CN113564521B - 一种金属表面的蜂巢结构多层膜及其制备方法 - Google Patents

一种金属表面的蜂巢结构多层膜及其制备方法 Download PDF

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CN113564521B
CN113564521B CN202110816749.3A CN202110816749A CN113564521B CN 113564521 B CN113564521 B CN 113564521B CN 202110816749 A CN202110816749 A CN 202110816749A CN 113564521 B CN113564521 B CN 113564521B
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赵梓源
王慧陶
曹龙
李均明
钟黎声
赵明轩
许云华
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Xian University of Technology
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Abstract

本发明公开了一种金属表面的蜂巢结构多层膜及其制备方法。包括以下步骤：首先采用掩膜刻蚀的方法，在金属基体表面刻蚀出蜂巢骨架；其次利用薄膜沉积技术沿着基体表面蜂巢骨架内壁沉积多层膜，最后沉积一层使表面平整，得到蜂巢结构多层膜。这种蜂巢结构多层薄膜将层状结构的排列方向三维化，能够有效阻碍裂纹沿三个维度的扩展，提高了韧性；金属基体表面的蜂巢骨架有助于提高抗剪强度。

Description

一种金属表面的蜂巢结构多层膜及其制备方法
技术领域
本发明属于金属材料的表面改性领域，具体涉及一种金属表面多层膜的结构设计和制备方法。
背景技术
制造业的快速发展对金属材料的表面强度和韧性的要求越来越苛刻。制备多层膜是提高表面强度和韧性的有效途径。微纳米尺度组元的尺寸效应、多界面结构的几何约束效应以及层状复合构型所特有的钝化裂纹和诱导裂纹偏转的能力赋予了多层膜优异的强度/硬度和韧性匹配。
按照多层膜的物相组成，用于制造业的金属表面多层膜主要包括金属/金属多层膜、陶瓷/金属多层膜和陶瓷/陶瓷多层膜。多层膜性能的优化主要包括结构调控和材料优化。在结构调控方面，国内外学者在保持多层膜逐层平铺这一结构特点的基础上，通过调控层厚、层厚比这两个结构参量在一定程度上实现了强韧性的优化。
然而，受制于多层膜现有的结构特点，多层膜强度/硬度与韧性的进一步提升出现了新的瓶颈。一方面，多层膜的层状结构沿垂直于表面的方向排列，对沿平行于表面方向扩展的裂纹抵抗力不佳，影响韧性的提升。另一方面，层间界面平面度高的结构特点使多层膜易沿层间界面断裂失效，受到外力作用可能发生层间分离的现象，影响多层膜强度的提高。由上述分析可知，多层膜强韧性的进一步提升受制于其层状结构只沿单一方向排列的结构特点，只有打破这一结构上的束缚，引入更多的强韧化机制和可调结构参量才有望突破性地提升强度/硬度与韧性。
发明内容
本发明的目的是提供一种金属表面的蜂巢结构多层膜；解决了现有技术中存在的多层膜层状结构只沿单一方向排列的结构特点造成的强韧性不足的问题。蜂巢结构多层膜是一种多层膜的构型设计，与材料无关；蜂巢结构多层膜可以是金属/金属多层膜、陶瓷/金属多层膜或陶瓷/陶瓷多层膜，相应的基体可以是表面能够被选择性刻蚀的任意金属材料。
本发明的目的还在于，提供一种金属表面的蜂巢结构多层膜的制备方法。
一种金属表面的蜂巢结构多层膜，包括基体表面蜂巢骨架和沿蜂巢骨架内壁沉积的多层膜。一种金属表面的蜂巢结构多层膜的制备方法，采用权利要求1所述一种金属表面的蜂巢结构多层膜的结构，这种蜂巢结构多层膜的制备包括以下步骤：
步骤1：将需要表面制备多层膜的金属基体表面进行预处理，并对金属基体进行表面选择性刻蚀，形成金属基体表面蜂巢结构骨架；
步骤2：在金属基体表面蜂巢结构骨架的内壁交替沉积两种材料，形成多层膜；最后沉积一层使表面实现平坦化。
本发明的特点还在于：
步骤1中所述金属基体可以是表面能够被选择性刻蚀的任意金属材料，金属基体包括钢铁、钛、铝、镁、钨、钽、铌、钼、铬，及以其中一种元素为主要成分的合金。
