脉冲高能量密度等离子体沉积(Ti,Al)N薄膜组织及其性能研究

利用脉冲高能量密度等离子体技术在室温条件下在45＃钢基材表面沉积了高硬度耐腐蚀(Ti, Al)N薄膜. 利用扫描电子显微镜、X射线衍射、X射线光电子能谱、俄歇电子能谱分析了薄膜的显微组织.利用纳米压痕仪测试了薄膜的纳米硬度.测试了薄膜在05mol/L H2SO4水溶液中的耐蚀性. 测试结果表明：薄膜主要组成相为(Ti, Al)N，同时含有少量的AlN,薄膜的纳米硬度高达26 GPa,薄膜具有良好的耐蚀性，与1Cr18Ni9Ti奥氏体不锈钢相比，耐蚀性提高了一个数量级. 关键词： 脉冲高能量密度等离子体 薄膜 纳米硬度 耐蚀性     

TiN/Al2O3纳米多层膜的共格外延生长及超硬效应

采用多靶磁控溅射法制备了一系列具有不同Al2O3调制层厚度的TiN/Al2O3纳米多层膜.利用X射线能量色散谱、X射线衍射、扫描电子显微镜、高分辨透射电子显微镜和微力学探针表征了多层膜的成分、微结构和力学性能.研究结果表明,在TiN/Al2O3纳米多层膜中,单层膜时以非晶态存在的Al2O3层在厚度小于1.5 nm时因TiN晶体层的模板效应而晶化,并与TiN层形成共格外延生长,相应地,多层膜产生硬度明显升高的超硬效应,最高硬度可达37.9 GPa.进一步增加多层膜中Al2O3调制层的层厚度,Al2O3层逐渐形成非晶结构并破坏了多层膜的共格外延生长,使得多层膜的硬度逐步降低.     

共溅射Al-Zr合金薄膜的非晶化及其力学性能

为研究合金薄膜非晶化后力学性能持续提高的原因,通过双靶磁控共溅射方法制备了一系列不同Zr含量的Al-Zr合金薄膜,采用EDS,XRD,TEM和纳米力学探针表征了薄膜的微结构和力学性能.结果表明:在溅射粒子高分散性和薄膜生长非平衡性的共同作用下,较低Zr含量的薄膜形成超过饱和固溶体,剧烈的晶格畸变使薄膜的晶粒纳米化,其硬度相应迅速提高.随Zr含量的进一步增加薄膜形成非晶结构,非晶薄膜的硬度因Al-Zr键数量的增加持续提高,并在含33.3 at.%Zr达到9.8 GPa后增幅减缓.研究结果揭示了非晶薄膜中Al-Zr键对薄膜力学性能的显著作用.     

脉冲偏压电弧离子镀C-N-V薄膜的成分、结构与性能

用脉冲偏压电弧离子镀方法在硬质合金基体上制备了一系列不同成分的C-N-V薄膜.用X射线光电子能谱、激光Raman光谱、 X射线衍射(XRD)、透射电子显微镜(TEM)和纳米压痕等方法分别研究了薄膜的成分、结构与性能.Raman光谱,XRD和TEM结果表明,所制备的薄膜为在类金刚石(DLC)非晶基体上匹配有VN晶体的碳基复合薄膜.随V和N含量的增加,薄膜硬度与弹性模量先增加后下降,在N含量为204%,V含量为218%时薄膜硬度与弹性模量具有最大值,分别为368和5697 GPa,高于相同条件下制备的 关键词： C-N-V薄膜 类金刚石薄膜 纳米复合薄膜 电弧离子镀     

TiN和Ti1-xSixNy薄膜的微观结构分析

使用x射线衍射(XRD)、x射线光电子谱(XPS)、高分辨透射电子显微镜(HRTEM)和原子力显微镜(AFM)多种观测手段分析了TiN薄膜和Ti1-xSixNy纳米复合薄膜的微观结构.实验分析证明Ti1-xSixNy薄膜是由直径为3-5nm的纳米晶TiN和非晶Si3N4相构成,并且Ti1-xSixNy薄膜的表面粗糙度小于相同条件下制备的TiN薄膜,在Ti1-xSixNy薄膜体系的自由能中引入界面能的概念,在此基础上分析了体系中TiN晶粒的取向问题.     

