源气浓度对CVD ZrC涂层的影响

以ZrCl4、CH4为源气,H2和Ar为稀释气体和载气,采用化学气相沉积法(CVD)制备了ZrC涂层,研究了源气C/Zr比对ZrC涂层组成及形貌的影响。通过表征得出ZrC涂层表面比较粗糙,随着源气中C/Zr减小,ZrC涂层表面块状颗粒更致密,颗粒大小趋于一致;ZrC涂层中有Zr、C、O元素,含有化学计量比为1:1的ZrC相和自由碳相,随着源气中C/Zr减小,涂层中Zr的原子分数相应增大,涂层中只有约20%的Zr元素与C结合形成ZrC。     

Si/Zr质量比对SiC/ZrC涂层微观结构及其抗氧化性能的影响

采用反应熔体浸渗工艺在C/C复合材料表面制备了SiC和SiC/ZrC抗氧化涂层,并利用XRD、SEM和EDS等分析手段研究了浸渗粉料中Si/Zr质量比对抗氧化涂层的相组成和微观结构的影响,考察了SiC和SiC/ZrC涂层在1 400℃静态空气气氛中的抗氧化性能,初步探讨了SiC/ZrC涂层的抗氧化机制。研究结果表明,随着浸渗粉料中Si/Zr质量比由4.5∶1.5降至2∶4,制得的SiC/ZrC涂层表面涂层致密性呈现先增后降的趋势,而涂层厚度则逐渐减小。当Si/Zr质量比为3∶3时,制得SiC/ZrC涂层C/C复合材料表现出优良的抗氧化性能,在空气气氛中1 400℃氧化6h后增重0.5%左右,而SiC涂层C/C复合材料在相同条件下氧化5h后失重率达到26.71%。SiC/ZrC涂层优异的抗氧化性能与其表面形成的一层致密、连续的ZrSiO4-SiO2-ZrO2玻璃膜有关。     

固态输送ZrCl4低压化学气相沉积制备ZrC涂层的特征

采用ZrCl4-CH4-H2-Ar反应体系、固态输送ZrCl4粉末低压化学气相沉积(CVD)制备ZrC涂层。研究温度对低压化学气相沉积ZrC涂层物相组成、晶体择优生长、涂层表面形貌、断面结构、涂层生长速度和沉积均匀性等方面的影响。结果表明:不同温度下沉积的涂层主要由ZrC和C相组成;随着温度的升高,ZrC晶粒(200)晶面择优生长增强,颗粒直径增大,表面致密性增加,沉积速率上升;涂层断面结构以柱状晶为主;随着离进料口距离的增加,涂层的沉积速率逐渐减小;1 500℃时,沉积系统的均匀性比1 450℃时的差。     

气体流量对LPCVD ZrC涂层结构和沉积机理的影响

利用低压化学气相沉积(LPCVD)工艺,采用Zr-Br2-C3H6-H2-Ar反应体系,在1200℃下,于石墨基底表面制备了ZrC涂层。研究了气体流量对ZrC涂层微观形貌和沉积机理的影响。结果表明,随着气体流量由200 mL/min向1000 mL/min增大,涂层的沉积速率先增大后减小,在800 mL/min时达到极值,极大值为3.37×10-3g·cm-2·h-1。同时,涂层的择优取向发生了明显的变化,在600~800 mL/min范围内,涂层具有稳定且强烈的(200)晶面择优取向。XPS分析结果表明,沉积产物中的C/Zr比也随气体流量的增大,相应的由0.85快速地升高到1.49。当气体流量为200 mL/min时,涂层致密光滑,ZrC晶粒具有典型的等轴晶结构特征;当气体流量为400~800 mL/min时,涂层光滑平坦,ZrC晶粒具有规则的四面体结构;当气体流量为1000 mL/min时,涂层表面存在着大量不规则的岛状、弓状颗粒。基底表面边界层厚度的变化是影响涂层沉积过程的主要因素。     

氢气浓度对常压化学气相沉积ZrC涂层的影响

采用ZrCl4-CH4-H2-Ar体系在C/C材料基体上进行常压化学气相沉积(APCVD)制备碳化锆(ZrC)涂层.通过X射线衍射技术(XRD)和扫描电镜(SEM)对不同H2浓度下制备的ZrC涂层进行分析.对H2在沉积过程中的作用机制进行了讨论.结果表明:H2浓度对涂层的相组成、晶体的择优取向和结构形态有重要影响;无H2或H2浓度较低时,涂层含有大量的热解碳,由ZrC和碳两相组成,涂层呈多孔颗粒状;当H2浓度(体积分数)增加到30%以上时,涂层的相成分变为单一ZrC相;当H2的浓度增加到90%时,ZrC晶体取向由(111)、(200)转变为强烈的(220)择优取向,晶粒形貌变为纳米针状.     

