CN111647851A - 兼具高硬度和高韧性Zr-B-N纳米复合涂层及其制备方法 - Google Patents
兼具高硬度和高韧性Zr-B-N纳米复合涂层及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种兼具高硬度和高韧性Zr‑B‑N纳米复合涂层及其制备方法，属于纳米复合涂层制备技术领域。所述Zr‑B‑N纳米复合涂层包括非晶BN相和ZrB2晶相，其中ZrB2相沿(001)晶面择优生长。采用脉冲直流磁控溅射技术在金属或合金基体上沉积Zr‑B‑N纳米复合涂层。为提高涂层与基体的结合力，镀膜前先通入Ar气，利用电弧离子镀Cr靶对基体表面进行离子轰击清洗，然后通入N2和H2的混合气体，沉积CrN过渡层。之后关闭Cr靶电源，将ZrB2靶连接到脉冲直流磁控溅射阴极，并在Ar、N2和H2的混合气氛中沉积Zr‑B‑N涂层。本发明涉及的Zr‑B‑N纳米复合涂层制备重复性好，并且容易工业化生产；制备出的Zr‑B‑N涂层具有较高的硬度和弹性模量，良好的耐磨性能，且组织结构致密、涂层与基体间的结合力强。
Description
技术领域
本发明涉及复合涂层及其制备技术领域，具体涉及一种兼具高硬度和高韧性Zr-B-N纳米复合涂层及其制备方法。
背景技术
随着现代化材料制造技术的快速发展，各种高硬度、高韧性的难加工材料日益增多，虽然工程材料的性能得到提升，但也导致了加工材料时刀具磨损加剧。而刀具涂层技术的发展，显著提高了刀具的耐磨性和抗冲击韧性，改善了刀具的切削性能，提高了刀具的加工效率和使用寿命。ZrB2涂层为密排六方晶体结构，具有高的热导率和良好的抗热震性能，同时ZrB2涂层还具有高硬度、高熔点、高抗氧化性、低阻率、良好的导电性能等优点。但是ZrB2在高温时易与氧气反应生成ZrO2/B2O3氧化层，单晶相ZrB2无法在高于1200℃的氧化环境中使用。并且涂层中的柱状晶(001)织构使其具有各向异性，且为垂直于表面的晶界提供了短的裂纹扩展路径，使其韧性大大降低。因此为提高涂层的韧性和耐磨性能，可以通过向ZrB2涂层中添加N元素，形成具有纳米复合结构的Zr-B-N涂层。
经研究发现，真空室内的真空度只有在10-8Pa时，涂层中才检测不到氧杂质的存在，而真空室中残余的氧杂质易与B发生反应生成非晶相B2O3，导致非晶骨架不致密降低非晶/纳米晶层的结合力，破坏纳米复合结构，从而使涂层性能大幅度下降。并且生成的B2O3在高温环境下极易挥发，会严重降低涂层的高温性能。
发明内容
本发明的目的在于提供一种兼具高硬度和高韧性的Zr-B-N纳米复合涂层及其制备方法，通过向真空室中通入还原性气体，利用还原反应去除真空室中残余O杂质，抑制氧杂质对涂层性能的影响，从而提高涂层耐磨性能及韧性。
为实现上述目的，本发明所采用的技术方案如下：
一种兼具高硬度和高韧性Zr-B-N纳米复合涂层，制备于金属、合金或陶瓷材料基体上，所述Zr-B-N纳米复合涂层与基体之间沉积有CrN过渡层；其中，所述Zr-B-N纳米复合涂层包括非晶BN相和ZrB2晶相。
所述Zr-B-N纳米复合涂层，ZrB2相沿(001)晶面择优生长。
所述Zr-B-N纳米复合涂层与基体间的临界载荷大于41N，涂层硬度大于41GPa，涂层平均摩擦系数小于0.69，涂层的磨损率小于1.2×10-14m3/N·m。
所述Zr-B-N纳米复合涂层是采用脉冲直流磁控溅射技术在基体表面沉积获得，具体包括如下步骤：
(1)利用电弧离子镀技术蒸发金属Cr靶，对基体表面进行离子轰击清洗；
(2)通入高纯Ar、N2和H2的混合气体，沉积CrN过渡层，沉积完成后关闭Cr靶电源；
(3)在高纯Ar、N2和H2的混合气氛中，利用脉冲直流磁控溅射技术溅射ZrB2靶，反应沉积Zr-B-N纳米复合涂层。
上述步骤(1)离子轰击清洗前，先进行辉光放电清洗，具体过程如下：将真空室的本底真空抽至3.0×10-3Pa或以下，然后通入高纯氩气并加载-800V直流偏压对基体表面进行辉光放电清洗，工作压强保持在1.5Pa，辉光放电清洗时间15min。
上述步骤(1)中，所述离子轰击清洗过程为：向真空室内通入氩气流量100sccm，工作压强保持在6.0×10-1Pa，开启电弧离子镀电源，调节平均输出电流至90A，控制金属Cr靶起弧，输出电压为18～25V，偏压仍保持在-800V，进行离子轰击清洗8min。
上述步骤(2)中，沉积CrN过渡层的过程为：将基体偏压调至-150V，真空室内通入高纯Ar、N2和H2的混合气体，保持气体流量比(N2+H2)/(Ar+N2+H2)＝4/5，控制工作压强为9.0×10-1Pa，沉积CrN过渡层10min，之后关闭Cr靶电源。
