不同等离子源形成的DLC涂层对NiTi合金腐蚀行为的影响

采用等离子浸没离子注入和沉积(PIIID)法分别以C2H2和石墨为等离子源在NiTi合金表面形成DLC涂层来提高该合金的耐腐蚀性.利用Raman光谱和扫描电镜分析膜层结构.利用电化学测试和原子吸收光谱测试涂层前后基体的耐腐蚀性和Ni离子析出.结果表明:采用等离子浸没离子注入和沉积法以乙炔和石墨为等离子源在NiTi合金表面形成均匀致密、结合力良好的DLC涂层.两种涂层都明显地提高了NiTi合金的耐腐蚀性能和有效地抑制了Ni离子的溶出.     

镀覆NiTi根管锉的钛锆氮氧膜的制备工艺与性能

采用多弧离子镀技术在NiTi合金根管锉表面制备TiZrNO膜层,考查了沉积偏压、氧气流量对膜层表面组织形貌、成分等方面的影响;通过模拟临床制备根管(备牙)试验,观察镀膜根管锉表面形貌变化,进而确定其耐磨性能;通过电化学试验,确定了TiZrNO镀膜根管锉的耐腐蚀性能;在对试验结果综合对比分析的基础上,获得了优化的NiTi合金根管锉表面镀覆TiZrNO膜层的沉积工艺,确认了TiZrNO膜层具有良好的耐磨性和耐蚀性。     

多孔NiTi记忆合金化学氧化和热氧化表面改性的对比研究

研究了多孔NiTi记忆合金在H2O2＋HCl溶液中的低温化学氧化过程和500℃的高温热氧化过程。通过对比分析2种表面氧化处理后合金表面氧化膜的形貌、Ni/Ti比及膜层生长动力学曲线,探讨了多孔NiTi合金表面和孔内氧化膜的生长特点。结果表明,利用2种表面氧化技术在合金表面和孔内获得的氧化膜Ni含量均明显低于基体,且合金孔内氧化膜Ni含量低于表面氧化膜;多孔NiTi合金孔内的氧化对于与氧亲和力弱的Ni而言更加困难,孔内氧化膜的生长速率低于表面氧化膜的生长速率。     

Cr及Cr-Ni掺杂对不同偏压下TiAlN薄膜性能的影响

为了使4Cr13不锈钢表面性能得到更好的优化和获得镀膜最佳的偏压工艺,在不同的偏压工艺下,采用多弧离子镀技术和磁控溅射技术在4Cr13不锈钢表面沉积掺杂Cr和同时掺杂Cr、Ni的TiAlN薄膜.采用附着力自动划痕仪研究不同偏压条件下薄膜与基体的结合力,采用扫描电子显微镜观察和分析薄膜的表面形貌,采用XRD技术检测薄膜的相结构,采用显微硬度计测量薄膜的显微硬度.结果表明:适当的偏压可以提高薄膜的硬度和结合力,在偏压为-250 V时,薄膜的表面硬度达到最大值2 259 HV0.1 N,结合力为36 N;并且掺杂Ni元素能够起到增强膜基结合力的效果.     

TC4钛合金表面电弧离子镀TiN/CrN纳米多层薄膜研究

用电弧离子镀技术在TC4钛合金基体上通过改变偏压制备了4组TiN/CrN薄膜,对薄膜的表面形貌、厚度、相结构、硬度、膜基结合力和摩擦系数等组织、性能进行了测试表征。结果表明,薄膜是由TiN相和CrN交替叠加构成的纳米多层薄膜,薄膜的调制周期为60 nm,总的厚度约为480 nm。与基体钛合金相比,镀膜后样品的表面性能与偏压幅值密切相关并有显著提高:显微硬度从基体的3 GPa提高到16.5~24.7 GPa;摩擦系数从基体的0.35大幅度降低到0.14~0.17;薄膜与基体结合牢固,膜基临界载荷在60~80N之间。经电弧离子镀TiN/CrN纳米多层薄膜处理后,TC4钛合金可以满足沙粒和尘埃磨损条件下的耐磨性能要求。     

多弧离子镀(Ti,Al,Zr,Cr)N多组元氮化物膜的研究

采用多弧离子镀技术,使用Ti Al Zr合金靶和Cr靶,在W18Cr4V高速钢基体上沉积(Ti,Al,Zr,Cr)N多组元氮化物膜.利用扫描电镜(SEM)、电子能谱仪(EDS)和X射线衍射(XRD)对薄膜的成分、结构和微观组织进行测量和表征;利用划痕仪、显微硬度计测评薄膜的力学性能.结果表明,获得的多组元氮化物膜仍具有B1 NaCl型的TiN面心立方结构;薄膜的成分除-50V偏压外,其它偏压下的变化均不明显;增大偏压可减少薄膜表面的液滴污染,提高薄膜的显微硬度及膜/基结合力,最高值可分别达到HV3300和190N.     

