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作者简介:

冷啸,男,1997年出生,硕士研究生。主要研究方向为材料表面工程。E-mail: lengxiaolut@163.com

通讯作者:

张定军,男,1972年出生,博士,教授,硕士研究生导师。主要研究方向为高分子材料及其相关材料。E-mail: zhangdingjunlut@163.com

中图分类号:TG71

DOI:10.11933/j.issn.1007-9289.20231114002

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目录contents

    摘要

    机械加工工艺的进步对切削刀具的性能提出了愈发严苛的要求,一方面刀具应具有更高强度及韧性以便应对高速切削带来的冲击载荷;另一方面刀具还应兼具优异的耐高温、抗氧化性能以满足极端工况下的服役需求。然而,传统刀具硬度的提升往往以牺牲韧性为代价,且传统刀具耐高温、抗氧化性能较差。通过在刀具表面沉积一层硬质、耐高温、抗氧化薄膜可有效解决这些问题。TiB2 具有高硬度、耐高温、抗氧化以及同金属间化学亲和力低等特性,因此,通过在零部件表面沉积 TiB2 薄膜可显著改善切削刀具因摩擦磨损而导致的失效问题。采用直流磁控溅射技术在 Inconel 718 表面沉积一系列 TiB2薄膜,研究在溅射沉积阶段通过调控靶电流(3.0、4.0、5.0 和 6.0 A)对制备 TiB2 薄膜在微观形貌、力学性能及摩擦学性能等方面的影响。结果表明:不同电流条件下沉积薄膜的截面形貌均为柱状结构,随着靶电流增加,薄膜沉积厚度、结晶度及晶粒尺寸增加;弱电流条件下沉积制备薄膜的硬度较低,使得其抗磨损性能较差;强电流条件下沉积制备的薄膜残余应力较大、膜基结合强度较差,从而导致其抗磨损性能较差;靶电流为 4.0 A 时,沉积薄膜拥有最佳综合性能,体现在最低的磨损率 W=6.347× 10−6 mm3 / (N·m)、较高的膜基结合强度 L=36.78 N 以及较低的残余应力 σ=0.145 GPa。探究 TiB2最佳直流磁控溅射制备工艺,揭示 TiB2薄膜在溅射沉积阶段中不同电流强度对其结晶度、硬度及抗磨损性能的影响因素,将其沉积于切削刀具表面可改善切削刀具在高速切削过程中面临的摩擦磨损而导致的凹坑磨损问题。薄膜作为刀具表面涂层可有效防止刀具的高温氧化及元素扩散而导致的切削刀具过快失效问题,延长刀具使用寿命,改善加工精度,同时为高速切削刀具防护薄膜的后续研究提供一定的借鉴。

