磁控溅射工艺对FeCrCoNiMn氧化物薄膜质量的影响

目的 探究氧气浓度、基底温度和溅射功率对高熵合金氧化物薄膜成分、膜基结合力和硬度的影响,分别找出某一工艺参数的改变对性能的影响趋势,并总结影响因素和规律。方法 采用射频磁控溅射方法在Si(100)基体上制备不同工艺参数下的(FeCrCoNiMn)Ox薄膜,结合X射线衍射仪(XRD)、能谱仪(EDS)、划痕仪、纳米压痕仪分析薄膜的物相结构、成分组成、膜基结合力、硬度和弹性模量。结果 薄膜为FCC结构。膜基结合力、硬度和弹性模量随着氧气浓度的增加,分别由4.85 N、6.06 GPa、137.8 GPa提高至6.56 N、14.51 GPa、189.4 GPa,最后降至3.75 N、7.52 GPa、144.9 GPa。薄膜的膜基结合力、硬度和弹性模量随着基底温度的升高而升高,分别由3.6 N、12.58 GPa、164.2 GPa升高到5.05 N、14.51 GPa、189.4 GPa。随着溅射功率的提高,膜基结合力由5.05 N提高至8.25 N,硬度和弹性模量呈先升高后降低的趋势。结论 与普通FeCrCoNiMn合金薄膜相比,氧原子的引入使(FeCrCoNiMn)Ox薄膜拥有更大的混合熵,增强了其固溶强化效应。氧气浓度和溅射功率对薄膜成分的影响较大,基底温度对成分无明显影响。适当提高氧气浓度和溅射功率可以有效提高薄膜的力学性能,在温度为350 ℃时膜基结合力和硬度均最好。     

激光熔覆CoCrNiMnTix高熵合金涂层组织及耐磨性能研究

目的 针对高铁制动盘等高速强力磨损的关键件,设计激光熔覆CoCrNiMnTix高熵合金涂层,提高表面的硬度和耐磨性。方法 采用激光熔覆技术在Q235钢表面制备CoCrNiMnTix高熵合金涂层,利用XRD和SEM对涂层微观组织进行表征,通过显微硬度计和纳米压痕仪测试涂层硬度,运用摩擦磨损试验机和三维形貌仪研究涂层的摩擦磨损性能。结果 在激光熔覆CoCrNiMnTix涂层中,随着Ti含量的增加,涂层物相由单一的FCC相转变为FCC+Laves相。由于固溶强化以及Laves相含量增多,涂层的显微硬度不断提高,CoCrMnNiTi硬度达到523HV0.1,最高纳米硬度达到6.91 GPa。CoCrNiMnTix系涂层的弹性模量大小相近。随着Ti含量的增加,涂层的耐磨性呈现升高趋势,当Ti的摩尔分数增加至0.75时,涂层具有最好的耐磨性,但进一步增加Ti含量时,由于脆硬性的Laves相逐渐增多,磨损形式由低Ti含量时的粘着磨损逐渐转变为高Ti含量时的磨粒磨损,使涂层耐磨性能下降。结论 激光熔覆CoCrMnNiTix涂层可以显著提高基体的耐磨性,Ti的摩尔分数为0.75时,在FCC基体中形成了少量Laves相,既提高硬度,又实现强韧配合,涂层表现出最佳的耐磨损性能。     

真空阴极多弧离子镀沉积纳米超硬氮化钛薄膜

利用真空阴极多弧离子镀系统在Cr12Mo4V钢基材上制备出膜基间结合很好的纳米超硬氮化钛(TiN)薄膜.利用纳米硬度计、划痕仪、球一盘试验机、X射线衍射仪、透射电子显微镜和扫描电子显微镜分别考察了薄膜的纳米硬度、膜基间结合力、摩擦磨损性能和显微结构.结果表明,气体压力和脉冲基体负偏压对薄膜性能有重要影响;超硬TiN薄膜的纳米硬度为47.6 GPa、临界载荷为63 N、摩擦因数在0.5至0.8之间;结构细密的超硬薄膜在(111)晶面有强烈的择优取向.     

