不锈钢表面防护TiC/a-C∶H纳米复合薄膜的耐腐蚀性能

采用直流反应磁控溅射技术在304不锈钢表面沉积TiC/a-C∶H纳米复合薄膜,并研究了TiC/a-C∶H纳米复合薄膜对不锈钢耐腐蚀性能的影响。通过扫描电子显微镜(SEM)和原子力显微镜(AFM)观察,结果表明薄膜表面光滑且薄膜结构均匀致密。Raman光谱和XRD测试结果表明,薄膜具有纳米晶TiC镶嵌非晶碳基质的典型纳米复合微结构。通过测量薄膜的静态接触角分析薄膜的润湿性,不锈钢表面沉积TiC/a-C∶H纳米复合薄膜后疏水性能明显提高,水接触角高达98°。电化学腐蚀测试结果表明,不锈钢表面沉积TiC/a-C∶H纳米复合薄膜体系在质量分数为3.5%的NaCl溶液中自腐蚀电位约为-0.09V,腐蚀电流密度为2.43×10-8 A·cm-2,与无薄膜防护的裸露不锈钢相比,其耐腐蚀性能得到明显改善。     

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.     

磁过滤电弧离子镀TiN薄膜的制备及其强化机理研究

采用电弧离子镀(AIP)和磁过滤电弧离子镀(MFAIP)方法分别在不锈钢和硅片上制备了两种不同的TiN薄膜.利用扫描电镜(SEM)观察了薄膜的表面形貌及组织结构;利用X射线衍射(XRD)及透射电镜(TEM)进行相鉴定;用纳米力学测试系统(NHT)测量了薄膜的硬度.结果表明:MFAIP TiN薄膜具有强烈的(111)面择优取向,薄膜表面光滑、表面熔滴颗粒(MP)少、薄膜的柱状晶组织细小、致密,薄膜具有较高的硬度.并在此基础上讨论了薄膜的强化机理,认为磁过滤器是制备高质量TiN薄膜及其复合薄膜行之有效的一种方法,是今后制备高性能TiN及其复合膜的发展方向.     

在室温条件下制备高质量纳米结构TiN薄膜研究

在室温条件下,利用磁过滤等离子体在单晶硅和不锈钢表面上制备了性能优异的纳米结构TiN薄膜.运用原子力显微镜和掠角入射X射线衍射仪对其结构与形貌进行了表征,利用纳米压痕仪测量了TiN薄膜的硬度和弹性模量.结果表明:TiN薄膜表面光滑,致密,无柱状晶;TiN晶粒的平均尺寸为50nm,薄膜硬度达50 GPa,是传统CVD和PVD技术沉积氮化钛的两倍多;XRD衍射试验表明,纳米TiN的衍射角都普遍向小角度移动,TiN晶粒沿(111)择优生长.     

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。     

电弧离子镀TiN/Ti纳米多层膜的力学性能

采用多弧离子镀技术,在不同沉积参数下合成具有纳米调制周期的TiN/Ti多层膜。利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、XP-2台阶仪、XP型纳米压痕仪、X射线能谱仪(EDS)研究了调制周期对TiN/Ti纳米多层膜微观结构、表面形貌以及力学性能的影响。结果表明,膜层由TiN和Ti交替组成,不存在其它杂相,且TiN薄膜以面心立方结构沿(111)密排面择优生长;TiN/Ti多层膜外观致密、平滑、颜色均匀金黄,随着调制周期的减小,薄膜表面大颗粒数量和尺寸均减小,且氮含量逐渐升高,膜层硬度呈现出增大的趋势。     

高速钢上磁控溅射氮化碳薄膜的摩擦学性能研究

采用磁控溅射法在高速钢(HSS)基片上制备了氮化碳(CNx/TiN)复合薄膜,并采用球-盘式摩擦试验法对其摩擦学性能进行了研究.通过分析薄膜的摩擦系数变化曲线,并辅之以薄膜摩擦表面形貌的显微观察分析以及EDS微区成分分析,对薄膜的摩擦学性能进行了表征.结果表明,CNx/TiN复合薄膜与对偶球(Si3N4)之间的摩擦系数约为0.3.具有较好的减摩性能,但复合薄膜的耐磨性能受制备工艺的影响较大.沉积合适的TiN/Ti过渡层可以显著提高薄膜的耐磨性能.薄膜的磨损机理主要为磨粒磨损与黏着磨损以及疲劳磨损相互结合.     