    Abstract

    With the continual advancement of machining processes, cutting tools are facing increasingly demanding requirements. However, traditional tools often exchange hardness for toughness and have poor resistance to high temperatures and oxidation, which presents challenges in meeting high-speed cutting conditions. The deposition of a hard oxidation-resistant film on the tool surface can effectively address these issues. However, conventional protective films such as TiN and TiC fail to meet the demands of high-speed cutting and high-precision machining in terms of tool hardness, high-temperature resistance, and anti-adhesion. TiB2 is an ideal protective film for high-speed cutting tools due to its high hardness, high-temperature resistance, antioxidation properties, and low chemical affinity for intermetallic materials. In this study, a closed-field unbalanced DC magnetron sputtering technique was employed to deposit thin-film materials on P(100)-type silicon wafers and Inconel 718, which is a high-temperature nickel-based alloy. The results revealed a close correlation between the properties of the deposited TiB2 films and the magnitude of the target current during sputtering deposition. Specifically, increasing the TiB2 target current led to a higher target power, resulting in the deposition of thicker films within the given time frame, where the average thickness increased from 1.468 to 2.168 μm. In addition, increasing the frequency of target sputtering particle bombardment and the temperature in the deposition chamber enhanced the crystallinity of the films and increased the grain size, where the half-peak width of the preferred crystal plane decreased from 2.795°to 1.993°. The difference in the thermal expansion coefficients of the film bases resulted in residual stresses in the films after cooling to room temperature. As the target current strength increased, the chamber temperature increased, leading to a greater temperature difference between the chamber and room. Consequently, the residual stress of the film increased with the target current. Specifically, the minimum residual stress of the deposited film under a target current of 3.0 A was 0.1099 GPa, whereas the maximum residual stress under a target current of 6.0 A was 0.3829 GPa. Moreover, the hardness of the film initially increased and then decreased with an increase in the target current, reaching a peak of 3.0 A under a hardness of 0.3829 GPa. The lowest hardness of the film occurred under the condition of 3.0 A, measuring 14.40 GPa, whereas the highest hardness was under the condition of 5.0 A, measuring 18.66 GPa. This hardness was closely associated with the crystallinity of the film and the ratio of boron-rich tissue phases. Enhancing the crystallinity of the film reduced the number of defects and concentrated the boron-rich phases at the grain boundaries, thereby preventing slippage when an external force was applied. This improvement was beneficial in enhancing the mechanical properties of the films. Depositing the film at 4.0 A yielded the highest hardness of 0.3829 GPa. In addition, films deposited at 4.0 A exhibited the lowest wear rate (W = 6.347×10−6 mm3 / (N·m)) within the system. This study explored the optimal DC magnetron sputtering preparation of TiB2 and elucidated the effects of different current strengths on the crystallinity, hardness, and antiwear properties of TiB2 thin films during sputtering deposition. The deposition of TiB2 thin films on cutting tool surfaces effectively mitigates wear problems caused by frictional wear during high-speed cutting, serving as a protective film that efficiently prevents excessive tool failure resulting from high temperature and oxidation. Additionally, it safeguards against wear caused by high temperature and oxidation, prolonging the tool’s service life and improving machining accuracy. These findings provide valuable insights for the research and development of protective films for high-speed cutting tools.

  • 0 前言

  • 传统刀具难以解决高速切削过程中冲击载荷对刀具造成的性能下降过快及难以实现精密度加工的问题,通过在刀具表面沉积制备一层硬质薄膜,使得切削刀具同时具有高强度和高韧性,以此削弱冲击载荷对刀具性能的影响,使其能够承受更快的切削速度,实现更为精密的加工需求。而随着工艺的进步和要求的提高,现有的 TiN、TiC 等刀具防护薄膜面对越来越高的切削速度及更高的加工温度也显得越来越力不从心。切削刀具防护薄膜的发展现已成为制约我国高速、高精密切削制造发展的一大重要因素,而这其中摩擦磨损是造成切削刀具失效的重要因素。抗磨损技术的应用不仅可以降低能源、材料的损耗,并且对提高切削加工速度及工艺精度也有极大的帮助。

  • TiB2 是一种较为常见的硬质陶瓷[1],不仅具有高硬度[1-2]、出色的化学惰性[1]、耐高温[2]及同常见硬质刀具基体具有较强的膜基结合力等理化性能,还具有耐氧化、耐磨损[3]以及同有色金属间化学亲和力低[24]等特性,可显著减少切削过程中刀具的损耗、氧化失效以及因磨屑堆积与界面结合而导致的磨损加剧等问题。同时,TiB2 具有与常见金属相近的热膨胀系数,使得其不仅能够在常温下对沉积包覆的基材起到保护作用,而且也能在高温及热循环过程中对材料起到较好的减磨效果,可缓解在高速、重负载以及热流屑等综合因素影响下,刀具表面产生的凹坑磨损、元素迁移及高温氧化等不利影响,确保刀具在极端使用条件下仍具有优异的性能表现。此外,TiB2 满足刀具高速切削、耐磨损及防冷焊等方面的应用需求,因此被广泛应用于切削刀具防护薄膜、高温模具以及航空耐高温材料[5]等领域。

