钛合金表面TiN/CrN纳米多层薄膜的制备及耐磨、耐腐蚀性能

纳米多层涂层在钛合金磨蚀防护领域具有重要应用。本实验采用电弧离子镀膜技术,在TC4钛合金表面制备TiN、CrN及TiN/CrN纳米多层涂层,分别对涂层的微观形貌、相结构、硬度、膜基结合力、摩擦磨损性能和电化学腐蚀性能进行了系统研究。结果表明,TiN/CrN纳米多层涂层沿(111)面择优取向生长,结构致密,调制周期为25 nm,硬度为24 GPa,多层结构打断柱状晶生长,有效阻断腐蚀介质扩散到基体的通道。相较于TiN、CrN涂层,TiN/CrN膜基结合力有显著提高。TiN/CrN涂层磨损率为3.44×10~(-7)mm~3·N~(-1)·m~(-1),自腐蚀电流密度(i_(corr))为3.16×10~(-8)A/cm~2,显著低于TC4及TiN、CrN涂层,说明TiN/CrN纳米多层涂层的耐磨/耐腐蚀性能优于TiN、CrN单层涂层,并能对TC4基体在摩擦腐蚀环境下提供更好的防护。     

真空阴极离子镀法制备Ti/TiN/Zr/ZrN多层膜

过去,在不锈钢上沉积10μm以上多元多层软硬交替Ti/TiN/Zr/ZrN厚膜用以提高材料耐腐蚀性能的报道不多.采用阴极电弧离子镀结合脉冲偏压的方法制备了厚度选15 μm的Ti/TiN/Zr/ZrN多层膜.运用扫描电镜(SEM)、X射线衍射(XRD)、显微硬度计、划痕仪等考察了多层膜的形貌、厚度、相组成、硬度以及膜/基结合力,并利用电化学方法评价了基体、单层TiN薄膜以及多层膜的电化学腐蚀性能.结果表明:制备的Ti/TiN/Zr/ZrN多层膜界面明晰、结构致密、晶粒细小;膜/基结合力大于70 N,显微硬度达28 GPa;多层膜比单层TiN膜在提高1Cr11Ni2W2MOV基体的抗腐蚀能力方面具有更显著的作用.     

脉冲偏压对离子束辅助电弧离子镀TiN/Cu纳米复合膜结构及硬度的影响

采用离子束辅助电弧离子镀技术在高速钢基体上制备TiN/Cu纳米复合薄膜,考察了基体脉冲负偏压对薄膜成分、结构及硬度的影响。用X射线光电子谱、X射线衍射、扫描电镜、透射电镜和纳米压痕等方法分别测试了薄膜的化学成分、结构、表面形貌、硬度以及弹性模量。结果表明,在氮离子束的轰击作用下,随着脉冲偏压幅值从-100 V增加到-900 V时,薄膜中Cu含量先增加而后略有降低,在1.05%~2.50%(原子比)范围内变化。同时,脉冲偏压对薄膜的结构也有明显影响,在-100 V出现TiN(111)择优取向,当基体偏压增加到-300 V以上时,择优取向改变为TiN(220)择优。薄膜的Cu2p峰均对应纯金属Cu,薄膜的晶粒尺寸约在11~17 nm范围内变化。硬度和弹性模量随着偏压幅值增加而增大,当偏压为-900 V时,薄膜硬度和弹性模量达到最大值,分别为29.92 GPa,476 GPa,对应的铜含量为1.91%。     

TiN纳米薄膜的高硬度及其产生机制

用脉冲直流多弧离子镀方法在W18Cr4V高速钢基体上沉积具有纳米结构的TiN薄膜,用XP纳米压入仪测量薄膜的硬度,研究了其硬度产生的机制.结果表明,厚度为2-3 μm、晶粒尺寸约为13-16 nm的TiN薄膜,硬度为36-43 GPa,远高于TiN的本征硬度(22-24 GPa).高温去应力退火实验证实,具有纳米结构的TiN薄膜的超高硬度不仅是由沉积过程中载能粒子轰击产生的残余应力引起,面心立方结构的TiN薄膜沿(111)密排面择优生长、纳米晶界强化以及膜层组织结构的致密性也是重要的原因.     