等离子体基离子注入制备TiN膜的成分结构

采用Ti、N等离子体基离子注入和先在基体表面沉积纯钛层然后离子注氮混合两种方法在铝合金基体上制备了TiN膜.利用XPS分析了两种方法制备TiN薄膜的成分深度分布和元素化学价态,并用力学性能显微探针测试对比了TiN膜的纳米硬度.研究表明:两种方法制备的薄膜均由TiN组成,Ti、N等离子体基离子注入薄膜中Ti/N≈1.1,而离子注入混合薄膜中Ti/N≈1.3,Ti、N等离子体基离子注入薄膜表面区域为TiN和TiO2的混合组织,TiN含量多于TiO2,离子注入混合薄膜表面主要是TiO2;Ti、N等离子体基离子注入所制备的薄膜的纳米硬度峰值为12.26 GPa,高于离子注入混合的7.98 GPa.     

全方位离子注入与沉积TiN薄膜的纳米压痕和纳米划擦行为

用等离子体浸没离子注入与沉积(PIIID)复合改性技术在AISI52100轴承钢基体表面合成了高硬耐磨的TiN薄膜。膜层的相组成及其表面形貌分别用X射线衍射(XRD)和原子力显微镜(AFM)表征。合成薄膜前后试样的力学性能经纳米压痕和划痕实验评价。XRD结果表明,膜层中主要存在TiN相,择优取向(200),同时含有少量TiO2和钛氮氧的化合物。AFM形貌显示出试样表面TiN呈定向排列,膜层均匀完整,结构致密。纳米压痕测试结果表明,膜层具有较高的纳米硬度和弹性模量,最大值分别达到22.5和330 GPa,较基体分别增长104.5%和50%。根据纳米划痕形貌和划痕深度随划痕位置的变化关系分析出,薄膜在纳米划擦过程中先后经历了弹性变形,弹塑性变形,加载开裂或卸载剥落三个阶段。划擦剥落抗力达到80mN,表明TiN薄膜具有很好的弹性恢复能力和较强的疲劳剥落抗力。     

薄膜

20001134 脉冲激光沉积TiN薄膜--Lu Y F．Journal of LaserApplications,1999,11(4)：169(英文) 研究了用激光照射TiN靶材(纯度99．9％)在硅基片上沉积TiN薄膜,KrF激光器产生的激光波长为248 nm,脉冲宽度为23ns,在沉积过程中真空室压力保持为1．33×10-3Pa,基片温度从室温到600℃。测试了薄膜晶体结构和性能,分析了薄膜硬度、化合价和晶体结构与基片温度的关系。测试结果表明,在600℃时,TiN(200)峰半高宽为0．24,薄膜硬度值为26GPa。用拉曼光谱仪研究了基片温度对薄膜电子特性的影响,并测试了薄膜粗糙度。20001135 用阴极电弧蒸镀及直接合成反应技术制备多元薄膜--Eizner B A．Materials and Manufacturing Processes,1999,14(5)：679(英文) 研究了用阳极电弧蒸镀(CAE)及直接合成反应技术制备多元薄膜,研究表明,薄膜中组分与相形成能有关,分析了沉积多元薄膜和单元薄膜时相变过程。沉积的薄膜有氮化钛、硅和硅化钛,蒸镀材料为Ti-0．7Si,氮气压力可调。20001136 溶胶-凝胶薄膜--Weiner M．Technische Rundschau,1999,91(19)：10(英文)     

High energy xenon ion beam assisted deposition of TiN film and its industrial application

TiN films have been synthesized by ion beam assisted deposition employing xenon ions with an energy of 40 keV. The formed TiN films were investigated systematically in respect of surface morphology, composition, structure and mechanical properties. Then, they were applied to surface protection of scoring dies. Atomic force microscopy and interferometric observation showed that the TiN film is relatively smooth. Rutherford backscattering spectroscopy analysis indicated that few xenon atoms are retained in the film. It was found by transmission electron microscopy and X-ray diffraction experiments that the formed TiN is a nanocrystal (< 10 nm) film and exhibits slightly (200) preferred orientation. An ultra low load microhardness indentor system was used to examine the plastic property of the film and a hardness of 2300 kgf mm^–2 was calculated from the measured data. Scratch tests showed that the adhesion of TiN film deposited by ion beam assisted deposition at ambient temperature is superior to that of high temperature physical vapour deposited (PVD) TiN film. Both a pin-on-dick tribotest and SRV wear test revealed that the wear resistance of the specimen can be greatly improved by TiN coating. A five times increase of service life of different scoring dies could be obtained by protection of TiN coating.     