步骤1中所述的表面预处理是指对金属基体表面进行研磨和抛光，再分别用丙酮、酒精在超声波中清洗。
步骤1中所述的选择性刻蚀方法如下：
首先制作具有与蜂巢壁结构表面投影图案的掩膜板，然后在掩膜条件下，进行湿法刻蚀或干法刻蚀。
所述湿法刻蚀包括化学溶液腐蚀，干法刻蚀包括激光刻蚀或等离子刻蚀。
根据权利要求2所述的一种金属表面的蜂巢结构多层膜的制备方法，其特征在于，蜂巢结构六边形边长L的范围为10-1000微米，蜂巢壁厚δ的范围为2-200微米，刻蚀深度H为5-50微米。
步骤2中所述的沉积采用物理气相沉积。具体包括真空蒸镀、溅射镀膜、离子镀；多层膜相邻两层厚度之比d1/d2的变化范围为1-10，单层厚度范围为10纳米至4微米；最后沉积一层实现表面平坦化，其材料可以与多层膜材料相同或不同，其厚度不受多层膜层厚和层厚比限制。
步骤2中所述的两种材料可以是两种金属、陶瓷和金属以及两种陶瓷，分别形成金属/金属多层膜、陶瓷/金属多层膜以及陶瓷/陶瓷多层膜；两种材料形成的多层膜包括TiN/Ti、CrN/Cr、CrN/AlN、TiN/Si3N4、Cu/Cr、TiN/CrN、Cu/Zr、Al2O3/Al、SiC/Al、WN/Ni、WC/Ni、WN/TaN、WC/Mo2C。
本发明的有益效果在于：
1)蜂巢正六棱柱体结构具有优秀的几何力学性能，以其极佳的抗压、抗弯和抗断裂特性而闻名于世。在图1所示结构中，三维连通的蜂巢结构基体骨架能够提升抗剪强度。
2)蜂巢构型化增韧与多层膜增韧相结合，形成多尺度增韧机制，提高对裂纹沿平行于表面方向扩展的阻碍能力。蜂巢几何结构保证了裂纹沿平行于表面的方向扩展时必遇多层膜。当裂纹遇多层膜偏转时，不但可发挥多层膜自身的增韧效果，而且由于蜂巢六边形的边长处于101-102微米量级，远大于多层膜的层厚(10-1-101微米量级)，则可显著增大裂纹扩展路径，形成多尺度增韧，再次提高韧性。若裂纹遇到多层膜时不发生明显偏转，则继续向前扩展需要不断穿过多层膜，可多次发挥多层膜自身的增韧效果。
因此，将多层膜设计成蜂巢结构能够进一步突破当前多层膜强韧化的瓶颈，实现综合力学性能的再次提升。
附图说明
图1为本发明金属表面蜂巢结构多层膜的制备方法示意图
具体实施方式：
下面结合具体实施方式对本发明进行详细说明。
本发明提出一种金属表面的蜂巢构型多层膜，其制备方法具体包括以下步骤：
步骤1：将需要表面制备多层膜的金属基体表面进行预处理，并对金属基体进行表面选择性刻蚀，形成金属基体表面蜂巢结构骨架。
步骤1.1：选取需要表面制备多层膜的金属作为基体，将表面进行研磨和抛光，再分别用丙酮、酒精在超声波中清洗。
优选的，基体材料可以是钢铁、钛、铝、镁、钨、钽、铌、钼、铬，及以其中一种元素为主要成分的合金。
步骤1.2：制作具有与蜂巢壁结构表面投影图案的掩膜板。蜂巢六边形边长L的范围为10-1000微米，蜂巢壁厚δ范围为2-200微米。
步骤1.3：然后在掩膜板遮盖条件下，进行湿法刻蚀(化学溶液腐蚀)或干法刻蚀(如激光刻蚀或等离子刻蚀)。刻蚀深度(即蜂巢壁高度H)为5-50微米。
步骤2：利用物理气相沉积镀膜，通过控制相关变量，在刻蚀后的基体表面交替沉积两种材料，相邻两层厚度之比的变化范围为1-10，单层厚度范围为10纳米-4微米。多层薄膜可以为金属/金属多层膜、金属/陶瓷多层膜或者陶瓷/陶瓷多层膜。优选的，多层膜包括TiN/Ti、CrN/Cr、CrN/AlN、TiN/Si3N4、Cu/Cr、TiN/CrN、Cu/Zr、Al2O3/Al、SiC/Al、WN/Ni、WC/Ni、WN/TaN、WC/Mo2C。最后沉积一层至表面平整，其材料可以与多层膜材料相同或不同，其厚度不受多层膜层厚和层厚比限制。
实施例1：
本实例在低碳钢Q235表面制备蜂巢结构Ti/TiN多层膜，包括以下步骤：
步骤1：将低碳钢(Q235)板表面进行预处理，并对低碳钢(Q235)板进行表面选择性刻蚀，形成低碳钢(Q235)基体表面蜂巢结构骨架。
步骤1.1：基体清洗。准备一块低碳钢(Q235)板，对其表面进行砂纸研磨和抛光，再分别用丙酮、酒精对其表面进行清洗。
步骤1.2：制作具有蜂巢壁结构表面投影图案的掩膜板。蜂巢六边形边长L为1000微米，蜂巢壁厚为200微米。
步骤1.3：采用湿法刻蚀(盐酸溶液)在低碳钢Q235基体表面刻蚀出蜂巢结构。刻蚀深度为50微米。
步骤2：采用磁控溅射制备Ti/TiN多层膜。TiN层厚4微米，Ti层厚0.4微米，沉积共10层。最后一层沉积TiN，使表面平坦化。