  • 当前,制备 TiB2薄膜的方法主要有:大气等离子喷涂(Atmospheric plasma spraying,APS)[5-6]、放电等离子烧结技术(Spark plasma sintering,SPS)[57]、化学气相沉积(Chemical vapor deposition,CVD)[8]、溶胶-凝胶法(Solution-gel method,SOL-GEL)[8]以及物理气相沉积(Physical vapor deposition,PVD)[29-12] 等,不同工艺制备的 TiB2薄膜的性能表现存在较大差异。谢刚等[6]通过大气等离子喷涂在阴极炭块上制备了 TiB2 薄膜,发现相较于直流磁控溅射制备的 TiB2,其具有较高的孔隙率,且存在一定的氧化产物。PESHEV[13]通过采用 B2H6 作为反应 B 源制备了具有较好绕镀性的 TiB2薄膜,但相较于直流磁控溅射,反应 B 源为剧毒物质且易爆,使用存在安全风险。蒙延双等[8]通过溶胶-凝胶制备了性能稳定且耐腐蚀的 TiB2 薄膜,但相较于直流磁控溅射制备的薄膜,膜基结合强度存在一定的不足。此外,直流磁控溅射技术相较阴极电弧离子镀膜技术,具有制备的薄膜表面无大液滴、形貌光洁[14]的特点;与真空蒸发镀相比,具有溅射粒子能量大、沉积薄膜膜基结合强度高、厚度均匀等优点[14]。磁控溅射工艺中靶电流的大小是影响薄膜性能的重要参数。靶电流的变化不仅会使得靶材粒子溅射量受到影响,还将会进一步影响薄膜中元素的化学计量比、结晶度等,并导致薄膜力学性能及摩擦学性能的差异[14]

  • 直流磁控溅射( Direct current magnetron sputtering,DCMS)技术属于物理气相沉积的一种,具有成膜孔隙率低、绕镀性好、膜基结合强度高以及薄膜沉积厚度均匀等特性[14]。靶材激发溅射过程中大量能量以热能形式耗散,导致腔室温度受靶电流影响显著,在较强电流条件下沉积的薄膜会因此具有较高的残余应力[14-15],进而对薄膜力学性能及摩擦学性能产生影响[16]。HELLGREN 等[17]研究了气压和温度对直流磁控溅射沉积 TiB2 薄膜的影响。结果显示,随着沉积温度升高,薄膜 B / Ti 化学计量增大,而随着气压增加,薄膜中 B / Ti 化学计量减小。ZHANG 等[18]通过改变直流磁控溅射过程中腔室内沉积温度的方式,研究了沉积温度对 TiB2 薄膜的结构和性能的影响。结果显示,随着沉积温度的提高,沉积薄膜的硬度及抗磨损性能得到增强。

  • 当前,已有学者探究了直流磁控溅射技术沉积 TiB2 薄膜过程中沉积温度以及偏压改变对薄膜性能的影响,但靶电流条件的影响却较少得到人们的关注。本文采用直流磁控溅射技术,探究不同靶电流条件下,沉积的 TiB2 薄膜结构与性能的差异及其影响机理,并筛选出综合性能最佳的靶电流条件,以应用于切削刀具防护薄膜等[19],改善刀具在高速切削时面临的极端高温及冲击载荷对其的不利影响,缓解刀具在极端服役工况下加工精度过快衰减及刀具失效等问题。

  • 1 试验准备

  • 1.1 薄膜制备

  • 试验使用 Teer CF-800 型直流磁控溅射镀膜设备,采用闭合磁场设计和非平衡稳态直流磁控溅射技术进行薄膜的制备。极性相反的靶头之间相互吸引,磁力线相互交联,整个镀膜室内形成闭合磁场。磁力线分布在靶面前方及两侧,磁场向空间扩展,可以将电子束缚在镀膜室内,以增强磁控溅射等离子体密度,且相邻靶的磁感线全部闭合,整个镀膜室内的电子全部被束缚起来进行旋转运动,增加了与 Ar 气碰撞电离的几率,提高了靶材离化率和薄膜沉积速率。沉积腔室内分别选用对称平行分布的两个纯 TiB2靶(纯度:99.9%)和两个纯 Ti 靶(纯度: 99.9%),靶材均为 470 mm×145 mm 的标准尺寸; 使用 Ar 气(纯度:99.99%)作为工作气体;选择以 Incomel718 高温镍合金(φ 25 mm×9 mm)和 p(100)型硅片(10 mm×10 mm×0.53 mm)为基底进行 TiB2薄膜的沉积制备[20-21]