Microstructure, chemistry and coating properties of ion-plated TiN on type 304 stainless steel

Characterization of TiN coatings on type 304 stainless steel was carried out using a Zeiss EM 902A energy filtering transmission electron microscope equipped with an electron energy loss spectroscopy (EELS) detector. TiN thin films were produced by a hollow cathode discharge ion plating coater. It was found by plan-view transmission electron microscopy that the microstructure of the TiN coatings is thickness dependent. The grain size of TiN ranges from 88 nm at the coating surface down to 9 nm near the TiN/steel interface. In addition, the TiN surface layer shows some degree of texture, but the subsurface and internal TiN layers are mainly equiaxial and randomly oriented. Chemical analysis by EELS shows that the relative oxygen content increases linearly from the TiN surface to the TiN/steel interface, whereas the relative nitrogen content first decreases slowly and then drops rapidly near the interface. The presence of a Ti₂N phase and the deficiency of nitrogen near the TiN/steel interface suggest that the early-deposited TiN is nonstoichiometric. By the periodic cracking method, the ultimate shear stress at the TiN/steel interface and the residual stress in the TiN thin film were estimated to be 2.2 GPa and 12.8 GPa, respectively.     

Thick TiN films prepared by vacuum arc deposition and high energetic nitrogen ion beam dynamic mixing implantation

TiN films have many features, such as high wear resistance, high corrosion resistance and good oxidization resistance. With the technology of vacuum arc deposition and high current density nitrogen ion beam dynamic mixing implantation (DMI), the TiN film with a thickness of 33 μm and adhesion 58 N is synthesized on hard alloy and high-speed steel substrates. X-ray diffraction has been used to examine the crystal structure of the films. The results showed that the main phases presented in DMI films are TiN and Ti₂N and that the films revealed random growth. Cross-sectional scanning electron microscopy revealed the dense morphology and the thickness of the films. Micro-hardness tests showed that the average hardness of the films was about 2500 HK. Electrochemical experimental results indicated that DMI-TiN film had excellent corrosion resistance both in 3% NaCl solution and in 0.5 Mol H₂SO₄ solution.     

Titanium nitride diffusion barrier for copper metallization on gallium arsenide

The diffusion properties of Cu, Cu/titanium nitride (TiN) and Cu/TiN/Ti metallization on GaAs, including as-deposited film and others annealed at 350-550 °C, were investigated and compared. Data obtained from X-ray diffractometry, resistivity measurements, scanning electron microscopy, energy dispersive spectrometer and Auger electron spectroscopy indicated that in the as-deposited Cu/GaAs structure, copper diffused into GaAs substrate, and a diffusion barrier was required to block the fast diffusion. For the Cu/TiN/GaAs structure, the columnar grain structure of TiN films provided paths for diffusion at higher temperatures above 450 °C. The Cu/TiN/Ti films on GaAs substrate were very stable up to 550 °C without any interfacial interaction. These results show that a TiN/Ti composite film forms a good diffusion barrier for copper metallization with GaAs.     

X-ray reflectivity study on TiN/Ti/Si structures before and after annealing

X-ray reflectivity was employed as a powerful tool for studying the surface and interface roughness and thickness, as well as density, of TiN/Ti/Si layers. X-ray reflectivity of the as-deposited samples, with nominal thickness of 17.5 nm of Ti and 3.0 nm of TiN, shows uniform oscillations. When the samples are annealed at 710°C, residual strongly attenuated oscillations are still observed, while the 850°C-annealed sample does not show oscillations, indicating high surface and interface roughness of the formed nitride and silicide layers. It is demonstrated that increased interface roughness, even for a layer with a larger average electron density difference, reduces the oscillations in the reflectivity curve very rapidly. For comparison, cross sectional transmission electron microscopy was employed to find the thickness of the surface and interface layers in silicide structures, which are in good agreement with the X-ray reflectivity results. The work was also supported by tapping mode atomic force microscopy observations, where we have observed nearly flat structures for the as-deposited sample surface and needle-like protrusions for the annealed samples. The surface roughness of the top TiN layer was used to obtain simulated X-ray reflectivity spectra in good agreement with the experimental results. Preliminarily, the crystallography of the layers in the samples was determined by the grazing angle X-ray diffraction technique, to acquire knowledge on the Ti and Si compounds formed in the samples after the annealing.     