通过上述方法，得到的蜂巢结构TiN/Ti多层膜具体以下特征：1)表面硬度约为2300HV；2)断裂韧性为8.1MPa m1/2；3)大幅度提高了基体的表面耐磨性能(比基体的耐磨性提高了约40倍)。
实施例2：
本实例在钛合金(Ti6Al4V)表面制备蜂巢结构Ti/TiN多层膜，包括以下步骤：
步骤1：将钛合金(Ti6Al4V)板表面进行预处理，并对钛合金(Ti6Al4V)板进行表面选择性刻蚀，形成钛合金(Ti6Al4V)基体表面蜂巢结构骨架。
步骤1.1：基体清洗。准备一块钛合金(Ti6Al4V)板，对其表面进行砂纸研磨和抛光，再分别用丙酮、酒精对其表面进行清洗。
步骤1.2：制作具有蜂巢壁结构表面投影图案的掩膜板。蜂巢六边形边长L为10微米，蜂巢壁厚为2微米。
步骤1.3：采用激光刻蚀在钛合金(Ti6Al4V)基体表面制备蜂巢结构骨架。刻蚀深度为5微米。
步骤2：采用阴极弧离子镀制备Ti/TiN多层膜。TiN层厚0.1微米，Ti层厚10纳米，共80层。最后一层沉积TiN，使表面平坦化。
通过上述方法，得到的蜂巢结构TiN/Ti多层膜具体以下特征：1)表面硬度约为1700HV；2)断裂韧性为8.9MPa m1/2；3)大幅度提高了基体的表面耐磨性能(比基体的耐磨性提高了约30倍)。
实施例3：
本实例在镁合金(AZ91D)表面制备蜂巢结构CrN/TiN多层膜，包括以下步骤：
步骤1：将镁合金(AZ91D)板表面进行预处理，并对镁合金(AZ91D)板进行表面选择性刻蚀，形成镁合金(AZ91D)基体表面蜂巢结构骨架。
步骤1.1：基体清洗。准备一块镁合金(AZ91D)板，对其表面进行砂纸研磨和抛光，再分别用丙酮、酒精对其表面进行清洗。
步骤1.2：制作具有蜂巢壁结构表面投影图案的掩膜板。蜂巢六边形边长L为500微米，蜂巢壁厚为100微米。
步骤1.3：采用等离子刻蚀在镁合金(AZ91D)基体表面制备蜂巢结构骨架，刻蚀深度为25微米。
步骤2：采用磁控溅射离子镀沉积CrN/TiN多层膜。CrN层厚1微米，TiN层厚1微米，共20层。最后一层沉积TiN，使表面平坦化。
通过上述方法，得到的蜂巢结构CrN/TiN多层膜具体以下特征：1)表面硬度约为2500HV；2)断裂韧性为6.4MPa m1/2；3)大幅度提高了基体的表面耐磨性能(比基体的耐磨性提高了约70倍)。
实施例4：
本实例在铝合金(6010)表面制备蜂巢结构Al2O3/Al多层膜，包括以下步骤：
步骤1：将铝合金(6010)板表面进行预处理，并对铝合金(6010)板进行表面选择性刻蚀，形成铝合金(6010)基体表面蜂巢结构骨架。
步骤1.1：基体清洗。准备一块铝合金(6010)板，对其表面进行砂纸研磨和抛光，再分别用丙酮、酒精对其表面进行清洗。
步骤1.2：制作具有蜂巢壁结构表面投影图案的掩膜板。蜂巢六边形边长L为100微米，蜂巢壁厚为10微米。
步骤1.3：采用等离子刻蚀在铝合金(6010)基体表面制备蜂巢结构骨架，刻蚀深度为15微米。
步骤2：采用磁控溅射离子镀沉积Al2O3/Al多层膜。Al2O3层厚0.5微米，Al层厚0.1微米，共20层。最后一层沉积Al2O3，使表面平坦化。
通过上述方法，得到的蜂巢结构Al2O3/Al多层膜具体以下特征：1)表面硬度约为2400HV；2)断裂韧性为7.1MPa m1/2；3)大幅度提高了基体的表面耐磨性能(比基体的耐磨性提高了约60倍)。
实施例5：
本实例在铝合金(6010)表面制备蜂巢结构Cu/Cr多层膜，包括以下步骤：
步骤1：将铝合金(6010)板表面进行预处理，并对铝合金(6010)板进行表面选择性刻蚀，形成铝合金(6010)基体表面蜂巢结构骨架。
步骤1：基体清洗。准备一块铝合金(6010)板，对其表面进行砂纸研磨和抛光，再分别用丙酮、酒精对其表面进行清洗。
步骤2：制作具有蜂巢壁结构表面投影图案的掩膜板。蜂巢六边形边长L为50微米，蜂巢壁厚为10微米。
步骤3：采用等离子刻蚀在铝合金(6010)基体表面制备蜂巢结构骨架，刻蚀深度为20微米。
步骤4：采用磁控溅射离子镀沉积Cu/Cr多层膜。Cu层厚0.5微米，Cr层厚2微米，共14层。最后一层沉积镍(Ni)，使表面平坦化。
通过上述方法，得到的蜂巢结构Cu/Cr多层膜具体以下特征：1)表面硬度约为800HV；2)断裂韧性为10.2MPa m1/2；3)大幅度提高了基体的表面耐磨性能(比基体的耐磨性提高了约10倍)。

