CN106119776B - 一种纳米织构化CrN/WS2固体润滑薄膜的制备方法 - Google Patents

一种纳米织构化CrN/WS2固体润滑薄膜的制备方法 Download PDF

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CN106119776B
CN106119776B CN201610815941.XA CN201610815941A CN106119776B CN 106119776 B CN106119776 B CN 106119776B CN 201610815941 A CN201610815941 A CN 201610815941A CN 106119776 B CN106119776 B CN 106119776B
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王德生
胡明
翁立军
孙嘉奕
高晓明
姜栋
伏彦龙
杨军
王琴琴
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0623—Sulfides, selenides or tellurides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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Abstract

本发明公开了一种纳米织构化CrN/WS2固体润滑薄膜的制备方法，具体步骤为：1)采用超声清洗法清洗基片；2)用氩离子溅射清洗基片；3)采用中频磁控溅射技术沉积表面具有纳米锥状阵列结构的CrN层；4)通过射频磁控溅射技术沉积WS2润滑薄膜层。本发明所述薄膜结构致密，与基底材料的结合牢固，纳米锥状阵列结构的CrN提供良好的支撑和保存WS2润滑膜的作用，整体薄膜呈现出明显改善的摩擦学性能，具有良好的应用前景。

Description

一种纳米织构化CrN/WS2固体润滑薄膜的制备方法
技术领域
本发明涉及一种纳米织构化CrN/WS2固体润滑薄膜的制备方法。
背景技术
过渡族金属二硫属化合物因具有良好的真空防冷焊和润滑性能，作为一种良好的固体润滑材料，已广泛应用于航天结构中各类运动部件。随着航天技术的快随发展，对整个航天设备的技术可靠性和工作寿命提出了更高的要求，也迫切需要具有更高耐磨损和长寿命的固体润滑材料。在二硫化钨（WS2）润滑性能的提升的研究方面，通过机械手段或激光加工技术对金属基体材料表面制备具有周期性的微坑、凹槽等微结构，之后通过润滑剂的填充，实现微结构对润滑剂的储存，可达到摩擦副的持续润滑和寿命的提高。另外，通过生物模板等技术可以实现在纳米尺度下织构化薄膜的沉积，实现薄膜摩擦学性能的改善。总体而言，在目前阶段的实际工业应用中，激光织构存在明显的成本方面和复杂零部件使用的局限性，生物模板等技术制备的纳米织构化薄膜无法实现高载荷和高转速条件下的应用。另外，在微/纳米尺度下，通过传统的气相沉积技术，实现纳米织构化WS2润滑薄膜的研究和应用的则很少。
发明内容
本发明的目的在于提供一种纳米织构化CrN/WS2固体润滑薄膜的制备方法。
本发明通过磁控溅射技术首先在金属基体上制备具有织构化结构的硬质CrN薄膜层，之后沉积WS2构筑纳米织构化的WS2润滑薄膜层，实现了薄膜摩擦学性能和工作寿命的提高。本发明制备的薄膜以表面具有纳米锥状阵列结构的硬质CrN层作为支撑层，结合表面的WS2润滑层，从而实现提高薄膜体系的耐磨损、长寿命的特性。
本发明的关键之一在于采用中频磁控溅射技术沉积CrN层，通过控制沉积过程中Ar气和反应N2的流量比，制备具有良好（111）面优先生长、表面呈现纳米锥状阵列结构的CrN薄膜层，以此作为纳米织构化WS2薄膜的底层。一方面，这种纳米结构表面有利于提高膜层之间的结合，可以促进表层WS2薄膜层的致密生长，另一方面，这种纳米阵列结构有利于在摩擦过程中保存WS2润滑剂，实现薄膜体系润滑寿命的提高。
本发明涉及到的表面WS2层采用射频磁控溅射技术制备。本发明涉及的真空镀膜设备同时安装有中频磁控溅射和射频磁控溅射靶位。底层CrN沉积结束后，通过真空腔室内的旋转机构，将基体移至射频溅射WS2靶位，进行WS2薄膜层的沉积。
一种纳米织构化CrN/WS2固体润滑薄膜的制备方法，其特征在于该制备方法的具体步骤为：
1）靶材安装
将直径60～90mm、厚度4～6mm、纯度99.99%的Cr靶安装在中频磁控溅射靶座；将直径60～90mm、厚度4～6mm、纯度99.99%的WS2靶安装在射频磁控溅射靶座，分别连接中频溅射电源和射频溅射电源；
2）基体材料准备安装
基体材料依次在丙酮、无水乙醇中超声清洗，干燥后置入真空室工件架上，并调整基体至靶材间距至60～90 mm；
3）Ar离子轰击处理
将真空室本底真空抽至5.0×10-4～2.0×10-3Pa，充入高纯Ar气，维持气压至1.5～5.0 Pa，离子轰击电压-500～-1000V，轰击时间15～30 min；
4）CrN层沉积
向真空室充入N2，调节N2和Ar气流量，维持气压至8.5×10-1～1.5Pa，偏压加至-50～-100V，开启中频溅射电源，靶电流设为1.2～1.6A，靶电压250V～350V，溅射沉积CrN层，溅射时间30～60min；
5）WS2层沉积
关闭中频溅射电源，关闭N2，调节Ar气流量至气压1.0～1.5Pa，将基体旋转至WS2靶前，偏压加至-30～-100V，开启射频电源，功率调至250～400W，溅射20～60 min，镀膜结束后自然降温至室温。
所述基体为不锈钢。
步骤4）中所述Ar与N2的流量比为1.5～2.5。
本发明制备的薄膜厚度为1.2～3 μm，薄膜与基体以及薄膜中层与层之间的结合良好，薄膜润滑寿命与纯WS2薄膜相比有明显的提高。
附图说明
图1为实施例1 制备的具有纳米锥状阵列结构的CrN的场发射电镜照片。
图2为实施例2制备的薄膜的场发射电镜照片。
图3为实施例2制备的薄膜的摩擦试验曲线。
具体实施方式
实施例1
选择9Cr18钢作为基体材料，将基体材料依次放入分析纯丙酮和无水乙醇中各超声清洗15分钟，放入红外烘箱中烘干，随后放入真空室中，将基体材料镀膜表面与Cr靶及WS2靶之间的距离调整至80 mm。
对真空室抽气，当本底气压达到2.0×10-3 Pa后，向真空室充入氩气，气压维持在2.0Pa，离子轰击20分钟；
通入Ar和N2，Ar与N2流量比为2:1，气压调至1.0 Pa，开启中频溅射电源，沉积CrN薄膜。保持靶电流为1.5A，靶电压300 V，工件偏压-50V；镀膜60分钟；
取出试样测量薄膜厚度约0.7μm，图1为中频溅射CrN之后薄膜的表面及断面的场发射扫面电镜照片，可以看出CrN表面呈现出纳米锥状阵列结构，锥状结构周期约为150nm，锥高度约120 nm。
实施例2
选择9Cr18钢作为基体材料，将基体材料依次放入分析纯丙酮和无水乙醇中各超声清洗15分钟，放入红外烘箱中烘干，随后放入真空室中，将基体材料镀膜表面与Cr靶及WS2靶之间的距离调整至80 mm。
对真空室抽气，当本底气压达到2.0×10-3 Pa后，向真空室充入氩气，气压维持在2.0Pa，离子轰击20分钟；
通入Ar和N2，Ar与N2流量比为2:1，气压调至1.0 Pa，开启中频溅射电源，沉积CrN薄膜。保持靶电流为1.5A，靶电压300 V，工件偏压-50V；镀膜60分钟；
关闭N2，调节Ar流量至气压1.5Pa，调节偏压值-100V，开启射频电源，设置功率350W，沉积WS2薄膜，沉积时间30 min。
取出试样测量薄膜厚度约为1.47 μm，CrN层0.71μm，WS2层0.76 μm。图2 为薄膜的场发射扫描电镜照片，图3为所制备薄膜的球盘摩擦试验曲线，其中上试样为Φ8 mm的9Cr18钢球，下试样为镀膜试样，加载5N，转速1000 r/min。通过与相同条件下溅射的纯WS2对比，可以看出，所制备的织构化薄膜的耐磨寿命远远高于纯WS2薄膜。