反应溅射TiN纳米晶薄膜的结构特征和耐蚀性

利用直流反应溅射技术在不锈钢和硅基体上沉积了TiN纳米晶薄膜,采用场发射扫描电镜(FESEM)、X射线衍射(XRD)和电化学阻抗谱(EIS)技术研究了薄膜的表面形貌、相结构和耐蚀性与偏压的关系。结果表明,TiN薄膜的表面结构明显取决于所施加的偏压,适当提高偏压有利于获得细小、均匀、致密和光滑的膜层。XRD分析发现,TiN薄膜为面心立方结构,其择优取向为(111)面。实验显示,对应0V和-35V偏压的薄膜为欠化学计量比的,而偏压增加至-70V和-105V时的薄膜为化学计量比的TiN。EIS结果表明,较高偏压下的TiN薄膜几乎在整个频率范围内均表现为容抗特征,其阻抗模值明显高于低偏压下的膜层,这主要与较高偏压下的薄膜具有相对致密的微结构有关。较低偏压的TiN薄膜因结构缺陷较多其耐蚀性低于基体不锈钢。EIS所揭示的薄膜结构特征与FESEM观测结果一致。可见,减少穿膜针孔等结构缺陷有利于改善反应溅射TiN纳米晶薄膜耐蚀性。     

NiTi 合金表面激光原位反应合成TiN增强金属基复合材料涂层

采用连续高功率固体Nd-YA G激光辐照, 使预置于NiTi 合金表面的Ti 粉在N₂ 环境中形成TiN 增强Ti 基复合材料涂层。选择适当的激光辐照工艺参数, 获得致密的TiN 增强金属基复合材料激光改性层。SEM 观察及EDAX 成分分析结果表明, TiN/ Ti 金属基复合材料表面改性层与基体NiTi 合金存在良好的冶金结合, 界面处成分均匀过渡, 表面Ni 含量极低。显微硬度测试及磨损实验表明, TiN/ Ti 金属基复合材料改性层显著提高了NiTi 合金的表面硬度和耐磨性, 激光表面改性层可有效地改善NiTi 合金作为生物医学材料使用的表面成分和性能。      

不同弧源电流TiN薄膜的表面形貌及其摩擦学性能研究

本文使用AIP-01型国产多弧离子镀膜设备,采用不同的弧源电流在不锈钢衬底及Si片上制备了TiN薄膜,对其硬度、表面形貌以及摩擦系数等进行了测试,从电弧沉积的物理机制角度详细分析了弧源电流对TiN薄膜表面熔滴的影响,结果表明:随着弧源电流的增大,薄膜沉积速率增大、硬度提高,但薄膜表面熔滴(MP)数量增多、尺寸变大,表面粗糙,摩擦系数增大,因此控制最佳弧源电流来获得最好的薄膜性能是离子镀TiN薄膜的关键问题之一.     

电弧离子镀制备CrN_x薄膜中熔滴的结构表征与形成机制

应用电弧离子镀技术,在不同的氮气分压(0.5~2.5 Pa)和脉冲偏压(0~-300 V)条件下对TC4基体沉积CrNx薄膜,采用扫描电镜和透射电镜对镀膜过程中产生的熔滴现象进行分析研究。结果表明,升高氮气分压能减少靶材排出粒子团数量,改变等离子体轰击作用,从而控制熔滴数量及尺寸,改善薄膜表面平整度;脉冲偏压能够使熔滴与薄膜紧密结合,改变熔滴成分,在一定范围内能促进靶材成分熔滴的形成。     

Structural,Wettability and Optical Investigation of Titanium Oxynitride Coatings:Effect of Various Sputtering Parameters