硬质合金表面多弧离子镀(Ti,Al,Zr,Cr)N多元氮化物膜

采用Ti-Al-Zr合金靶和Cr靶,用多弧离子镀技术在WC-8%Co硬质合金基体上沉积(Ti,Al,Zr,Cr)N多元氮化物膜。分析了薄膜的成分、形貌、粗糙度和结构,研究了薄膜的显微硬度、膜/基结合力和抗高温氧化性能。结果表明,获得的多元氮化物膜仍是B1-NaCl型TiN面心立方结构;适当控制偏压条件可以改善薄膜的表面形貌;在不同的偏压条件下,(Al+Zr+Cr)/(Ti+Al+Zr+Cr)的成分比为0.41～0.43,当其比值趋于0.4时,薄膜的显微硬度和膜/基结合力达到最大值3600HV0.01和200N;同时薄膜的抗高温氧化性能提高,最高温度可达700℃左右。     

光发射谱对CrTiAlN涂层性能的影响

在不同光发射谱(OEM)条件下,采用闭合场非平衡磁控溅射技术(CFUBMSIP)在SDC99冷作模具钢表面沉积CrTiAlN涂层,采用X射线衍射仪(XRD)、显微硬度仪、原位纳米力学测试系统和销盘摩擦磨损试验机(POD)测试分析涂层的相结构、表面硬度以及耐磨损性能。结果表明:各条件下制备的CrTiAlN涂层均为FCC结构,且在(200)晶面择优取向;光发射谱值为65时,制备的CrTiAlN涂层具有较高的表面承载能力以及膜基结合力,纳米硬度和弹性模量分别为22.7 GPa和276.4 GPa;OEM65制备的CrTiAlN涂层较OEM70、OEM80制备的CrTiAlN涂层具有更低的摩擦因数和磨损率,表现出更佳的摩擦磨损性能。     

Zr掺杂类金刚石薄膜摩擦性能及耐腐蚀性能的影响

目的改善不锈钢摩擦性能及耐腐蚀性能。方法通过线性阳极层离子源辅助非平衡磁控溅射法,制备了不同Zr含量的类金刚石(DLC)薄膜,采用扫描电子显微镜、拉曼光谱仪、纳米硬度仪、高温销盘磨损仪、电化学工作站,对薄膜的化学成分、显微结构、纳米硬度、薄膜摩擦性能及耐腐蚀性能进行测试研究。结果随着Zr靶功率的增大,Zr含量线性增加。Zr含量从4.9%增加至16.3%时,I_D/I_G增大,薄膜硬度从12.1 GPa逐渐下降至8.4 GPa;Zr含量增大至21.2%时,I_D/I_G减小,薄膜硬度增大至11.4 GPa。涂镀类金刚石薄膜的不锈钢基体比无涂层的不锈钢基体有更低的摩擦系数,更好的耐磨损性能。Zr掺杂DLC薄膜的最小摩擦系数为0.07。Zr含量从4.9%增加至16.3%,DLC薄膜的耐腐蚀性能减弱;Zr含量继续增加,DLC薄膜的耐腐蚀性能增强。当Zr含量不大于11.9%时,沉积Zr掺杂DLC膜的不锈钢基体的耐腐蚀性能比不锈钢基体的更强。结论 Zr含量不大于11.9%时,Zr掺杂类金刚石薄膜既可以有效地改善不锈钢基体的摩擦磨损性能,又可以大幅提高耐腐蚀性能。     

中频对靶磁控溅射制备含铬类金刚石薄膜

利用新型中频对靶磁控溅射在硅和M2高速钢基体上沉积了一系列无氢含铬类金刚石膜.考察了类金刚石膜的表面形貌、显微结构、硬度、结合力和摩擦磨损性能.结果表明：合成的类金刚石薄膜具有优良的综合性能,硬度为30-46GPa、结合力Lc达50-65N、大气环境下摩擦系数约为0.1.     