  • 1.1.1 溅射沉积过程

  • 溅射沉积前,须对已抛光处理的基底样品进行清洁干燥处理。分别将其置于无水乙醇、石油醚、丙酮溶剂中进行 25 min 超声清洁,使用干燥 N2吹干,将其挂于镀膜台上[20]。关闭舱门,开启机械泵抽真空至腔室内的基础气压达到 0.5 mPa 后开启镀膜程序:通入 Ar 气,调节系统偏压至-400 V,调节两 Ti 靶电流至 0.5 A,进行 20 min 离子刻蚀清洁,以除去基底材料表面氧化层及污染物,并为后续沉积粒子增添附着位点;将系统偏压降至-80 V、Ti 靶电流增至4.0 A后开始进行Ti打底层的溅射沉积,历时 20 min;最后 TiB2靶电流逐渐增强至电流设定值,Ti靶电流逐渐减弱至0 A,进行时长180 min TiB2 目标层的溅射沉积制备。不同靶电流下制备的薄膜相关参数如表1 所示。

  • 表1 不同靶电流下 TiB2薄膜溅射工艺参数及元素计量比

  • Table1 Process parameters and elemental stoichiometry ratios for sputtering TiB2 thin films at different target currents

  • 1.2 薄膜成分及结构分析

  • 使用 SU8020 型超高分辨场发射扫描电子显微镜(SEM)分别对薄膜表、截面微观形貌进行观测; 使用 MultiMode8 型原子力显微镜(AFM)使用 Advantage 模式对薄膜表面形貌及表面粗糙度进行定性测量、分析;使用 NHT2 型纳米压痕仪(载荷 10 mN、保压 10 s、加载速度 20 mN / min),借助经典的 Oliver-Pharr[20-22]方法对测试样品的加、卸载曲线进行处理分析,从而获得其硬度、弹性模量等数据,并进一步对其抗磨损性能以及抗塑性变形能力等力学性能进行计算评价;使用 OXFORD 型能量色散光谱仪对薄膜元素进行采集分析处理;使用 REVETEST 型划痕仪借助光镜照片、噪声信号及深度应变曲线对薄膜与基底间的结合强度进行表征判定;采用 EMPYREAN 型 X 射线衍射仪(Cu 靶 Kα 辐射,入射波长 λ=0.154 nm,工作电压 45 kV,工作电流 40 mA,掠射角为 1°,扫描范围为 20°~80°),结合 JADE 软件对不同制备条件的薄膜的物相组成和晶面结构进行分析[15];使用 ESCALAB 250Xi 型 X 射线光电能谱仪对薄膜内元素组分进行精确表征;使用 THT01 型球盘摩擦磨损试验机对薄膜的摩擦学性能进行表征,试验条件:旋转摩擦, 3 N 载荷,使用φ 6 mm 氧化铝陶瓷对偶球进行试验,重复三次;使用 Olympus STM 6 型光学显微镜对薄膜摩擦后薄膜表面磨痕进行观测记录;使用 MicroXAM-3D 型三维表面轮廓仪对磨损体积及薄膜曲率[20]进行测算,并分别将其带入磨损率计算公式[20]及 Stoney[216]公式对薄膜磨损率、残余应力进行定量计算分析;通过聚焦离子束(Focused ion beam,FIB)对磨痕处薄膜进行减薄制备,并使用高分辨率透射电镜( High resolution transmission electron microscope,HRTEM)对薄膜润滑膜层和原始薄膜进行观察,分析薄膜耐磨损原因[20]

  • 2 结果与讨论

  • 2.1 薄膜形貌分析

  • 由图1 可知,随着溅射沉积阶段靶电流增加,靶材粒子溅射速率加快,使得薄膜沉积厚度增加。各靶电流条件下,薄膜截面均为柱状结构,无明显变化[23-24]。当薄膜沉积溅射阶段靶电流为 6.0 A 时,薄膜沉积厚度达到最大值,平均厚度达 2.168 μm。这是由于随着靶电流的提升,Ar 气电离程度增加, Ar+ 对靶材的轰击频率升高,使得靶材激发溅射的粒子密度和最终到达基底的溅射粒子总量增加,进而导致薄膜沉积厚度增加。

  • 图1 不同靶电流条件下 TiB2薄膜的沉积厚度及截面形貌

  • Fig.1 Deposition thickness and cross-section morphology of TiB2 films under different target current conditions