炭/炭复合材料ZrC涂层的制备及显微组织结构

通过冷态输送ZrCl4粉末,利用低压化学气相沉积法在C/C复合材料表面制备ZrC涂层。采用X射线衍射和扫描电镜研究沉积温度和沉积位置对ZrC涂层物相成分和微观形貌的影响。结果表明:在1 400~1 600℃时,沉积涂层物相均为单一的ZrC。ZrC晶粒择优取向随沉积温度的升高而发生变化;在1 400和1 500℃时,ZrC晶粒择优取向面为(200);1 600℃时,晶粒择优取向面转变为(220)和(200),且择优不明显;随着沉积温度的进一步升高,涂层晶粒尺寸明显增大,涂层表面ZrC颗粒由球形逐渐转变为金字塔形多面体。在1 400~1 600℃沉积时,反应器的100~230mm沉积区间内可以得到成分单一、择优取向一致、表面形貌相同的ZrC涂层。     

SiZr液相烧结法制备SiC-ZrC涂层对C/SiC复合材料抗氧化性能的影响

使用Si-25％Zr(质量分数)合金通过液相烧结法在C/SiC复合材料表面制备了SiC-ZrC抗氧化涂层,研究了烧结过程中涂层的相结构演化,并测试了1400℃及空气气氛下材料的抗氧化性能,分析了涂层氧化前后显微结构的变化,以及氧化对C/SiC复合材料弯曲性能的影响.结果表明,Zr元素在涂层中以ZrC相的形式存在,ZrC颗粒的引入细化了反应SiC层的组织,在氧化过程中形成致密连续的SiO2薄膜,并在氧化500 s后试样出现增重,制备了SiC-ZrC抗氧化涂层的C/SiC样品在1000 s的氧化实验后弯曲强度下降低于5％.     

温度对CVD-TaC涂层组成、形貌与结构的影响

利用TaCl5-C3H6-H2-Ar反应体系,用化学气相沉积法(CVD)成功地在C/C复合材料表面沉积TaC涂层及C-TaC复合涂层.研究了温度对TaC涂层的相组成和表面形貌的影响以及CVD-TaC涂层的沉积机理.结果表明:在1373～1673 K温度范围内能够在C/C复合材料表面制备碳化钽涂层,它由TaC和游离碳组成.提高沉积温度和H2/C3H6的流量比,TaC涂层中游离碳的含量减少;随着沉积温度的升高,TaC涂层的颗粒尺寸增大,均匀程度下降;在1 573 K时颗粒间出现明显的烧结界面,结构致密无裂纹.制备出成分波动的C-TaC复合涂层,该涂层与基体间具有良好的机械相容性.分析了低应力、无裂纹TaC复合涂层的形成机制.     

基于冷喷涂制备ZrC掺杂NiAl热障涂层粘结层

目的开发NiAl金属间化合物热障涂层粘结层。方法通过机械合金化技术制备了Ni/Al、Ni/Al+0.5%ZrC与Ni/Al+0.07%三种复合结构粉末。采用冷喷涂在镍基高温合金(IN738)基体上制备Ni/Al、Ni/Al+0.5%ZrC与Ni/Al+0.07%三种复合涂层,然后在保护气氛Ar气中进行热扩散制备这三种金属间化合物涂层。结果低温球磨8 h后可以获得具有亚微米层状结构的Ni/Al+ZrC复合结构粉末。喷涂态Ni/Al合金复合涂层保留了粉末的结构,经1080℃保温10 h后,形成了致密的NiAl金属间化合物涂层。结论掺杂ZrC(0.07%和0.5%)的Ni/Al粉末在球磨后比未掺杂ZrC的粉末更均匀。掺杂ZrC的粉末形成了部分NiAl金属间化合物,而没有掺杂ZrC的粉末则无NiAl金属间化合物形成。冷喷涂可以制备几乎无氧化Ni/Al粉末粘结层。热处理后原喷涂态涂层中的亚微米的层状结构已基本消失,变成了较为均匀的组织。     

硬质合金刀具ZrC涂层的沉积

采用原位卤化反应直接形成的ZrCl4气体作为Zr源,在硬质合金刀具上沉积CVD-ZrC涂层。用SEM,XRD分析检测了合金刀具基底不同表面上沉积生长ZrC涂层的厚度均匀性、沉积速率、形貌组织、织构取向;通过理论计算与工艺实际的涂层沉积转化率对比,定量表征了该沉积体系工艺参数下ZrC涂层的沉积转化率。结果显示,CVD涂层炉内不同位置合金刀片表面沉积的ZrC涂层均匀;由于工艺温度限制,涂层沉积速率较低;ZrCl4转化为ZrC涂层的工艺实际转化率约11%,在理论最大转化率14%范围内;相同温度下随着沉积压力升高,涂层的沉积转化率缓慢降低到10%并趋于稳定;直接在合金基底沉积形成的ZrC涂层为细小的颗粒状形貌,而在合金基底TiN涂层表面上沉积生长的ZrC具有典型的片状组织形貌;对应的涂层生长织构取向从(311)到(111)转变。     