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。     

脉冲偏压电弧离子镀CrAlN薄膜研究

在高速钢和不锈钢基体上用脉冲偏压电弧离子镀技术制备了CrAlN薄膜,研究了脉冲偏压对薄膜成分、结构和性能的影响,并进行了900℃下的高温抗氧化性能检测。结果表明,薄膜中Al的相对含量随着脉冲偏压的增加而降低;薄膜的相结构由立方CrN和Al相组成;薄膜的硬度随脉冲偏压的增加而增大,在偏压幅值为-500 V时,硬度可达21.5 GPa;薄膜具有高达70 N的膜基结合力;此外,薄膜在900℃的大气中保温10 h,没有出现明显的氧化现象;在合成的三种薄膜中,在脉冲偏压为-500 V×40 kHz×40%时的薄膜具有最好的综合性能。     

辉光弧光协同共放电方式制备TiN薄膜的研究

分别采用中频磁控溅射、电弧离子镀及辉光弧光协同共放电混合镀(APSCD)三种方式在碳钢基体上制备TiN薄膜,采用原子力学显微镜、显微硬度计、台阶膜厚仪、电化学技术对薄膜表面形貌、显微硬度、膜厚、耐腐蚀性进行测试.研究结果表明:多弧离子镀薄膜颗粒的平均粗糙度为7.066 nm,混合镀薄膜颗粒的平均粗糙度为4.687 nm,在相同时间条件下,磁控溅射薄膜厚度为658 nm,混合镀膜厚度为1345 nm,混合镀工艺具有降低多弧离子镀粗糙度又可以克服磁控溅射沉积速率慢的优点.经过混合镀TiN薄膜后,基体表面显微硬度从226HV提高到1238 HV,在天然海水中测得混合镀膜层腐蚀电位比基体提高104 mV.     

Influence of Pulsed Bias Voltage on Surface Properties of TiN Thin Films Deposited by Arc Ion Plating with Big Rectangle Shaped Targets

采用矩形平面大弧源离子镀技术在201奥氏体不锈钢基体表面制备TiN硬质薄膜, 研究了脉冲偏压对TiN膜层的表面形貌、相结构、硬度和耐磨性能的影响. 结果表明, 随着脉冲偏压的增大, 薄膜中大颗粒的数目先增加后减少, 这是大颗粒受到离子拖曳力和电场力双重作用的结果. 存在一个最佳的脉冲偏压, 使得制备出的TiN膜层具有较高的I(111)/I(200)比例和较高的耐磨性. 脉冲偏压为-300 V时制备的TiN膜层具有最好的综合性能.     

脉冲偏压对矩形平面大弧源离子镀TiN 膜层性能的影响

采用矩形平面大弧源离子镀技术在201奥氏体不锈钢基体表面制备TiN硬质薄膜,研究了脉冲偏压对TiN膜层的表面形貌、相结构、硬度和耐磨性能的影响.结果表明,随着脉冲偏压的增大,薄膜中大颗粒的数目先增加后减少,这是大颗粒受到离子拖曳力和电场力双重作用的结果.存在一个最佳的脉冲偏压,使得制备出的TiN膜层具有较高的I(111)/I(200)比例和较高的耐磨性.脉冲偏压为-300 V时制备的TiN膜层具有最好的综合性能.     

氮气流量对电弧离子镀CrN薄膜组织结构和性能的影响

利用电弧离子镀技术在高速钢基体上于不同氮气流量条件下制备CrN薄膜样品,通过纳米压痕仪、XP-2台阶仪、SEM和XRD测试分析了薄膜的硬度、弹性模量、厚度、表面形貌和物相结构.实验结果表明,氮气流量对CrN薄膜的组织结构和力学性能都具有较为明显的影响.     