镁合金表面磁控溅射DLC/SiC薄膜的纳米压痕与摩擦磨损性能

采用室温磁控溅射技术在镁合金(AZ91D)表面制备出DLC/SiC(类金刚石/碳化硅)双层薄膜(SiC为中间层),研究了薄膜的纳米压痕行为、膜基黏附力和膜基系统的摩擦磨损性能.结果表明:DLC薄膜具有低的纳米硬度(3.05 GPa)、低的弹性模量(24.67 GPa)和高的硬弹比(0.122);膜基系统具有高的界面黏附力和好的摩擦磨损性能;在以氮化硅球为对摩件的室温干摩擦条件下其磨损速率在10~(-6)mm~3·m~(-1)·N~(-1)级,摩擦系数约为0.175.分析表明:膜基系统具有的良好抗磨性能与其薄膜具有高的塑性和硬弹比、膜基系统具有好的弹性模量匹配是相一致的;DLC薄膜具有的不寻常力学行为(很低的硬度和弹性模量等)与其基材是镁有关.     

类富勒烯/非晶多层碳膜的制备及性能

针对碳基薄膜存在的高应力问题,利用单极脉冲等离子体增强化学气相沉积技术在单晶硅衬底上制备了含氢类富勒烯/非晶层交替构成的类金刚石多层膜。采用高分辨透射电子显微镜和激光拉曼光谱仪分析了多层膜的结构特征;用X射线光电子能谱分析了薄膜的化学键状态;用纳米压痕仪测定了薄膜的硬度和弹性模量;在CSM往复式摩擦磨损试验机上考察了薄膜在大气下的摩擦学性能,同时比较了多层膜与非晶、类富勒烯薄膜的力学性能和摩擦磨损性能。结果表明:多层膜的硬度高于非晶和类富勒烯单层薄膜,达到28.78GPa;在大气环境下与Si3N4球对摩时平均摩擦因数略低于类富勒烯单层膜,耐磨性明显优于单层非晶和类富勒烯薄膜。     

MoS2/Ti3C2Tx对磷酸盐涂层宽温域摩擦学性能的影响

目的 以MoS2/Ti3C2Tx为固体润滑剂,在25(室温)~400 ℃下制备具有优异摩擦学性能的MoS2/Ti3C2Tx磷酸盐涂层,并研究它在不同温度下的减摩抗磨机制。方法 以氢氟酸为MAX相(Ti3AlC2)粉体的蚀刻剂,制备具有“手风琴”形貌的Ti3C2Tx MXene。以硫脲、钼酸铵、MXene为原料,制备MoS2/Ti3C2Tx复合材料。以Al(H2PO4)3为黏结剂,以CuO为固化剂,分别以Ti3C2Tx和MoS2/Ti3C2Tx为固体润滑剂,制备Ti3C2Tx磷酸盐涂层和MoS2/Ti3C2Tx磷酸盐涂层。通过高温摩擦磨损试验机和光学数码显微镜测试涂层在25~400 ℃时的摩擦因数和磨损率,采用扫描电子显微镜和显微共焦激光拉曼光谱仪分析磨痕表面形貌、物相,进而探讨磨损机理。结果 当Ti3C2Tx与Al(H2PO4)3的质量比为2∶1时,Ti3C2Tx磷酸盐涂层在室温(25 ℃)下的摩擦因数和磨损率均最低,分别为0.38和2.75×10⁻⁴ mm³/(N.m)。在Ti3C2Tx表面负载MoS2,将MoS2/Ti3C2Tx作为固体润滑剂,能够显著降低磷酸盐涂层在25~400 ℃下的摩擦因数,同时磨损率也有所降低。MoS2/Ti3C2Tx磷酸盐涂层在室温下的摩擦因数低至0.11,相较于Ti3C2Tx磷酸盐涂层降低了71.1%,其磨损率相较于Ti3C2Tx磷酸盐涂层降低了1个数量级。在25~400 ℃范围内,MoS2/Ti3C2Tx磷酸盐涂层的摩擦因数均低于0.21。随着温度的升高,摩擦因数呈先减小后增大的趋势,磨损率整体上呈增大趋势。结论 相较于Ti3C2Tx磷酸盐涂层,MoS2/Ti3C2Tx磷酸盐涂层在25~400 ℃下的摩擦学性能均得到显著提升。     

