基体偏压对多弧离子镀制备CrAlN薄膜组织和性能的影响

采用多弧离子镀技术在H13模具钢表面制备CrAlN薄膜,通过扫描电镜(SEM)和X射线衍射仪(XRD)研究了CrAlN薄膜的表面形貌与物相组成,测试了CrAlN薄膜的显微硬度及其与基材的结合力,使用箱式电阻炉考察了CrAlN薄膜在800°C下的抗氧化性能,通过动电位极化曲线测量分析了CrAlN薄膜的耐腐蚀性能。结果表明：随着偏压增大,CrAlN薄膜表面大颗粒先减少后增多,晶粒尺寸先减小后增大。CrAlN薄膜表面检测出CrN(200)、CrN(220)及AlN(101)衍射峰,且偏压变化不影响物相组成。随着偏压增大,CrAlN薄膜的力学性能、抗高温氧化性能及耐腐蚀性能先提高后降低。偏压为100 V时,CrAlN薄膜最均匀致密,表面大颗粒最少,显微硬度及膜基结合力最高(分别约为2 300 HV和23 N),抗高温氧化及耐腐蚀性能最佳。     

TiN硬质陶瓷薄膜研究进展

TiN薄膜具有优异的综合性能而受到广泛应用和研究。综述了TiN薄膜的多种制备技术，介绍了制备技术和工艺参数对TiN薄膜结构和性能影响，阐述了TiN薄膜应用领域，最后展望了TiN薄膜未来发展方向。     

聚苯胺/氮化铬纳米复合材料的制备及表征

以纳米氧化铬(Cr2O3)为原料,采用氨气氮化法制备了纳米氮化铬(CrN)粉体.通过原位聚合的方法,在冰水浴中制得CrN/聚苯胺(PAM)纳米复合材料.纳米CaN掺杂的聚苯胺电导率较聚苯胺提高了一个数量级,较文献报道TiN/PANI高一个数量级.     

喷涂距离对APCVD制备的TiN薄膜性能的影响

以TiCl4和NH3为原料,用常压化学气相沉积法在玻璃基板表面沉积得到了TiN薄膜.采用X射线衍射、场发射扫描电子显微镜、电阻仪、紫外-可见光谱仪等研究了喷涂距离(输入TiCl4管道末端到基板之间的距离)对沉积的TiN薄膜的结晶性能和表面形貌,以及薄膜的电学性能和光学性能的影响.结果表明:当喷涂距离为5cm和10cm时,玻璃基板表面形成电阻较高、反射率较低的较疏松薄膜.当喷涂距离增加到13cm和15cm时,可以得到结晶良好、低电阻、高反射、致密的TiN薄膜.当喷涂距离进一步增加到20cm以上,得到的薄膜的电阻率随之升高而反射率下降.对喷涂距离对薄膜性能的影响机理进行了分析,认为喷涂距离的变化会影响扩散到达并吸附在基板表面的反应物分子数量比例,进而影响沉积薄膜的性能.     

氮氩流量比对玻璃基TiN薄膜的结构和硬度的影响

采用直流磁控溅射镀膜工艺,在不同的氮氩流量比条件下,制备了玻璃基TiN薄膜.通过X射线衍射仪(XRD)、场发射扫描电子显微镜(SEM、EDS)、纳米显微硬度仪,研究了TiN薄膜的组织结构、物相组成、表面形貌、元素成份、维氏硬度,分析了氮氩流量比对TiN薄膜结晶取向、硬度的影响机理.结果表明,在低的氮氩流量比条件下,TiN薄膜以(111)晶面择优取向;随着氮氩流量比增加,择优取向由(111)晶面向(200)晶面过渡;氮氩流量比为1∶2时薄膜以(200)晶面择优取向;继续增加氮氩流量比(1∶2 ～2∶1),TiN薄膜衍射峰强度降低,晶粒尺寸减小;当氮氩流量比增加到2∶1时,薄膜开始呈现非晶态.随着氮氩流量比的增加,薄膜硬度呈现先增加后减小的趋势;当氮氩流量比为1∶1时,TiN薄膜以(200)晶面择优取向结晶,组织致密均匀,晶粒尺寸最小,具有最大的硬度值(825 HV),相比未镀膜的玻璃基片,硬度值增加了20.44％.     