  • 不同靶电流条件下,溅射沉积的薄膜表面形貌 SEM 及 AFM 如图2 所示。通过对比照片发现,不同靶电流下制备的薄膜表面均为岛状生长类型。对比不同靶电流条件下沉积薄膜的 AFM 图可知,随着靶电流的增加,薄膜表面粗糙度呈先降后升趋势。这是由于靶电流增加,基底表面沉积粒子总量增加,使得基底上沉积粒子数量显著增加,从而导致一定限度内靶电流较高条件下制备的薄膜具有较低的表面粗糙度。但随着靶电流的持续增加,溅射粒子密度过大,最终导致通过等离子体传输到达并沉积到基底处的溅射粒子没有足够时间完成自由扩散,进而引起薄膜表面粗糙度的升高[14]

  • 图2 不同靶电流下沉积的 TiB2薄膜的表面粗糙度及形貌

  • Fig.2 Surface morphology and roughness of TiB2 films deposited under different target current strengths

  • 2.2 薄膜物相分析

  • 如图3 所示,薄膜中主要包含 TiB2(ICDD 卡片数据库检索号#35-0741)的(001)、(100)、(101)、(002)、(102)晶面。直流磁控溅射制备薄膜过程中,溅射粒子轰击沉积薄膜,促使其生长形核。由于薄膜整体遵循最低能态沉积规则,沉积薄膜表面能与应变能相互竞争,引起沉积薄膜晶面织构占比的差异。而随着靶电流增加,溅射功率提高,溅射粒子能量增大,促进薄膜形核生长[15]。在较厚的膜厚度和较高的衬底温度下,应变能占主导地位,由于(101)晶面具有低应变能的特性,薄膜内(101)晶面取向占据主导地位[15],因此沉积薄膜趋向以(101)为择优晶面[15]。随着靶电流的增加,薄膜结晶度呈明显递增趋势,这与靶电流提高引起的靶功率提升有关[14]。靶电流较低时,溅射粒子能量处于较低水平,致使粒子轰击形核能力受到抑制,腔室内较低的温度限制了晶核的成核尺寸和晶粒生长,这是导致 3.0 A 条件下制备的薄膜结晶度较低的主要原因。随着靶电流的提高,靶功率强度增加,致使溅射粒子轰击形核能力增强,薄膜生长愈加充分,同时引起腔室内部温度升高,使得成核所需临界尺寸增加[25]。总体而言,随着靶电流的增加,薄膜结晶度提高,半峰宽(Full width at half maxima,FWHM) 收窄,晶粒尺寸增加。

  • 图3 不同靶电流下沉积 TiB2薄膜的 XRD 图谱

  • Fig.3 XRD patterns of TiB2 films deposited at different target currents

  • 2.3 薄膜元素分析

  • 由图4 可知,所制备薄膜材料均呈现过化学计量比(B / Ti>2)的情况[26-28],由于 Ar+ 的激发导致靶材粒子的溅射。一方面,B 元素相较于 Ti 元素在等离子体传输过程中具有更小的碰撞截面积,且在碰撞过程中的动量损失更小[1];另一方面,Ar+ 与靶材激发粒子之间存在较大质量差异,B 元素的溢出角较 Ti 元素更为集中,因此 B 元素更易于沿法线方向通过等离子体传输沉积在垂直于法线的基底材料表面[27]。这都使得平行于靶材的基底材料上 B 元素相较 Ti 元素更为富集,致使薄膜中 B 元素呈现过计量比的情况。而薄膜中 B 元素过量引起富 B 元素组织相在晶界处形成、富集,这阻碍了外力作用情况下薄膜晶界的滑移,使得薄膜硬度提高[28-29]

  • 图4 不同靶电流条件下沉积薄膜的元素化学计量比

  • Fig.4 Elemental stoichiometric ratios of films deposited under different target current conditions