Control of morphology (ZrN crystallite size and SiNx layer thickness) in Zr-Si-N nanocomposite thin films

DC reactive magnetron sputtering was used for the deposition of Zr-Si-N thin films. Four series of samples have been deposited at various substrate temperatures T_S: 300 K, 510 K, 710 K and 910 K. Depending on T_S, different N₂ partial pressures p_N2 were required to obtain nearly stoichiometric ZrN films. Si content (C_Si) was varied in each series by changing the power applied on the Si target, whereas the power on the Zr target was kept constant. The microstructure of the coatings was examined by XRD and in cross-section by transmission electron microscopy (TEM). Depending on T_S and p_N2, the deposition rate showed significant variations from 0.04 to 0.18 nm/s. The correlation between film morphology (preferential orientation of crystallites, grain size, column dimensions, thickness of the SiN_x layer covering ZrN crystallites) and the deposition conditions (power applied on Si target, temperature, nitrogen partial pressure and deposition rate) provides useful information for optimizing the deposition process.     

工艺参数对直流磁控溅射膜沉积的影响

在为进一步了解工艺参数对溅射膜沉积的影响,开展了不同工作气体压强、不同溅射功率和有无负偏压条件下的Zr、Cu、Ni单金属溅射膜和Zr—Cu、Zr-Ni二元合金溅射膜的溅射沉积实验。使用称重法,分析了溅射膜沉积量随工作气体压强、溅射功率的变化规律;通过分层溅射和共溅工艺实验,对比了相同溅射功率下Zr与Cu、Zr与Ni元素间分层溅射膜和共溅膜的沉积量;采用扫描电子显微镜,分析、研究了溅射过程中负偏压对Cu溅射膜膜层生长方式的影响。结果表明,由于工作气体压强对电子与气体分子以及对靶材原子与气体分子碰撞几率的影响,使得膜层的沉积量不是随着工作气体压强的升高单纯地呈下降趋势,而是有一最佳压强范围;随着溅射功率的增大,膜层沉积量增加,在溅射功率相等的条件下,由于辉光放电电场叠加增大了工作气体的离化率,使得共溅膜比分层溅射膜的沉积量大得多;溅射过程中施加较高负偏压可以抑制柱状结构生长,细化晶粒,提高膜层致密度。     

High power pulsed magnetron sputtering: A review on scientific and engineering state of the art

High power pulsed magnetron sputtering (HPPMS) is an emerging technology that has gained substantial interest among academics and industrials alike. HPPMS, also known as HIPIMS (high power impulse magnetron sputtering), is a physical vapor deposition technique in which the power is applied to the target in pulses of low duty cycle (< 10%) and frequency (< 10 kHz) leading to pulse target power densities of several kW cm^− 2. This mode of operation results in generation of ultra-dense plasmas with unique properties, such as a high degree of ionization of the sputtered atoms and an off-normal transport of ionized species, with respect to the target. These features make possible the deposition of dense and smooth coatings on complex-shaped substrates, and provide new and added parameters to control the deposition process, tailor the properties and optimize the performance of elemental and compound films.     

N2流量比对复合磁控溅射Zr-B-N薄膜结构和性能的影响

目的 在反应沉积时补充金属离子,增加薄膜中金属氮化物硬质相的数量,优化复合磁控溅射Zr-B-N薄膜的制备工艺,揭示N2流量比（N2/(N2+Ar)）对Zr-B-N薄膜结构和性能的影响规律,进一步强化Zr-B-N纳米复合薄膜。方法 采用高功率脉冲磁控溅射和脉冲直流磁控溅射复合镀膜技术沉积Zr-B-N薄膜,借助X射线衍射仪、能谱仪、扫描电镜、纳米压痕仪、划痕测试仪和摩擦试验机,研究N2流量比对Zr-B-N薄膜成分、微观结构、力学性能和摩擦性能的影响。结果 Zr-B-N薄膜具有典型的纳米复合结构,即BN非晶层包裹着ZrB2、Zr3N4、Zr2N、ZrN等纳米晶,所有Zr-B-N薄膜均沿（100）晶面择优生长。随着N2流量的增加,（100）晶面的衍射峰宽化加剧;薄膜硬度由36.2 GPa下降到21.0 GPa;膜/基结合力逐渐增强,临界载荷从34.8 N增加到55.8 N;摩擦系数逐渐增大。当N2流量比为42.9%时,摩擦系数相对较低,约为0.48,归因于薄膜内形成了沿（220）晶面生长的ZrN相,从而起到了良好的减摩作用。结论 当N2流量比为42.9%时,Zr-B-N薄膜具有纳米复合结构和良好的各项性能。     