The objective of the present work is to investigate the effect of various sputtering parameters such as nitrogen flow rate,deposition time and sputtering pressure on structural,wettability and optical properties of titanium oxynitride films deposited on glass substrate by reactive magnetron sputtering.The X-ray diffraction graphs of titanium oxynitride films show evolution of various textures of TiO_xN_y and TiN phases with increasing nitrogen flow rate and deposition time,but an increase in sputtering pressure from 4.0 to 8.0 Pa results in decline of various textures observed for TiO_xN_y and TiN phases.The stress and strain calculated by sin~2Ψ method are compressive,which decrease with increasing nitrogen flow rate from 55 to 100 sccm(standard cubic centimeter per minute) and increase with increasing deposition time from 80 to 140 min due to atomic penning effect and increasing thickness of the deposited films.The titanium oxynitride films have contact angle values above 90 deg.,indicating that films are hydrophobic.The maximum contact angle of 109.1 deg.is observed at deposition time of 140 min.This water repellent property can add value to potential protective,wear and corrosion resistant application of titanium oxynitride films.The band gap decreases from 1.98 to 1.83 eV as nitrogen flow rate is increased from 55 to 100 sccm;it decreases from 1.93 to 1.79 eV as deposition time is increased from 80 to 140 min as more nitrogen incorporation results in higher negative potential of valence band N2p orbital.But it increases from 2.26 to 2.34 eV for titanium oxynitride films as sputtering pressure increases from 4.0 to 8.0 Pa.     

Structure and properties of TiC/Ti coatings fabricated on NiTi by plasma immersion ion implantation and deposition

A titanium carbide (TiC) nanostructured coating and Ti intermediate layer are fabricated on NiTi by plasma immersion ion implantation and deposition (PIII&D) to improve the surface properties. The chemical composition and structure are determined by X-ray diffraction, Auger electron spectroscopy, scanning electron microscopy, and atomic force microscopy. Nano-indentation is used to evaluate the mechanical properties of the thin film and the biological characteristics are assessed by electrochemical measurement and soaking tests in simulated body fluids. Based on the potentiodynamic polarization and Ni release data after the polarization test, the Ti/TiC nanostructure coating has better corrosion resistance compared to the NiTi substrate and there is significantly less Ni ion release from the NiTi substrate into the simulated body fluids than the uncoated NiTi alloy.     

Effect of bias voltage on microstructure and mechanical properties of nanocrystalline TiN films deposited by reactive magnetron sputtering

Nanocrystalline TiN films deposited under various bias voltages have been prepared by a reactive magnetron sputtering. The effect of bias voltage on the microstructural morphologies of the TiN films was characterized by FE-SEM and AFM. The texture of the TiN films was characterized by XRD. It is also observed that the crystallite size decreases with increasing bias voltages. However, rms roughness increases with increasing bias voltages. The changes in roughness and crystallite size in the TiN thin films are due to one or a combination of factors such as resputtering, ion bombardment, surface diffusivity and adatom mobility; the influence of each factor depends on the processing conditions.     

Microstructural evolution of titanium nitride (TiN) coatings produced by reactive ion beam-assisted, electron beam physical vapor deposition (RIBA, EB-PVD)

Titanium nitride (TiN) coatings have been successfully deposited on 304 stainless steel substrates by reactive ion beam-assisted, electron beam-physical vapor deposition (RIBA, EB-PVD). The hardness values of the TiN coatings varied from 800 to 2500 VHN depending on the processing condition. The lattice parameter and hardness variation were correlated with processing parameters such as: deposition rate, bias, ion source energies, process gas, substrate temperature, and coating composition. The hardness of the TiN coatings increased with increasing ion energy. The ion energies combined with the deposition rate were the limiting factors controlling the degree of surface texturing. Surface texturing was only observed for those coatings deposited >8 Å/s.     

Chemical vapor deposition of aluminum from methylpyrrolidine alane complex

Chemical vapor deposition of aluminum from a recently developed precursor, methylpyrrolidine alane complex, has been studied. Aluminum films deposited on conducting surfaces (titanium nitride, copper, gold), but not on insulating surfaces (silicon, silicon dioxide, glass) at low substrate temperatures, showing deposition selectivity, while the deposition selectivity was lost at high substrate temperatures (> 210 °C). Al deposition rates on TiN and Cu were very close, but much higher than on Au. Deposition rates on all conducting substrates increased with the temperature and reached maximum at 180 °C. Al films deposited on as-sputtered TiN or Cu have no preferred orientations. Al–Au alloys and intermetallics were observed in the films deposited on Au. Surface morphology observation revealed that the film growth on TiN or Cu is different from that on Au. The surface roughness of Al films increased with the deposition time or the film thickness.     