Claims (2)

1.一种纳米织构化CrN/WS2固体润滑薄膜的制备方法，其特征在于该制备方法的具体步骤为：
1）靶材安装
将直径60～90mm、厚度4～6mm、纯度99.99%的Cr靶安装在中频磁控溅射靶座；将直径60～90mm、厚度4～6mm、纯度99.99%的WS2靶安装在射频磁控溅射靶座，分别连接中频溅射电源和射频溅射电源；
2）基体材料准备安装
基体材料依次在丙酮、无水乙醇中超声清洗，干燥后置入真空室工件架上，并调整基体至靶材间距至60～90 mm；
3）Ar离子轰击处理
将真空室本底真空抽至5.0×10-4～2.0×10-3Pa，充入高纯Ar气，维持气压至1.5～5.0Pa，离子轰击电压-500～-1000V，轰击时间15～30 min；
4）CrN层沉积
向真空室充入N2，调节N2和Ar气流量，维持气压至8.5×10-1～1.5Pa，偏压加至-50～-100V，开启中频溅射电源，靶电流设为1.2～1.6A，靶电压250V～350V，溅射沉积CrN层，溅射时间30～60min；所述Ar与N2的流量比为1.5～2.5；
5）WS2层沉积
关闭中频溅射电源，关闭N2，调节Ar气流量至气压1.0～1.5Pa，将基体旋转至WS2靶前，偏压加至-30～-100V，开启射频电源，功率调至250～400W，溅射20～60 min，镀膜结束后自然降温至室温。
2.如权利要求1所述的制备方法，其特征在于所述基体为不锈钢。
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