Characterisation of R.F. magnetron sputtered Cr-N,Cr-Zr-N and Zr-N coatings

Binary Cr-N, Zr-N and Cr-Zr-N films were synthesised using a R.F. reactive magnetron sputtering technique by co-sputtering Cr and Zr. The crystalline structure, morphology, mechanical and tribological properties of the films as a function of Zr content were characterised by X-ray diffraction, microanalysis X (WDS, EDS), X-ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, nanoindentation, scratch adhesion and pin-on-disc sliding wear tests. The residual stress was calculated with the Stoney formula. The Cr-Zr-N films exhibit a two-phase microstructure, containing a cubic (CrN, ZrN) with hexagonal (Cr₂N, Zr₂N) phases, as shown by X-ray diffraction. As the Zr content increased, a columnar and compact structure is developed with a low surface roughness. The results reveal that the mechanical and tribological properties of the films were found to depend on the Zr content and the hardness (maximum 26.3?GPa) is greatly improved in comparison with CrN and ZrN films, especially at 31?at.-% Zr. In the scratch test, the hardest film (Cr_0.18Zr_0.31N_0.47) exhibited an adhesive failure at Lc_2?=?34.3?N.     

基于硅靶和碳化硅靶的碳化硅薄膜磁控溅射工艺对比

目的 通过基于碳化硅陶瓷靶的直接溅射和基于硅靶与甲烷的反应溅射,在Si(100)基底上沉积碳化硅薄膜,对比两种工艺制备碳化硅薄膜的异同.方法 采用直接磁控溅射与反应磁控溅射工艺制备碳化硅薄膜,通过白光干涉仪、轮廓仪、X光电子能谱仪(XPS)分析薄膜粗糙度、厚度、沉积速率、组分,通过X射线衍射仪和扫描电子显微镜分析薄膜的物相结构和形貌.结果 基于硅靶和甲烷的反应溅射工艺,甲烷流量百分比为20％～70％时,沉积速率从11.3 nm/min升高到36.5 nm/min.甲烷流量百分比为20％～60％时,表面粗糙度Rq值变化不大;甲烷流量百分比为70％时,Rq值有增大的趋势.对于甲烷反应溅射工艺,硅碳元素比例可调,但甲烷气体不易控制.基于碳化硅陶瓷靶工艺,随沉积时间(即膜层沉积厚度)的增加,表面粗糙度Rq变化不大,硅碳原子比接近1:1.两种工艺制备的薄膜均为晶态,且为8H-SiC.结论 比较两种工艺,相同靶功率下,硅靶反应溅射的沉积速率明显快于碳化硅陶瓷靶.硅靶反应溅射的元素比例可调,但甲烷气体不易控制;碳化硅陶瓷靶的沉积过程稳定,硅碳原子比接近1:1.     

Recent advances in modulated pulsed power magnetron sputtering for surface engineering

Over the past 10 years, the development of high-power pulsed magnetron sputtering (HPPMS) has shown considerable potential in improving the quality of sputtered films by generating a high degree of ionization of the sputtered species to achieve high plasma density by using pulsed, high peak target power for a short period of time. However, the early HPPMS technique showed a significantly decreased deposition rate as compared to traditional magnetron sputtering. Recently, an alternative HPPMS deposition technique known as modulated pulsed power (MPP) magnetron sputtering has been developed. This new sputtering technique is capable of producing a high ionization fraction of sputter target species and while at the same time achieving a high deposition rate. This paper is aimed at giving a review of recent advances in the MPP technique in terms of the plasma properties, the improvements in the structure and properties of the thin films, and the important advances in the high rate deposition of high quality thick coatings on the order of 20–100 μm in thickness.     