Ti-Si-N复合膜的界面相研究

为了揭示Ti_Si_N复合膜中Si₃N₄界面相的存在方式及其对薄膜力学 性能的影响 ，采用x射线衍射仪、高分辨透射电子显微镜、俄歇电子能谱仪和显微硬度仪对比研究了磁 控溅射Ti_Si_N复合膜和TiN/Si₃N₄多层膜的微结构和力学性能. 实 验结果表明 ，Ti_Si_N复合膜均形成了Si₃N₄界面相包裹TiN纳米晶粒的微结构. 其中低Si 含量的Ti_Si_N复合膜中Si₃N₄界面相的厚度小于1nm，且以晶体态 存在，薄膜 呈现高硬度. 而高Si含量的Ti_Si_N复合膜中的Si₃N₄界面相以非晶 态存在，薄 膜的硬度也相应降低. 显然，Ti_Si_N复合膜中Si₃N₄界面相以晶体 态形式存在 是薄膜获得高硬度的重要微结构特征，其强化机制可能与多层膜的超硬效应是相同的. 关键词： Ti－Si－N复合膜 界面相 微结构 超硬效应     

Ti-B-C-N纳米复合薄膜结构及力学性能研究

利用反应磁控溅射方法在单晶硅和高速钢(W18Cr4V)基片上制备出不同C含量Ti-B-C-N纳米复合薄膜. 使用X射线衍射和高分辨透射电子显微镜研究了Ti-B-C-N纳米复合薄膜的组织和微观结构,用纳米压痕仪测试了它们的硬度和弹性模量. 结果表明,利用往真空室通入C₂H₂气体的方法制备得到的Ti-B-C-N纳米复合薄膜中,在所研究成分范围内只发现TiN基的纳米晶. 当C₂H₂流量较小时,C元素的加入可以促进Ti-B-C 关键词： Ti-B-C-N薄膜 磁控溅射 微观结构 力学性能     

超过饱和固溶W-B合金力学性质的第一性原理研究

针对小原子元素在金属合金中可同时提高硬度和韧性的现象,本文采用基于第一性原理方法,研究了W-B合金的超过饱和固溶结构和力学性能.计算结果表明：无论是几何结构的晶格畸变,还是热力学上的结合能,B原子以置换形式固溶于W晶体中均优于其他固溶形式,这主要是由于置换B原子与周围W原子形成以共价型为主兼有离子型的键合作用.在合金中添加B元素虽然降低了合金材料的弹性模量,杨氏模量由414.34 GPa降低至338.36 GPa,但却显著增加了材料的韧性,B/G值由1.97提高到2.30(纯W晶体相较于B含量6.25 at.%时).并且合金的各向异性显著地减弱.另外,合金中B元素的添加,还使得材料理想剪切强度和最大应变值也得到了增加,分别由原来的19.981 GPa和0.187增加至21.814 GPa和0.209.这说明B元素在W合金中的超过饱和固溶不仅增加了合金的强度,还提高了合金的韧性.     

(Zr,V)N复合膜的结构、力学性能及摩擦性能研究

通过非平衡磁控溅射的方法制备了不同V含量的(Zr,V)N复合薄膜, 采用EDS, XRD, XPS, 纳米压痕仪和摩擦磨损仪等对薄膜的化学成分、微结构、力学性能及摩擦性能进行了研究. 结果表明, V的加入虽未改变ZrN的fcc晶体结构, 但使薄膜的择优取向由ZrN的(200)面转变为(Zr,V)N的(111)面. 随着V含量增加, (Zr,V)N复合膜的硬度略有升高后缓慢降低, 并在含25.8 at.%V后迅速降低. 与此同时, 薄膜的常温摩擦系数亦有小幅降低. 高温摩擦研究表明, (Zr,V)N薄膜在300 ℃时出现V₂O₃, V₂O₅ 在500 ℃后形成, 其含量也随温度的提高而增加. 薄膜的摩擦系数因V₂O₅ 的形成而得到显著降低. 关键词： (Zr,V)N 薄膜 微结构 力学性能 摩擦性能     

过渡金属氮化物中单原子固溶和力学性能的第一性原理研究

基于密度泛函理论(DFT)的第一性原理,计算Si原子在Ti族和V族氮化物中以及B、C和Ge原子在TiN晶体中固溶的稳定结构,讨论置换型和间隙型固溶的低能量稳定结构与晶体间距的关系,研究金属氮化物和固溶原子固溶结构的力学性能.结果表明:Si原子在TiN、ZrN、HfN和TaN晶体中固溶以及Ge原子在TiN晶体中固溶情况为,单原子不进入对应过渡金属氮化物晶体中形成间隙固溶或置换固溶,随着晶体间距离变化单原子可以在晶体之间形成间隙固溶或置换固溶;Si原子在NbN以及B原子在TiN晶体中可以实现间隙固溶,而不能形成置换固溶;Si原子在VN和C原子在TiN晶体中固溶结构形式均为置换固溶.单原子固溶形成低能量置换型固溶体和间隙型固溶体的弹性常数、体模量和剪切模量均低于原过渡金属氮化物的对应值.     