ZrC-SiC-MoSi2涂覆C/C-SiC-ZrC陶瓷基复合材料在氧乙炔焰下的烧蚀行为及机理(英文)

为进一步提高C/C复合材料在不同烧蚀环境下的烧蚀性能,采用浆料刷涂法在C/C-SiC-ZrC陶瓷基复合材料上制备Zr含量分别为34%和60%(质量分数)的ZrC-SiC-MoSi₂涂层,并且利用氧乙炔焰研究涂层C/C-SiC-ZrC复合材料在3种不同氧气及乙炔流量下的烧蚀行为。结果表明：随着Zr含量的增加,涂层内部的ZrC和SiC颗粒尺寸明显减小,且颗粒分布更加均匀。Zr含量为60%的涂层线烧蚀率随氧气和乙炔流量的增加而增加,而Zr含量为34%的涂层线烧蚀率随氧气和乙炔流量的增加,先增加后降低。此外,详细讨论ZrC-SiC-MoSi₂涂层在不同条件下的烧蚀机理。随着氧气和乙炔流量的增加,主要的烧蚀机制由氧化变为氧化和蒸发的结合作用,最后变为氧化、蒸发及剥蚀的结合作用。     

Wear and Corrosion Behavior of Zr-Doped DLC on Ti-13Zr-13Nb Biomedical Alloy

Zirconium (Zr)-doped DLC was deposited on biomedical titanium alloy Ti-13Nb-13Zr by a combination of plasma-enhanced chemical vapor deposition and magnetron sputtering. The concentration of Zr in the films was varied by changing the parameters of the bi-polar pulsed power supply and the Ar/CH₄ gas composition. The coatings were characterized for composition, morphology, nanohardness, corrosion resistance in simulated body fluid (SBF) and tribological properties. X-ray photoelectron spectroscopy (XPS) studies on the samples were used to estimate the concentration of Zr in the films. XPS and micro-Raman studies were used to find the variation of I _D/I _G ratio with Zr concentration. These studies show that the disorder in the film increased with increasing Zr concentration as deduced from the I _D/I _G ratio. Nanohardness measurements showed no clear dependence of hardness and Young’s modulus on Zr concentration. Reciprocating wear studies showed a low coefficient of friction (0.04) at 1 N load and it increased toward 0.4 at higher loads. The wear volume was lower at all loads on the coated samples. The wear mechanism changed from abrasive wear on the substrate to adhesive wear after coating. The corrosion current in SBF was unaffected by the coating and corrosion potential moved toward nobler (more positive) values.     

Oxidation behavior of MoSi2 and Mo(Si,Al)2 coated Mo–0.5Ti–0.1Zr–0.02C alloy

MoSi₂ and Mo(Si, Al)₂ coatings were prepared on Mo–0.5Ti–0.1Zr–0.02C alloy using pack cementation process. Oxidation studies revealed that Mo(Si, Al)₂ coating had a much superior oxidation resistance in the temperature range from 400 to 900 °C, where pest disintegration of MoSi₂ occurs due to internal oxidation. The growth kinetics of Al₂O₃ layer formed on Mo(Si, Al)₂ coating was much slower than that of SiO₂ layer formed on MoSi₂ coatings during oxidation.     

Role of C: Zr stoichiometry in the formation of a nanocrystalline structure and magnetic properties in Fe87-x Zr13Cx films

X-ray diffraction analysis was used to study the structure of as-sputtered and annealed Fe-13 at. % Zr-C films, which were produced by reactive magnetron sputtering and characterized by stoichiometric and nonstoichiometric (with respect to ZrC) at. % C to at. % Zr ratios. A special packet of programs was used to resolve wide reflections observed in X-ray diffraction patterns of the films. The as-sputtered films of all compositions were found to be amorphous in terms of X-ray diffraction. The thermal stability of the amorphous phase increases as the C: Zr ratio in the films departs from the stoichiometric ratio (1: 1) characteristic of the monocarbide ZrC. Annealing leads to the formation of a mixed (amorphous + nanocrystalline) structure. Depending on the carbon content and annealing temperature, the phase composition of the films is represented by different combinations of phases, such as bcc α-Fe (the basis phase), fcc ZrC, monoclinic Fe₂C, monoclinic Fe_2.5C, orthorhombic Fe₃C, and Fe₂₃Zr₆. After annealing at 550°C, the best magnetic properties are characteristic of the films having the stoichiometric composition with respect to ZrC (at. % C: at. % Zr ～ 1).     