Claims (5)

1.一种金属表面的蜂巢结构多层膜的制备方法，其特征在于，蜂巢结构多层膜包括基体表面蜂巢骨架和沿蜂巢骨架内壁沉积的多层膜，这种蜂巢结构多层膜的制备包括以下步骤：
步骤1：将需要表面制备多层膜的金属基体表面进行预处理，并对金属基体进行表面选择性刻蚀，形成金属基体表面蜂巢结构骨架；
步骤2：在金属基体表面蜂巢结构骨架的内壁交替沉积两种材料，形成多层膜；最后沉积一层使表面实现平坦化；
步骤1中所述的表面预处理是指对金属基体表面进行研磨和抛光，再分别用丙酮、酒精在超声波中清洗；
蜂巢结构六边形边长L的范围为10-1000微米，蜂巢壁厚δ的范围为2-200微米，刻蚀深度H为5-50微米；
步骤2中所述的沉积采用物理气相沉积具体包括真空蒸镀、溅射镀膜、离子镀；多层膜相邻两层厚度之比d1/d2的变化范围为1-10，单层厚度范围为10纳米至4微米；最后沉积一层实现表面平坦化，其材料与多层膜材料相同或不同，其厚度不受多层膜层厚和层厚比限制；
步骤2中所述的两种材料包括两种金属、陶瓷和金属或两种陶瓷，分别形成金属/金属多层膜、陶瓷/金属多层膜以及陶瓷/陶瓷多层膜；两种材料形成的多层膜包括TiN/Ti、CrN/Cr、CrN/AlN、TiN/Si3N4、Cu/Cr、TiN/CrN、Cu/Zr、Al2O3/Al、SiC/Al、WN/Ni、WC/Ni、WN/TaN或WC/Mo2C；
所述步骤2中多层膜的层数具体为10层、20层或80层。
2.根据权利要求1所述的一种金属表面的蜂巢结构多层膜的制备方法，其特征在于，步骤1中所述金属基体为表面能够被选择性刻蚀的金属材料。
3.根据权利要求2所述的一种金属表面的蜂巢结构多层膜的制备方法，其特征在于，所述金属基体包括钛、铝、镁，及以其中一种元素为主要成分的合金，或钢铁。
4.根据权利要求1所述的一种金属表面的蜂巢结构多层膜的制备方法，其特征在于，步骤1中所述的选择性刻蚀方法如下：
首先制作具有与蜂巢壁结构表面投影图案的掩膜板，然后在掩膜条件下，进行湿法刻蚀或干法刻蚀。
5.根据权利要求4所述的一种金属表面的蜂巢结构多层膜的制备方法，其特征在于，所述湿法刻蚀包括化学溶液腐蚀，干法刻蚀包括激光刻蚀或等离子刻蚀。
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