Control of the bias voltage in d.c. PVD processes on insulator substrates

In plasma-PVD processes, ion bombardment during the growth of thin films has a strong influence on films properties such as morphology, composition, structure, stress, electrical conductivity, and others. Therefore, an accurate control of substrate bias voltage is needed in order to deposit films with the desired properties. For insulator substrates, dc biasing the substrate holder is useless, since the surface shall not follow the applied bias but it will be at the non-controlled floating potential.In this work we present a simple method for the effective control of the substrate bias in dc PVD processes with insulator substrates, based on placing a metallic grid at a certain distance from the non-conductive surfaces to be coated. The desired negative bias is applied to this metallic grid which accelerates ions from the plasma and directs them to the surface to cover. This method has been successfully applied to the deposition of TiN coatings on glass and decorative ceramics by Cathodic Arc Deposition. The deposited films showed good adhesion and gold color, in contrast with the bad adhered and brownish films deposited without the grid. The dependencies on the color and on the mechanical properties of our TiN films deposited on insulating substrates with the value of the bias voltage applied to the substrate are similar to those typically reported in the literature when conductive substrates are used.     

纳米结构TiN薄膜的制备及其摩擦学性能

在室温条件下,用磁过滤等离子体装置在单晶硅基底上制备了纳米结构TiN薄膜分析了薄膜的表面形貌、晶体结构,测量了TiN薄膜的硬度,研究了基底偏压对薄膜结构性能的影响.结果表明,用此方法制备的TiN薄膜表面平整光滑,颗粒尺寸为50～80 nm;随着基底偏压的增大薄膜发生(111)面的择优取向随着偏压的提高,薄膜的颗粒度稍有增大,摩擦系数增大,偏压提高,晶面在较密排的(111)面有强烈的择优取向,硬度也有所增大.在其它条件相同的情况下载荷越大,摩擦系数越大.不起用磁过滤等离子体法制备的纳米结构TiN薄膜具有较低的摩擦系数(0.14～0.25).     

Effects of the deposition temperature on the resistivity of copper films produced by low-pressure metal-organic chemical vapour deposition on a TiN barrier layer

Copper was deposited on to TiN by low-pressure metal-organic chemical vapour deposition, using hexafluoroacetylacetonate-Cu⁺¹-trimethylvinylsilane (hfacCu(I)TMVS) and argon carrier gas. The resistivity of the deposited copper films was investigated by observing the effects of the deposition temperature on the composition, microstructure and surface morphology of the copper films. The resistivity of the copper films decreases as the deposition temperature decreases. The copper films deposited at high temperatures, tend to contain the pores and or/ channels as well as carbon and oxygen, which results in the increase of the resistivity of the deposited films. The pores and/or channels come from the island-like growth of the copper films, while carbon and oxygen are due to the concurrent thermal decomposition of hfac during the disproportionation reaction between hfacCu(I) molecules.     

Deposition of TiN coatings on shape memory NiTi alloy by plasma immersion ion implantation and deposition

An investigation has been carried out to study the effect of pulse negative bias voltage on the morphology, microstructure, mechanical, adhesive and tribological properties of TiN coatings deposited on NiTi substrate by plasma immersion ion implantation and deposition. The surface morphologies were relatively smooth and uniform with lower root mean square values for the samples deposited at 15 kV and 20 kV negative bias voltages. X-ray diffraction results demonstrated that the pulse negative bias voltage can significantly change the microstructure of TiN coatings. The intensity of TiN(220) peak increased with the increase of negative bias voltage in the range of 5-20 kV. When the negative bias voltage increased to 30 kV, the preferred orientation was TiN(200). Nanoindentation test indicates that hardness and elastic modulus increased with the increase of the negative bias voltage (5 kV, 15 kV and 20 kV), and then dropped sharply at 30 kV. The adhesion between the TiN and NiTi alloy and tribological properties of TiN coated NiTi alloy depend strongly on the bias voltage parameter; the sample deposited at 20 kV possesses good adhesion strength and excellent tribological property.     

Improving hardness of biomedical Co-Cr by deposition of dense and uniform TiN films using negative substrate bias during reactive sputtering

This paper reports the deposition of a fully dense and uniform TiN film to improve the surface hardness of Co-Cr, particularly, by applying a negative substrate bias during reactive direct current (DC) sputtering. As the TiN film was deposited with a negative substrate bias voltage of 150 V, the microstructure of the films was shifted from a columnar to non-columnar one that was observed to have a dense, uniform and smooth surface. In addition, the preferred orientation was the (111) plane when the films were deposited with a negative substrate bias; however, the (200) plane when they were deposited without a substrate bias. The deposition of the dense and uniform TiN film resulted in a significant increase of the hardness of the Co-Cr. The TiN-deposited Co-Cr with a negative substrate bias showed a very high hardness of 44.7 ± 1.7 GPa, which was much higher than those of the bare Co-Cr (4.2 ± 0.3 GPa) and TiN-deposited Co-Cr without a negative substrate bias (23.6 ± 2.8 GPa).