ZrC增强激光熔覆CoCrNi合金熔覆层的组织及性能

本研究采用激光熔覆技术,在低碳钢表面制备了ZrC增强的CoCrNi合金涂层。研究了ZrC的不同分数(0, 1, 3, 5 wt.%)对CoCrNi基中熵合金涂层组织、硬度和耐磨性的影响。利用X射线衍射仪、扫描电镜和能谱仪分析了涂层的相组成及微观组织结构,并采用显微硬度和摩擦磨损试验对样品的硬度和耐磨性进行了测试。结果表明：熔覆层与基体形成了良好的冶金结合,没有出现明显的裂纹和及空洞等缺陷。不含ZrC的CoCrNi中熵合金涂层由单相FCC结构组成,随着涂层中ZrC的加入,涂层中的物相组成变为了FCC+ ZrC_0.7+Cr₂₃C₆+ZrO₂。涂层的晶粒得到了明显细化,实现了晶界强化、固溶强化和弥散强化(Orowan)的共同作用,形成的碳化物Cr₂₃C₆相与FCC固溶体结合形成共晶碳化物,起到了协同强化作用,有效地提高了涂层的硬度和耐磨性。然而ZrC中的Zr与空气中的杂质O结合生成的ZrO₂也对涂层的性能产生了不利影响,主要是因为ZrO₂的存在会导致涂层中颗粒分布不均匀加剧,弱化弥散强化的作用。所以当ZrC较少时,涂层的性能并未得到较好的提升,但是当涂层中ZrC含量增加到5wt.%时,涂层中析出了较多的强化相ZrC0.7能够有效的提高材料的性能,该涂层的最大硬度为651±15 HV_0.1,摩擦系数为0.161,相较于不含ZrC的涂层均有较大的提升。     

The history of hard CVD coatings for tool applications at the University of Technology Vienna

The history of chemical vapour deposition (CVD) started in the 19th century with the production of lamp filaments and by the Mond process for the nickel production. In the 20th century Van Arkel deposited metals from the gas phase for application in lamp industry.TiC was the first hard coating deposited by CVD in the 1950s. Nearly 20 years later Krupp Widia introduced the first commercial TiC coating on hardmetal tools.Prof. Richard Kieffer started with TiN deposition by the CVD process in the 1970s at the “Technischer Hochschule Wien” and Prof. Benno Lux continued with Al₂O₃- and diamond coatings.In the following years CVD processes for TiN, Ti(C,N), ZrC, (Ti,Zr)C, TiB₂, Al₂O₃, Ta_xC, Cr_xC_y, diamond, BN and BCN were investigated at the University of Technology Vienna.The depositions of new crystalline solid solutions (mixed crystals), nano-crystalline materials and nano-crystalline mixtures of phases have been research topics so far.     

Interdiffusion behavior of Al‐rich oxidation resistant coatings on ferritic–martensitic alloys

Interdiffusion of thin Al‐rich coatings synthesized by chemical vapor deposition (CVD) and pack cementation on 9Cr ferritic–martensitic alloys was investigated in the temperature range of 650–700 °C. The compositional changes after long‐term exposures in laboratory air and air + 10 vol% H₂O were examined experimentally. Interdiffusion was modeled by a modified coating oxidation and substrate interdiffusion model (COSIM) program. The modification enabled the program to directly input the concentration profiles of the as‐deposited coating determined by electron probe microanalysis (EPMA). Reasonable agreement was achieved between the simulated and experimental Al profiles after exposures. The model was also applied to predict coating lifetime at 650–700 °C based on a minimum Al content (C_b) required at the coating surface to re‐form protective oxide scale. In addition to a C_b value established from the failure of a thin CVD coating at 700 °C, values reported for slurry aluminide coatings were also included in lifetime predictions.     

激光熔覆原位制备ZrC增强涂层的颗粒行为特征

通过添加氧化锆和石墨的混合粉末到镍基合金粉末中,利用激光熔覆技术在中碳钢表面上制备了原位析出ZrC颗粒增强金属Ni基复合涂层。利用扫描电镜(SEM),能谱仪(EDS)和X射线衍射设备(XRD)对涂层的组织、物相和成分进行了观察、分析和探讨。对涂层内部的ZrC颗粒形貌、生成以及生长机理、分布特点进行了分析,探讨了颗粒分布对涂层硬度性能的影响。结果表明,ZrC颗粒在中上部分布较为均匀,主要以三角形和四边类似菱形和长轴形为主,颗粒在对流和界面斥力共同作用下发生的碰撞、烧结以及枝晶间的阻力是成形主因。由于ZrC颗粒以及内部碳化物如M₂₃C₆的生成分布,复合涂层的硬度得到了明显的提升,最终其硬度可达HV_0.2 720。