脉冲频率对HiPIMS制备TiN薄膜组织和力学性能的影响EI北大核心CSCD

为探究脉冲频率对通过高功率脉冲磁控溅射制备TiN薄膜组织力学性能的影响,选用Ti靶和N2气体,采用反应磁控溅射技术通过改变高功率脉冲磁控溅射(HiPIMS)电源脉冲频率在Si(100)晶片上制备不同种TiN薄膜。利用X射线衍射仪(XRD)、X射线光电子能谱仪和扫描电子显微镜(SEM)对所制薄膜晶体结构和成分、表面和断面形貌进行分析,利用纳米压痕仪对薄膜的硬度和弹性模量进行表征,并计算H/E和H^(3)/E^(2)。结果表明,高离化率Ti离子轰击促使薄膜以低应变能的晶面优先生长,所制TiN薄膜具有(111)晶面择优取向。薄膜平均晶粒尺寸均在10.3 nm以下,随着脉冲频率增大晶粒尺寸增大,结晶度和沉积速率降低,柱状生长明显,致密度下降,影响薄膜力学性能。在9 kHz时,TiN薄膜的晶粒尺寸可达8.9 nm,薄膜组织致密具有最高硬度为30 GPa,弹性模量374 GPa,弹性恢复为62.9%,具有最优的力学性能。     

Enhancement of aluminum oxide physical vapor deposition with a secondary plasma

Reactive sputtering of aluminum oxide in a planar magnetron system is conducted with a mixture of O₂ and Ar reacting with and bombarding an aluminum target. The aluminum target is powered by a pulsed directed current (DC) bias which functions to discharge the accumulated ions on the insulating AlO_x film surface during the positive duty cycle and suppresses arc formation. A seven-turn helical antenna sits below the magnetron sputtering system in the vacuum system and delivers radio-frequency (RF) power to generate a secondary plasma in the chamber. This plasma can efficiently ionize the sputtered flux, achieving ionized physical vapor deposition (IPVD). A gridded energy analyzer (GEA) and a quartz crystal microbalance (QCM) are located in the substrate plane to allow the ion and neutral deposition rates to be determined. Electron temperature and electron density are measured by a RF compensated Langmuir probe. A RF power of 500 W significantly increases the deposition rate of AlO_x up to half of the Al deposition rate in metallic mode at the total pressure of 1.33 Pa (10 mtorr). At 3.33 Pa (25 mtorr), the ionization fraction of Al atoms reaches 90%. In addition the RF power extends the range of O₂ partial pressure in which the sputtering occurs in the metallic mode. SEM photos show that the secondary RF plasma makes the films smoother and denser due to a moderate level of ion bombardment. The deposition rates and ionization fractions fluctuate as a function of O₂ partial pressure. These variations can be explained by the combined variation of sputtering at the target, electron temperature and electron density.     

Yttria-stabilized zirconia thin films deposited by pulsed-laser deposition and magnetron sputtering

Yttria-stabilized zirconia (YSZ, ZrO₂:Y₂O₃) was deposited on (100) silicon by two physical vapor deposition techniques: pulsed laser deposition (PLD) and reactive magnetron sputtering (RMS). PLD thin films were grown on silicon substrates at 500 °C from the ablation of a 8YSZ ceramic target by a KrF excimer laser. RMS thin films were obtained by direct current magnetron sputtering of a Zr/Y metallic target in an oxygen/argon atmosphere. The deposition rate of the PLD technique using an UV excimer laser delivering pulses at a repetition rate of 40 Hz was found two orders of magnitude lower than the RMS method one. Both techniques led to the growth of crystalline films with a (111) preferential orientation. PLD films were dense and featureless whereas RMS ones exhibited well defined but compact columnar structure. Growth of a YSZ film of about 1 μm covering a rough and porous commercial anode support (NiO-YSZ cermet) was successfully carried out with both methods.