Deposition,structure and hardness of Ti–Cu–N hard films prepared by pulse biased arc ion plating

In this work, Ti–Cu–N hard nanocomposite films were deposited on 304 stainless steel (SS) substrate by using pulse biased arc ion plating system with Ti–Cu alloy target. The effects of negative substrate pulse bias voltages on chemical composition, structure, morphology and mechanical properties were investigated. The composition and structure of these films was found to be dependent on the pulse bias, whereas the pulse biases put little influence on hardness of these films. The XPS spectra of Cu 2p showed that obtained peak values correspond to pure metallic Cu. Cu content in Ti–Cu–N nanocomposite films changed with pulse bias voltage. In addition, X-ray diffraction analysis showed that a pronounced TiN (111) texture is observed under low pulse bias voltage while it changed to TiN (220) orientation under high pulse bias voltage. Surface roughness of the Ti–Cu–N nanocomposite films achieved to the minimum value of 0.11 μm with the negative pulse bias voltage of −600 V. The average grain size of TiN was less than 17 nm. The mechanical properties of Ti–Cu–N hard films investigated by nanoindentation revealed that the hardness was about 22–24 GPa and the hardness enhancement was not obtained.     

Deposition,structure and hardness of Ti–Cu–N hard films prepared by pulse biased arc ion plating

In this work, Ti–Cu–N hard nanocomposite films were deposited on 304 stainless steel (SS) substrate by using pulse biased arc ion plating system with Ti–Cu alloy target. The effects of negative substrate pulse bias voltages on chemical composition, structure, morphology and mechanical properties were investigated. The composition and structure of these films was found to be dependent on the pulse bias, whereas the pulse biases put little influence on hardness of these films. The XPS spectra of Cu 2p showed that obtained peak values correspond to pure metallic Cu. Cu content in Ti–Cu–N nanocomposite films changed with pulse bias voltage. In addition, X-ray diffraction analysis showed that a pronounced TiN (111) texture is observed under low pulse bias voltage while it changed to TiN (220) orientation under high pulse bias voltage. Surface roughness of the Ti–Cu–N nanocomposite films achieved to the minimum value of 0.11 μm with the negative pulse bias voltage of ?600 V. The average grain size of TiN was less than 17 nm. The mechanical properties of Ti–Cu–N hard films investigated by nanoindentation revealed that the hardness was about 22–24 GPa and the hardness enhancement was not obtained.     

脉冲偏压幅值对TiN／TiAlN多层薄膜微观结构和性能的影响

采用电弧离子镀的方法,通过改变脉冲偏压幅值在M2高速钢表面制备了TiN／TiAlN多层薄膜,研究了脉冲电压幅值TiN／TiAlN多层薄膜微观结构和性能的变化。随着脉冲偏压幅值的增加,薄膜表面的大颗粒数目明显减少。EDX结果表明,脉冲偏压幅值的增加还引起Al／Ti原子比的降低。TiN／TiAlN多层薄膜主要以（111）晶...     

Nanometric-layered CrN/TiN thin films: mechanical strength and thermal stability

Nanometric-layered CrN/TiN coatings were deposited using unbalanced magnetron sputtering. The layered coating structure was characterised by X-ray diffractometry, and the mechanical properties were measured by nano-indentation and scratch test. High temperature annealing at 400-750 °C was carried out to investigate the thermal stability of the coating structure and mechanical properties. For comparison, samples of TiN and CrN deposited under similar conditions were also annealed and tested. The results showed that nano-layered CrN/TiN has excellent mechanical and thermal properties. Nano-hardness of 40 GPa and scratch adhesion of 80 N were achieved at a wavelength of 7.5 nm and a substrate bias of −80 V. The coating demonstrates application prospects in the stamping/cutting tools industry.     