Ti/TiN multilayer thin films deposited by pulse biased arc ion plating

In this work, the effect of modulation period (Λ) on Ti/TiN multilayer films deposited on high-speed-steel (HSS) substrates using pulse biased arc ion plating is reported. The crystallography structures and cross-sectional morphology of Ti/TiN multilayer films were characterized by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM), respectively. Their mechanical properties were determined via nanoindentation measurements, while the film/substrate adhesion via the scratch test. It was found that the highest hardness value reached 43 GPa for the modulation period of 54 nm, while the film/substrate adhesion also reached the highest value of 83 N. Furthermore, the hardness enhancement mechanism in the multilayer films is discussed.     

Microstructure and tribological properties of TiN, TiC and Ti(C, N) thin films prepared by closed-field unbalanced magnetron sputtering ion plating

TiN, TiC and Ti(C, N) films have been respectively prepared using closed-field unbalanced magnetron sputtering ion plating technology, with graphite target serving as the C supplier in an Ar-N₂ mixture gas. Bonding states and microstructure of the films are characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) in combination with transmission electron microscopy (TEM). The friction coefficients are measured by pin-on-disc test and the wear traces of deposited films are observed by optical microscope. Results show that the TiN film and Ti(C, N) film exhibit dense columnar structure while the TiC film exhibits a mixed microstructure of main nanocrystallite and little amorphous phases. The Ti(C, N) film has the highest microhardness value and the TiC film has the lowest. Because of small amount of pure carbon with sp² bonds existing in the film, the friction coefficients of Ti(C, N) and TiC multilayer films are lower than that of TiN film. In addition, the multilayer structure of films also contributes visually to decrease of friction coefficients. The TiC film has extremely low friction coefficient while the wear ratio is the highest in all of the films. The results also show that the Ti(C, N) film has excellent anti-abrasion property.     

Nanostructured two-phase nc-TiN/a-(TiB2, BN) nanocomposite thin films

Thin films of Ti-B-N with different N contents were deposited on Si(1 0 0) at room temperature by reactive unbalanced close-field dc-magnetron sputtering using three Ti targets and one TiB₂ target in an Ar-N₂ gas mixture. The effect of N content on bonding structure, microstructure, phase configuration, surface roughness and mechanical properties have been investigated using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), cross-sectional scanning electron microscopy (SEM), plan-view and cross-sectional high-resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM) and microindentation measurements. It was found that the N content significantly affected phase segregation and microstructure. The nitrogen-free TiB_0.65 films showed an amorphous compound consisting of Ti and TiB₂ (Ti-TiB₂). After adding about 28 at.% N, Ti was preferentially bonded to N to form TiN, accompanying with formation of small amounts of TiB and BN bonds. At this stage they combined TiB₂ to form a two-phase nanocomposite with microstructures comprising of nanocrystalline (nc-) TiN phase in nitrogen-containing amorphous (a-) TiB₂ matrix. Addition of more N promoted formation of BN bonding at cost of TiB₂, which resulted in formation of nanocomposite nc-TiN/a-(TiB₂, BN) thin films. A small grain less than 8 nm in size was found at low N content, and the grain size increased with increasing N content. A low microhardness value of about 20 GPa was obtained in the amorphous Ti-TiB₂ compound, and a maximum microhardness value of about 50 GPa was achieved in nc-TiN/a-TiB₂. A decrease of microhardness took place after formation of BN (i.e. amorphous matrix composed by both TiB₂ and BN) with further increasing N content, and a hardness value of about 35 GPa was followed at high N contents. The surface roughness strongly depended on the phase configuration. The higher the mole fraction of nanocrystalline TiN phase, the rougher the surface became.     

Characterization of Ti-Zr-N films deposited by cathodic vacuum arc with different substrate bias

Ti-Zr-N (multi-phase) films were prepared by cathodic vacuum arc technique with different substrate bias (0 to −500 V), using Ti and Zr plasma flows in residual N₂ atmosphere. It was found that the microstructure and mechanical properties of the composite films are strongly dependent on the deposition parameters. All the films studied in this paper are composed of ZrN, TiN, and TiZrN ternary phases. The grains change from equiaxial to columnar and exhibit preferred orientation as a function of substrate bias. With the increase of substrate bias the atomic ratio of Ti to Zr elements keeps almost constant, while the N to (Ti + Zr) ratio increases to about 1.1. The composite films present an enhanced nanohardness compared with the binary TiN and ZrN films deposited under the same condition. The film deposited with bias of −300 V possesses the maximum scratch critical load (L_c).     

Nanoindentation measurements on modified diamond-like carbon thin films

In the present study, we explored the effect of metallic interlayers (Cu and Ti) and indentation loads (5-20 mN) on the mechanical properties of plasma produced diamond-like carbon (DLC) thin films. Also a comparison has been made for mechanical properties of these films with pure DLC and nitrogen incorporated DLC films. Introduction of N in DLC led to a drastic decrease in residual stress (S) from 1.8 to 0.7 GPa, but with expenses of hardness (H) and other mechanical properties. In contrast, addition of Cu and Ti interlayers between substrate Si and DLC, results in significant decrease in S with little enhancement of hardness and other mechanical properties. Among various DLC films, maximum hardness 30.8 GPa is observed in Ti-DLC film. Besides hardness and elastic modulus, various other mechanical parameters have also been estimated using load versus displacement curves.     