  • 如图5 所示,分别对不同电流条件下沉积的薄膜样品进行 X 射线光电子能谱分析。试验前使用 Ar+ 对样品测试区域进行 100 s 刻蚀以消除薄膜表面污染及氧化层。使用 XPSPEAK 数据处理软件对 B 元素的精细谱进行分峰拟合处理,可见结合能峰位值分别为 188.4 eV(B-B 键)[15]和 187.3 eV(Ti-B 键)[1530]。靶电流为 3.0 A 时,沉积薄膜富 B 元素组织相占比最低,为 17.19%,此时薄膜的硬度和弹性模量均取得最小值,分别为 14.4、268.1 GPa。而随着靶电流的提高[14],富 B 元素组织相占比先增加后降低;靶电流达到 5.0 A 时,对应沉积薄膜的富 B 元素组织相占比最高,为 27.90%,此时薄膜硬度和弹性模量取得最大值,分别为 18.66、337.8 GPa。随靶电流改变,富 B 元素组织相占比与薄膜硬度的变化趋势基本吻合,即随着靶电流的增加,两者均呈现先增后降的变化趋势,且富 B 元素相占比越高的沉积薄膜对应的硬度越高,这与富 B 元素组织相能够抑制晶界的滑移,导致薄膜硬度增加的报道相吻合[27-2931]

  • 图5 不同靶电流下沉积的 TiB2薄膜 XPS 谱图

  • Fig.5 XPS spectra of TiB2 films deposited at different target current

  • 2.4 薄膜力学性能分析

  • 如图6 所示,随着溅射沉积阶段靶电流的增大,薄膜残余应力随之增加,而沉积薄膜膜基结合强度却随之降低。这是由于靶电流和靶功率增加,大量能量以热能的形式逸散,致使腔室内温度升高,由于薄膜与基底材料的热膨胀系数及弹性模量的差异,沉积温度冷却至室温过程中,沉积薄膜同基底间存在着冷缩速度的差异,从而导致薄膜内部产生相应的热应力[1416]。随着溅射沉积阶段靶电流增加,沉积腔室内温度同室温之间的温差变大,进而使得薄膜内部残余应力(本征与热应力之和)也随之增加。而薄膜内部较高的残余应力会使得薄膜膜基结合强度降低(L 为薄膜剥落时所对应的载荷),使得在受到外力影响下薄膜更容易屈曲、皲裂甚至剥离,致使对刀具的防护作用失效。

  • 图6 不同靶电流条件下 TiB2薄膜的薄膜应力及划痕形貌

  • Fig.6 Film stress and scratch morphology of TiB2 films under different target current conditions

  • 使用纳米压痕仪对不同靶电流下制备的TiB2薄膜进行测试:载荷 10 mN、保压时间 10 s、加卸载速率 20 mN / min。并借助经典的 Oliver-Pharr[21]方法分析纳米压痕的加、卸载曲线,得到测试样品的硬度(H)和弹性模量(E),并借助 MUSIL 等[31] 的方法计算了薄膜的抗磨损性能(H / E[32]和抗塑性变形能力(H3 / E2[31],试验数据如图7 所示。

  • 图7 不同靶电流下沉积的 TiB2薄膜的力学性能

  • Fig.7 Mechanical properties of TiB2 films deposited at different target currents

  • 由图7 可知,薄膜的硬度、弹性模量及耐磨性等均随靶电流的升高而呈现先增后降的趋势。一方面,靶电流增加致使残余应力增大,一定程度上会使得薄膜硬度获得相应提升[3];另一方面,薄膜中富 B 元素组织相占比增高,使得对薄膜内部晶界滑移的抑制增强,进而导致薄膜硬度呈现先增后降的变化趋势[27]

  • LEYLAND 等[32]认为 H / E 的数值相较于单独硬度数据更适用于预测材料的耐磨性参数,越高的 H / E 表明材料可能具有更优异的耐磨性能。MUSIL 等[31]认为相较于相同载荷下对压头压入深度而言, H3 / E2 能够更为准确反映材料抗塑性变形的能力, H3 / E2 越大表明材料可能有更好的抗塑性变形能力。由图4 可知,靶电流为 3.0 A 时,H / EH3 / E2 均处于最低水平,而随着靶电流的增加,两者均呈先增后降的趋势,靶电流为 5.0 A 时,两者均处于最高水平。一方面,靶电流增加,溅射粒子密度增加,溅射粒子的轰击促进了薄膜的生长形核过程,进而使得薄膜的 H / EH3 / E2 增大;另一方面,靶电流增加,腔室温度相应升高,残余应力增加,使得 H / EH3 / E2 呈现先升后降的变化趋势[1231-34]

