控制其他实验参数(如电流密度、频率、占空比和氧化时间)一样的情况下进行实验,通过电子显微镜、涂层厚度测厚仪、显微维氏硬度计、X射线衍射和电化学工作站,分别从膜层的表面形貌、厚度、硬度、相组成及耐蚀性等方面,研究了Ti N颗粒对镁合金微弧氧化膜层性能的影响。结果在微弧氧化电解液中添加Ti N颗粒后,相同电化学参数下制得的微弧氧化膜层变得致密,厚度、硬度有所增加,氧化膜层主要由Mg、MgO、Mg2Zr5O12、Ti N组成。极化曲线显示,加入Ti N颗粒,制备的微弧氧化膜层比未加入Ti N颗粒制得的膜层的腐蚀电流下降了2个数量级。阻抗图谱表明,电阻值增加了1个数量级。结论 Ti N颗粒能够随镁合金的微弧氧化过程进入制得的氧化膜层中,并且能够增加膜层厚度和硬度,使膜层的耐磨、耐蚀性得到提高。     

304不锈钢表面单层/多层TiN基涂层制备及耐磨蚀性能研究

目的探究钢基表面TiN基涂层在海洋环境中的耐磨蚀性能。方法采用电弧离子镀技术,在304不锈钢和单晶硅表面分别沉积TiN、TiBN、TiBN/TiN涂层,并对3种涂层样品的表面–截面形貌、摩擦系数、在人工海水中的电化学性能和摩擦腐蚀行为进行测试。结果形貌表征和干摩擦测试结果显示,TiBN和TiBN/TiN涂层有着比TiN柱状晶更加致密的微观结构,3种涂层的摩擦系数相差不大,比304SS的摩擦系数低。在人工海水环境中的电化学测试结果表明,TiBN/TiN涂层的耐腐蚀性能最佳,TiBN涂层次之,TiN涂层则表现出比304不锈钢基底更差的耐腐蚀特性。在发生摩擦腐蚀的过程中,3种涂层的电位（OCP）均发生了下降。结论利用电弧离子镀技术在304不锈钢表面沉积的单层/多层TiN基涂层,在人工海水环境下,发生的摩擦会增加涂层发生腐蚀的趋势,结构致密,表面易形成钝化膜的涂层,其耐磨蚀性较好。     

Corrosion Behaviors of Nitride Coatings on Titanium Alloy in NaCl-Induced Hot Corrosion

TiN and TiAlN coatings were deposited by arc ion plating on titanium alloys to study their hot corrosion resistance when they were exposed to NaCl at 600 ℃.The microstructure and corrosion behaviors of nitride coatings were studied using scanning electron microscope,X-ray diffraction,electro-probe microanalyzer and X-ray photoelectron spectroscopy.The results showed that nitride coatings with the different compositions and the ones with the same composition but different thicknesses presented different hot corrosion resistance.TiN and thin TiAlN coatings showed poor corrosion resistance.Serious internal oxidation attacked the alloy substrate.Their corrosion products were mainly consisted of non-protective TiO2 and sodium salt.By contrast,the thick TiAlN coating presented outstanding corrosion resistance.Besides sodium salt,the corrosion products were composed of protective Al2O3.The increasing thickness of TiAlN significantly enhanced the hot corrosion resistance.The corrosion mechanisms of alloy,TiN and TiAlN coatings were discussed in detail.