Nanocomposite TiC/a-C：H film prepared on titanium aluminium alloy substrates by PSII assistant MW-ECRCVD

Thin films of titanium carbide and amorphous hydrogenated carbon have been synthesized on titanium aluminium alloy substrates by PSII assisted MW-ECRCVD with a mirror field. The microstructure, chemical composition and mechanical property were investigated. Using XPS and TEM, the films were identified to be a-C：H film containing TiC nanometre grains （namely, the so-called nanocomposite structure）. The size of TiC grains of nanocomposite TiC/DLC film is about 5 nm. The nanocomposite structure has obvious improvement in the mechanical properties of DLC film. The hardness of a-C：H film with Ti is enhanced to 34 G Pa~ while that of a-C：H film without Ti is about 12 G Pa, and the coherent strength is also obviously enhanced at the critical load of about 35N.     

Synthesis and characterization of superhard Ti-Si-N films obtained in an inductively coupled plasma enhanced chemical vapor deposition (ICP-CVD) with magnetic confinement

Using a novel inductively coupled plasma enhanced chemical vapor deposition (ICP-CVD) with magnetic confinement system, Ti-Si-N films were prepared on single-crystal silicon wafer substrates by sputtering Ti and Si (5 at.%:1 at.%) alloyed target in argon/nitrogen plasma. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffractometer (XRD), field emission scanning electron microscope (FESEM), atomic force microscopy (AFM) and Nano Indenter XP tester were employed to characterize nanostructure and performances of the films. These films were essentially composed of TiN nanocrystallites embedded in an amorphous Si₃N₄ matrix with maximum hardness value of 44 GPa. Experimental results showed that the film hardness was mainly dependent on the TiN crystallite size and preferred orientation, which could be tailored by the adjustment of the N₂/Ar ratio. When the N₂/Ar ratio was 3, the film possessed the minimum TiN size of 10.5 nm and the maximum hardness of 44 GPa.     

Effect of aluminum content on the mechanochemical synthesis of in-situ TiN in the Al–Ti–AlN system and subsequent shock consolidation

To determine the effect of aluminum content on the formation of in-situ TiN in the Al–Ti–AlN system, a mixture of aluminum, titanium and aluminum nitride powders was subjected to high energy milling. Al content of the mixture was changed according to the following stoichiometric reaction: Ti+AlN+XAl→TiN+(1+X)Al. The value of X was varied from 5.35 to 19.65 based on the stoichiometric calculation of the molar mass of each component expected to result in aluminum matrix composite with TiN weights of 30%, 20% and 10%, respectively, in addition to reaction corresponding to X=0(Ti+AlN→TiN+Al). Thermodynamic factors determine that the amount of Al in the mixture plays a key role in the formation of in-situ TiN. XRD and EPMA results showed that at lower Al content (X=0, 5.35), reaction proceed through a gradual mode. By increasing Al content (X=19.65), no mechanochemical reaction occurred between Ti and AlN. Continuation of the milling process allowed acquisition of in-situ TiN in the designed compositions of AlN–TiN, Al–Ti–AlN–30%TiN, and to some extent, of Al–Ti–AlN–20%TiN. A nanocrystalline solid solution evolved by mechanical alloying (MA) was sustained for prolonged milling time. The mean TiN crystallite size obtained was 10 nm for the AlN–TiN composition. The end product milled powder after 40 h of milling time, equating to the Al–Ti–AlN–30%TiN composition was consolidated into bulk compact using the underwater shock compaction method. The milled specimens were characterized by XRD, scanning electron microscopy (SEM), electron probe microanalysis (EPMA) and microhardness testing. The sample had a uniform and fine-grained composite structure with 99% theoretical density and average microhardness of 434 HV0.1. The results confirmed the possibility of fabricating reliable bulk nanostructured materials by imposing shock compaction on submicron sized powders.     

On the interface between iron and thin films of titanium and titanium nitride

Very thin films of TiN and Ti/TiN were prepared by physical vapor deposition on iron at 500°C to investigate the phenomena occurring at the coating/substrate interface during deposition. By means of depth selective Mössbauer spectroscopy, it was found that preliminary depositions of Ti films lead to the formation of α-Fe(Ti) solid solutions. Depending on the amount of deposited Ti, the α-Ti(Fe) solid solution and Fe?Ti intermetallic compounds can form. The influence of interfacial phases on the film adhesion is discussed.