40CrNi2MoA合金钢阴极电弧等离子沉积TiN/TiAlN薄膜及其性能

以40CrNi2MoA钢作为基体,通过阴极电弧等离子体沉积(CPAD)技术制备了TiN、TiAlN和TiN/TiAlN薄膜。通过扫描电镜、X射线衍射仪、纳米压痕仪、原子力显微镜、摩擦磨损试验、洛氏硬度计和电化学分析,对比了3种薄膜的组织结构、纳米硬度、表面粗糙度、耐磨性、附着力和耐蚀性。结果表明,TiN/TiAlN双层膜的综合性能最佳,其附着力为HF1级,摩擦因数为0.455,纳米硬度为36.59GPa,表面粗糙度(Ra)为0.09μm。     

调制比对磁控溅射Ti/TiN多层膜组织结构和结合力的影响

通过固定薄膜厚度与调制周期,改变Ti与TiN调制比(分别为1∶3、1∶5、1∶9和1∶11),采用反应磁控溅射法在硅片上制备Ti/TiN多层膜,研究调制比对薄膜微观组织结构及薄膜与基体结合力的影响。用X射线衍射仪(XRD)分析薄膜的晶体结构,用扫描电镜(SEM)观察薄膜的形貌,用纳米压痕仪测试薄膜的硬度,用纳米划痕仪测试薄膜与基体之间的结合力。结果表明:多层膜中TiN出现(220)晶面择优取向,Ti/TiN薄膜为柱状晶方式生长。柱状晶的细化程度随调制比的变化而发生周期性变化,柱状晶组织细化程度高的样品具有更高的硬度,但结合力更低。     

多弧离子镀TiCrSiCN硬质薄膜的微观结构与摩擦学性能

采用工业型多弧离子镀设备在4Cr5MoSiV1工业钢表面沉积TiCrSiCN硬质薄膜。借助扫描电子显微镜(SEM)、X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)、显微硬度计、划痕仪和摩擦磨损仪分析了TiCrSiCN薄膜的微观结构、力学性能和摩擦学性能。结果表明,TiCrSiCN薄膜为纳米晶和非晶的复合结构,其中的Ti(CN)和CrN纳米晶可显著提高硬度和耐磨性,而非晶相Si3N4与C起到减摩作用。高Cr和C含量的薄膜硬度高,与基材的结合力强,干滑动摩擦因数、干滑动磨损率和微磨料磨损率都明显降低,耐磨减摩效果好。     

沉积温度对射频磁控溅射TiN薄膜结构和表面形貌的影响

在不同沉积温度(25~400°C)下,利用射频磁控溅射技术在Si(100)基底上制备了TiN薄膜。采用X射线衍射仪和原子力显微镜研究了沉积温度对膜结构和表面形貌的影响,计算了晶面间距和晶格常数,分析了薄膜的应力性质。实验结果表明,不同沉积温度下制备的TiN薄膜主要含有(111)和(220)两种取向,以(220)为择优取向;随着温度的升高,薄膜晶化质量先提高然后趋于稳定。薄膜内应力为压应力,且随温度的升高而有所增大。随沉积温度升高,薄膜晶粒尺寸变小,表面结构更加均匀致密。     

工艺参数对磁控溅射TiN膜结构的影响

为研究工艺参数在磁控溅射中对TiN薄膜生长的影响,通过改变工艺参数使用直流磁控溅射设备在N_2流量5 sccm,N_2压强为5 Pa生长TiN薄膜。采用射频磁控溅射法在N_2流量5 sccm、N_2压强5 Pa等生长参数下,制备了TiN薄膜。采用电子扫描显微镜(SEM)、X射线衍射仪(XRD)对样品进行了分析,结果显示样品具有纳米级TiN薄膜的基本特征。实验表明,气氛中过多Ti原子的存在,影响了Ti原子和N原子的结合,也不利于TiN薄膜的生长。     

Hot filament chemical vapour deposition and wear resistance of diamond films on WC-Co substrates coated using PVD-arc deposition technique

Different Cr- and Ti-base films were deposited using PVD-arc deposition onto WC-Co substrates, and multilayered coatings were obtained from the superimposition of diamond coatings, deposited on the PVD interlayer using hot filament chemical vapour deposition (HFCVD). The behaviour of PVD-arc deposited CrN and CrC interlayers between diamond and WC-Co substrates was studied and compared to TiN, TiC, and Ti(C,N) interlayers. Tribological tests with alternative sliding motion were carried out to check the multilayer (PVD + diamond) film adhesion on WC-Co substrate. Multilayer films obtained using PVD arc, characterised by large surface droplets, demonstrated good wear resistance, while diamond deposited on smooth PVD TiN films was not adherent. Multilayered Ti(C,N) + diamond film samples generally showed poor wear resistance.Diamond adhesion on Cr-based PVD coatings deposited on WC-Co substrate was good. In particular, CrN interlayers improved diamond film properties and 6 μm-thick diamond films deposited on CrN showed excellent wear behaviour characterised by the absence of measurable wear volume after sling tests. Good diamond adhesion on Cr-based PVD films has been attributed to chromium carbide formation on PVD film surfaces during the CVD process.     