  • 2.5 薄膜摩擦学性能分析

  • 由图8 可知,不同靶电流条件下沉积薄膜的摩擦因数均位于 0.75~0.85,摩擦因数无明显差异,但磨损率差异显著,靶电流为 4.0 A 时磨损率 W 仅为 6.347×10−6 mm 3 /(N·m),磨损率远小于体系内其他电流条件下沉积的薄膜。较光洁的表面使得薄膜在摩擦试验中相较于表面结构较粗糙的薄膜能够尽可能地减少薄膜与对偶球间形成机械咬合的几率,促使其在摩擦接触中获得相对较低的磨损率;其次,靶电流较低时,残余应力小、膜基结合强度较高、粒子间结合紧密不易被剥离[35],靶电流较高时,薄膜内部残余应力较大,大的残余应力可能导致外力作用下薄膜易产生微裂纹或将导致薄膜与基底剥离,使得较高电流条件下制备的薄膜摩擦因数偏高,磨损加剧[216]

  • 图8 不同靶电流下沉积的 TiB2薄膜的摩擦磨损数据

  • Fig.8 Friction wear data of TiB2 films deposited at different target currents

  • 由图9 可知,靶电流为 4.0 A 时,沉积制备的薄膜在相同条件的摩擦试验后,磨痕宽度最窄,磨痕深度最浅,即防护薄膜损失最轻微。说明靶电流条件为 4.0 A 时薄膜具有最佳耐磨性能,能够更好地降低摩擦磨损带来的材料损失。

  • 图9 不同靶电流条件下制备的 TiB2薄膜在摩擦后磨痕形貌和相应的三维形貌图

  • Fig.9 Post-friction abrasion morphology and corresponding 3D morphology of TiB2 films prepared under different target current conditions

  • 为了进一步解释薄膜在摩擦接触过程中具有较好耐磨性能的原因,对靶电流为 4.0 A 条件下溅射沉积的薄膜进行了聚焦离子束制样(Focused ion beam,FIB)、透射电镜观察和选区电子衍射(Selected area electron diffraction,SAED)分析,结果如图10 所示。图10a 为未经摩擦处理的薄膜的透射电子显微镜(TEM)分析,可以明确地观察到仅有少且短的晶格条纹间距,而对经过摩擦处理后的磨痕处薄膜进行 FIB 制样后,通过 TEM 分析可清楚地观察到该区域内有着密集的晶格条纹间距,并且对相应区域进行 SAED 分析后发现,相应区域出现了更为清晰的 TiB2衍射环,这说明在摩擦接触过程中薄膜产生非晶相结构向晶相结构转变,薄膜结晶度提高,一定程度上致使薄膜的硬度及耐磨损性能增加,降低了薄膜在摩擦接触过程中的体积损失,使其拥有同体系中最佳的抗耐磨性能。

  • 图10 薄膜透射分析

  • Fig.10 Thin film transmission analysis

  • 3 结论

  • (1)采用直流磁控溅射技术,通过调节沉积过程中 TiB2 靶材靶电流大小的方式进行 TiB2 薄膜的溅射沉积制备。随着靶电流增大,薄膜沉积厚度增加。

  • (2)随着靶电流增大,一方面,薄膜半峰宽收窄,晶粒尺寸增加;另一方面,势能更高的溅射粒子的轰击促进了沉积薄膜的生长形核。

  • (3)B 元素相较于 Ti 元素在等离子体传输过程中具有更小的碰撞截面积和动量损失;Ar+ 与靶材激发粒子之间存在较大质量差异,使得 B 元素溢出角相较 Ti 元素更为集中,更易沿法线方向等离子体传输并沉积于基底,因此制备的薄膜均呈现 B 元素超化学计量比的现象。通过 XPS 可知,富集的 B 元素形成了富 B 元素相(B-B 键),富 B 元素相聚集在晶界处,阻碍了外力作用下晶界的滑移,使得薄膜具有较高的硬度及较优的耐磨损性能。

  • (4)靶电流增加,薄膜内部残余应力(本征应力和热应力之和)增强,使得膜基结合强度随靶电流增加而降低;薄膜硬度随富 B 元素组织相占比而同步呈现先升后降的演变趋势。

  • (5)4.0 A 靶电流下制备的 TiB2 薄膜具有最佳耐磨性能,主要由于摩擦接触过程中,薄膜摩擦接触区域产生了明显的非晶相结构向晶相结构的转变,因此薄膜硬度得到了提高,使其具有较优异的耐磨性能。

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