结构调制超硬Ti/TiN纳米多层膜的制备及其尺寸效应

使用多弧离子镀技术在高速钢基体上制备了调制周期为5~40 nm的Ti/TiN纳米多层膜,用扫描电子显微镜(SEM)、X射线能谱仪(EDS)、X射线衍射仪(XRD)、纳米压痕仪和划痕仪等手段表征薄膜的微观结构和性能,研究了调制周期对Ti/TiN纳米多层膜性能的影响,并讨论了在小调制周期条件下Ti/TiN纳米多层膜的超硬效应和多弧离子镀技术对纳米多层膜硬度的强化作用。结果表明,与单层TiN相比,本文制备的Ti/TiN纳米多层膜分层情况良好,薄膜均匀致密,没有明显的柱状晶结构,TiN以面心立方结构沿(111)方向择优生长。随着调制周期的减小薄膜的硬度呈现先增大后减小的趋势,并在调制周期为7.5 nm时具有最大的硬度42.9 GPa和H/E值。这表明,Ti/TiN在具有最大硬度的同时仍然具有良好的耐磨性和韧性。Ti/TiN纳米多层膜的附着力均比单层TiN薄膜的附着力高,调制周期为7.5 nm时多层膜的附着力为(58±0.9) N。     

镀TiN薄膜的保温节能遮阳玻璃

镀有 TiN 薄膜的玻璃是一种新的“热镜”材料。当 TiN 薄膜厚度大于90nm 时,它对红外线的反射率大于75%。小样试验结果表明:使用镀 TiN 的窗玻璃比用普通玻璃节省取暖能源50%以上。此外,TiN 薄膜与玻璃的结合力强,它不被酸、碱、海水所腐蚀,时延性好。     

面向基因测序芯片应用的TiN电极薄膜制备及性能研究

基因测序技术正处于快速发展阶段,作为灵敏度极高的测序技术——纳米孔测序,对薄膜电极的电阻率和储能特性提出了更高的要求。为了降低薄膜的电阻率并提高储能特性,本文利用反应磁控溅射方法,基于原位生长原理,分别制备了TiO_xN_y和Ti/TiN/TiO_xN_y电极薄膜。采用扫描电子显微镜、X射线衍射仪和电化学工作站对薄膜的微观结构、化学成分及其电化学性能进行研究。结果表明,在TiN高导电性和TiO_xN_y高比表面积的协同作用下,Ti/TiN/TiO_xN_y电极薄膜表现出优异的电化学性能。当电流密度为0.15 mA/cm²时获得7.01 mF/cm²的比电容,是TiO_xN_y电极薄膜比电容值的1.3倍。同时,与TiO_xN_y单电极相比,Ti/TiN/TiO_xN_y...     

Influence of multi-interfacial structure on mechanical and tribological properties of TiSiN/Ag multilayer coatings

The TiSiN/Ag multilayer coatings with bilayer periods of ~50, 65, 80, 115, 150, and 410 nm have been deposited on Ti6Al4 V alloy by arc ion plating. In order to improve the adhesion of the TiSiN/Ag multilayer coatings, TiN buffer layer was first deposited on titanium alloy. The multi-interfacial TiSiN/Ag layers possess alternating TiSiN and Ag layers. The TiSiN layers display a typical nanocrystalline/amorphous microstructure, with nanocrystalline TiN and amorphous Si₃N₄. TiN nanocrystallites embed in amorphous Si₃N₄ matrix exhibiting a fine-grained crystalline structure. The Ag layers exhibit ductile nanocrystalline metallic silver. The coatings appear to be a strong TiN (200)-preferred orientation for fiber texture growth. Moreover, the grain size of TiN decreases with the decrease of the bilayer periods. Evidence concluded from transmission electron microscopy revealed that multi-interfacial structures effectively limit continuous growth of single (200)-preferred orientation coarse columnar TiN crystals. The hardness of the coatings increases with the decreasing bilayer periods. Multi-interface can act as a lubricant, effectively hinder the cracks propagation and prevent aggressive seawater from permeating to substrate through the micro-pores to some extent, reducing the friction coefficient and wear rates. It was found that the TiSiN/Ag multilayer coating with a bilayer period of 50 nm shows an excellent wear resistance due to the fine grain size, high hardness, and silver-lubricated transfer films formed during wear tests.