Influence of Substrate Negative Bias on Structure and Properties of TiN Coatings Prepared by Hybrid HIPIMS Method

TiN coatings were deposited using a hybrid home-made high power impulse magnetron sputtering(HIPIMS)technique at room temperature.The effects of substrate negative bias voltage on the deposition rate,composition,crystal structure,surface morphology,microstructure and mechanical properties were investigated.The results revealed that with the increase in bias voltage from-50 to-400 V,TiN coatings exhibited a trend of densification and the crystal structure gradually evolved from(111) orientation to(200)orientation.The growth rate decreased from about 12.2 nm to 7.8 nm per minute with the coating densification.When the bias voltage was-300 V,the minimum surface roughness value of 10.1 nm was obtained,and the hardness and Young's modulus of TiN coatings reached the maximum value of 17.4 GPa and 263.8 GPa,respectively.Meanwhile,the highest adhesion of 59 N was obtained between coating and substrate.     

工业纯铁等离子体氮化及Ti/TiN多层薄膜沉积复合处理研究

为改善工业纯铁的耐磨抗腐蚀性能,本文采用低偏压高频等离子浸没离子注入及氮化技术(HLPⅢ)对工业纯铁进行表面改性,然后利用非平衡磁控溅射技术(UBMS)在低压高频等离子浸没离子注入及氮化处理样品表面制备Ti/TiN多层膜.研究发现,工业纯铁在3.5kV脉冲电压(频率15.15kHz,占空比25%)下等离子注入及氮化3h后,表面形成了深度达4μm的氮化层,其相结构以ε-Fe_3N和γ-Fe_4N结构为主.等离子氮化及Ti/TiN多层薄膜沉积复合处理后,工业纯铁的硬度、耐磨损性能以及抗腐蚀性能均得到大大提高,等离子注入及氮化形成的氮化层有利于提高Ti/TiN多层薄膜与工业纯铁基体之间的结合力和耐磨性.     

Effects of bias voltage on the microstructure and mechanical properties of (Ti,Al,Cr)N hard films with N-gradient distributions

(Ti,Al,Cr)N hard reactive films were deposited on high speed steel substrates by multi-arc ion plating (MAIP) technology using pure Cr and Ti-50Al(at.%) alloy targets. The partial pressure of N₂ was raised step by step in each deposition process. The surface morphology, the cross-sectional morphology of fracture sample, the surface compositions and the phase structure of the (Ti,Al,Cr)N films were investigated by scanning electronic microscope (SEM) and X-ray diffraction (XRD). The dense columnar microstructure was obtained in all of the (Ti,Al,Cr)N films, though micro-droplets evidently existed on the surface of the films. The micro-hardness of the film surface, the adhesive strength of the film/substrate and the thermal shock resistance were investigated. The results revealed the effects of bias voltage on the composition, phase structure, and mechanical properties. The improved balanced properties of a micro-hardness of about 50 GPa, an adhesive strength larger than 200 N and a thermal shock resistance of 7-8 cycles were reached at a bias voltage of 150 V. The present super-hard (Ti,Al,Cr)N films with N-gradient distribution may be an actual substitution of TiN, (Ti,Al)N, (Ti,Cr)N and single-layer (Ti,Al,Cr)N hard films.     

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.     

Intrinsic stress and preferred orientation in TiN coatings deposited on Al using plasma immersion ion implantation assisted deposition

TiN coatings were deposited on Al substrates using the plasma immersion ion implantation and deposition (PIIIAD) technique, employing a filtered Ti cathodic arc in a nitrogen atmosphere. Negative pulsed bias voltages between 0 to −4.0 kV were applied with varying duty cycles, at a constant time-averaged bias. Stress measurements using X-ray diffraction reveal an increase and then a decrease in the intrinsic compressive stress at increasing on-time bias. A bias-dependent preferred orientation of TiN is observed, i.e. {111}, {200} and {220} at low bias and predominantly {200} at higher bias. The hardness reduces from 29 GPa at lower bias to 20 GPa at higher bias. Thus, the time averaged energy of ion bombardment does not uniquely determine the properties of the growing coating, which can be adjusted by the on-time substrate bias applied for very short durations. A simplified subplantation model of stress development is formulated for the case of pulsed bias, the predictions of which are in reasonable agreement with the experimental data.