Blood compatibilities of carbon nitride film deposited on biomedical NiTi alloy

Carbon nitride (CNx) film, diamond-like carbon (DLC) film, and titanium nitride (TiN) film were deposited on biomedical NiTi alloy substrates using direct current magnetron sputtering, respectively. In order to improve the adhesive strength between the deposited hard film and the NiTi alloy, a Ti transition layer was pre-deposited firstly. We emphatically evaluated the blood compatibilities of the NiTi alloy substrate and the deposited hard films by haemolysis test and platelet conglutination test. It was shown that the blood compatibilities of NiTi alloy can be improved effectively by the deposition of hard films. In comparison with TiN and DLC film, CNx film had the best surface modification effects covering the minimum haemolysis ratio and the best anticoagulation property.     

氮氩气流量比对磁控溅射氮化钛薄膜微观结构的影响

采用扫描电镜(SEM)和X射线衍射仪(XRD)研究了氮气流量(5、10、25、50 sccm)及氮氩气流量比(4∶1、3∶2、2∶3、1∶4)对磁控溅射TiN薄膜微观形貌和相组成的影响。结果显示,所得样品具有纳米级TiN薄膜的基本特征。当N2与Ar的总流量为5 sccm,而它们的流量比为4∶1时,可以制得品质较好的蓝紫色TiN薄膜。     

Morphologic and crystallographic studies on electrochemically formed chromium nitride films

Chromium nitride films were prepared by anodically oxidizing nitride ions at 0.4-1.5 V versus Li⁺/Li on chromium substrates in molten LiCl-KCl-Li₃N systems at 723 K. A crystalline Cr₂N film was successfully prepared at 0.4-1.4 V, and was thicker at more positive electrolytic potential. At 1.5 V, a Cr-N film could be also obtained, but its growth rate was relatively low. The film prepared at 1.5 V consisted of two distinctive layers. The surface layer was amorphous Cr-N containing crystalline CrN particles, and the inner layer was crystalline CrN. It was considered the existence of the amorphous phase suppressed the film growth.     

A study of the oxidation behavior of CrN and CrZrN ceramic thin films prepared in a magnetron sputtering system

CrN and CrZrN ceramic thin films were produced by a planar type reactive sputtering system on glass and stainless steel substrates. We investigated oxidation resistance of CrN and CrZrN ceramic thin films with different Zr contents. The structure of the films at different thermal-annealing temperatures was investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and scanning electron microscopy (SEM). The mechanical properties of the films at different thermal-annealing temperatures were measured by nano-indentation. The results of this study showed that the addition of few amount of Zr (0.4 at%), can improve thermal stability of CrZrN ceramic thin film and increase the oxidation temperature of the film from 600 °C to 800 °C. The relatively good oxidation resistance (800 °C) and high hardness of the film with the lowest Zr content, indicates that this film is a good candidate for high temperature applications.     

Tribomechanical and microstructural properties of cathodic arc-deposited ternary nitride coatings

Sintered carbides are promising materials for surfaces that are exposed to extreme wear. Owing to their high service load, ceramic-based thin films are coated on carbides using different techniques. In this study, non-toxic and cobalt-free powder metallurgy-sintered carbide samples were coated with TiN, TiAlN, CrAlN, and TiSiN ceramic-based thin film coatings by cathodic arc physical vapor deposition. The microstructure (phase formation, coating thickness, surface roughness, and topography), mechanical properties (hardness, modulus of elasticity, and plasticity indices), and tribological properties (nanoscratch and wear behavior) of the thin film coatings were investigated. No cracks or defects were detected in these layers. The ceramic-based ternary nitride thin film coatings exhibited better mechanical performance than the TiN coating. The TiN thin film coating had the highest average surface roughness, which deteriorated its tribological performance. The ternary nitride thin film coatings exhibited high toughness, while the TiN thin film coating exhibited brittle behavior under applied loads when subjected to nanoscratch tests. The wear resistance of the ternary nitride coatings increased by nearly 9–17 times as compared to that of the TiN coating and substrate. Among all the samples investigated, the substrate showed the highest coefficient of friction (COF), while the TiSiN coating exhibited the lowest COF. The TiSiN thin film coating showed improved mechanical and tribological properties as compared to other binary and ternary nitride thin film coatings.     

生物医用氮化碳薄膜的力学性能比较研究

使用磁控溅射法在生物医用NiTi合金基体表面制备了Ti／TiN、Ti／DLC以及Ti／CNx梯度薄膜,利用扫描电镜研究了薄膜的截面形貌,并使用划痕仪及摩擦磨损仪研究比较了薄膜的力学性能。结果表明：薄膜均表面平整,与基底结合紧密。Ti／CNx薄膜与NiTi合金基底的结合力大于Ti／DLC薄膜,略低于Ti／TiN薄膜。3种梯度薄膜均能有效改善NiTi合金的耐磨损性能,其中,Ti／CNx薄膜拥有最低的摩擦系数和最完整的磨损表面,耐磨性最好。     

Electrochemical oxidation of ethanol in acid media on titanium nitride supported fuel cell catalysts

In the present study, titanium nitride, TiN that possesses good electronic conductivity, high corrosion resistance combined with the ability to support metallic particles, has been used to anchor Pt catalysts and subsequently used for ethanol oxidation. Platinum deposited on TiN (Pt–TiN) surface is contrasted with the conventional support material, Vulcan carbon for the electrochemical oxidation of ethanol in acidic medium. Though the comparison is not straight forward due to different morphology/particle size of the Pt catalyst on the two supports, the present investigations reveal that the TiN support lead to surface Ti–OH type functional groups that help in reducing the accumulation of carbon monoxide on the catalyst surface. The Tafel slopes are similar but the exchange current density on Pt–TiN is approximately twice that of the value observed on Pt–C. X-ray photoelectron spectroscopy data support the long term stability and electrocatalytic activity of Pt–TiN electrocatalyst.     

Nanostructured titanium nitride for highly sensitive localized surface plasmon resonance biosensing

Titanium nitride (TiN) as an alternative plasmonic ceramic material with superb properties including high hardness, outstanding corrosion resistance and excellent biocompatibility, has exhibited great potential for optical biochemical sensing applications. By sputtering about 35 nm–50 nm TiN on glass (f-TiN), the surface was found to provide sensing capability toward NaCl solution through the phenomenon of surface plasmon resonance. When the TiN film of about 27 nm–50 nm in thickness was sputtered onto a roughened glass surface (R–TiN), the sensing capability was improved. This was further improved when holes at nanoscale were created in the TiN film of about 19 nm–27 nm in thickness (NH–TiN). The roughened surface and nanohole patterns provided confinement of surface plasmons and significantly improved the sensitivity toward the local refractive index changes. In detail, the calculated refractive index resolution (RIR) of the optimal NH–TiN sensors for NaCl was found to be 9.5 × 10⁻⁸ refractive index unit (RIU), which had outperformed the f-TiN and R–TiN sensors. For biosensing, the optimized NH–TiN sensor was found to be capable to detect both small and large biomolecules, i.e. biotin (molecular weight of 244.3 g/mol) and human IgG (160,000 g/mol), in a label-free manner. Especially, the NH–TiN sensor significantly improved sensitivity in detecting small molecules due to the localized plasmonic confinement of electromagnetic field. Combining with the excellent mechanical and durability properties of TiN, the proposed NH–TiN can be a strong candidate for plasmonic biosensing applications.     

Electrochemical oxidation behavior of titanium nitride based electrocatalysts under PEM fuel cell conditions

Titanium nitride (TiN) is attracting attention as a promising material for low temperature proton exchange membrane fuel cells. With its high electrical conductivity and resistance to oxidation, TiN has a potential to act as a durable electrocatalyst material. Using electrochemical and spectroscopic techniques, the electrochemical oxidation properties of TiN nanoparticles (NP) are studied under PEM fuel cell conditions and compared with conventional carbon black supports. It is observed that TiN NP has a significantly lower rate of electrochemical oxidation than carbon black due to its inert nature and the presence of a native oxide/oxynitride layer on its surface. Depending on the temperature and the acidic media used in the electrochemical conditions, the open circuit potential (OCP) curves shows the overlayer dissolved in the acidic solution leading to the passivation of the exposed nitride surface. It is shown that TiN NP displays passive behavior under the tested conditions. The XPS characterization further supports the dissolution argument and shows that the surface becomes passivated with the O-H groups reducing the electrical conductivity of TiN NP. The long-term stability of the Pt/TiN electrocatalysts is tested under PEM fuel cell conditions and the trends of the measured electrochemical surface area at different temperatures is shown to agree with the proposed passivation model.