上述步骤(3)中，沉积Zr-B-N涂层的过程为：真空室内通入高纯Ar、N2和H2的混合气体，保持气体流量比(N2+H2)/(Ar+N2+H2)＝1/11，工作压强调至6.0×10-1Pa，开启脉冲直流磁控溅射电源，控制ZrB2靶起辉，输出功率0.8kW，靶电流为2.5～2.8A，占空比为50％，基体偏压保持为-150V，开始正对靶材沉积Zr-B-N涂层；沉积时间根据涂层厚度要求而定。
上述步骤(2)沉积CrN过渡层过程中，靶基距保持在280mm，沉积温度400℃；步骤(3)沉积Zr-B-N涂层过程中，靶基距为75mm，沉积温度400℃。
上述步骤(2)和步骤(3)沉积涂层过程中，真空室内N2与H2的气体体积比为9:1。
本发明设计机理如下：
本发明采用脉冲直流磁控溅射技术，在还原性气氛下向金属或合金基体表面沉积Zr-B-N纳米复合涂层，在保证涂层硬度的前提下，进一步改善其韧性和摩擦性能。本发明实现了利用大量的两相(非晶和纳米晶)界面阻挡微裂纹的萌生和拓展，从而提高了涂层的韧性。并且还原性反应气体的引入，通过还原反应去除了真空室内残余氧杂质，抑制了氧杂质对涂层性能的破坏。
本发明采用脉冲直流磁控溅射技术在金属或合金基体上沉积Zr-B-N纳米复合涂层，为提高涂层与基体之间的结合强度，在沉积Zr-B-N涂层之前，先利用电弧离子镀技术轰击清洗基体，之后沉积约300nm厚的CrN过渡层，起缓冲内应力的作用。为增加涂层中硬质相的含量，选用化合物ZrB2靶作为脉冲直流磁控溅射靶，在反应气体N2中混入适量还原性气体H2，镀膜过程中通过还原反应去除镀膜室内残余氧杂质及N2中混有的氧杂质，并优化沉积工艺，抑制涂层中非晶B2O3的形成，减少O元素对非晶层的破坏，提高涂层纯度和硬度；向涂层内掺杂适量N元素，是为形成非晶BN相，利用纳米复合结构来改善涂层韧性。镀膜时严格控制反应气体流量和靶材的溅射功率，制备出结构致密、高硬度、高韧性的Zr-B-N纳米复合涂层。
本发明的优点如下：
1.本发明研制的Zr-B-N涂层化学性能稳定，不与常见的化学腐蚀介质反应，具有良好的耐腐蚀性能。涂层中的非晶BN相与纳米晶界面可有效阻挡微裂纹的萌生与拓展，极大地提高了涂层韧性。
2.本发明研制的Zr-B-N涂层具有较高的硬度和弹性模量，耐磨性能优异。还原性气氛的引入提高了涂层纯度，减少了氧杂质对涂层硬度的损伤。
3.本发明研制的Zr-B-N涂层抗冲击载荷性能良好，可用于高速切削与干切削领域。
4.本发明研制的Zr-B-N涂层厚度均匀且结构致密，与基体结合良好。
5.本发明研制的Zr-B-N涂层制备工艺简单，重复性好，应用范围广，实用性强。
附图说明
图1为实施例1制备的Zr-B-N涂层的表面形貌。
图2为实施例1制备的Zr-B-N涂层的断面形貌。
图3为实施例1制备的Zr-B-N涂层的X射线衍射谱(XRD)。
图4为实施例2制备的Zr-B-N涂层的硬度。
图5为实施例2制备的Zr-B-N涂层的划痕形貌。
图6为实施例2制备的Zr-B-N涂层的摩擦系数曲线。
具体实施方式
下面通过实例对本发明作进一步详细说明。
实施例1
本实施例为在已镜面抛光的单晶Si片((100)晶面)上沉积Zr-B-N涂层，基片尺寸为50mm×10mm×0.7mm。镀膜前先将基片在酒精溶液中超声清洗20分钟，然后用高纯氮气吹干，再正对靶材放置于真空室内试样架上。镀膜过程在V-TECH AS610型脉冲直流磁控溅射镀膜机上进行，该镀膜机上也配置有电弧离子镀阴极，靶材分别选用金属Cr靶和化合物ZrB2靶(纯度均为99.9wt.％)，金属Cr靶用于基体表面的离子轰击清洗和沉积CrN过渡层，化合物ZrB2靶用于沉积Zr-B-N涂层；工作气体和反应气体分别选用高纯Ar(纯度99.999％)和N2+H2(气体体积比N2：H2＝9:1)。
先将真空室的本底真空抽至3.0×10-3Pa，然后通入氩气对试样表面进行辉光放电清洗，工作压强保持在1.5Pa，加载-800V直流偏压，放电清洗时间15min；之后降低氩气流量，将工作压强调至6.0×10-1Pa，开启电弧离子镀电源，控制金属Cr靶起弧，平均输出电流为90A，输出电压为18～25V，偏压保持-800V，轰击清洗8min；然后降低偏压为-150V，通入N2和H2的混合气体(气体体积比N2:H2＝9:1)，保持气体流量比(N2+H2)/(Ar+N2+H2)＝4/5，调节工作压强为9.0×10-1Pa，沉积CrN过渡层10min，靶基距保持在280mm，沉积温度400℃；随后关闭Cr靶电源，调节真空室内气体流量比至(N2+H2)/(Ar+N2+H2)＝1/11，控制节流阀将工作压强调至6.0×10-1Pa，同时开启脉冲直流电源，输出功率0.8kW，靶电流为2.5～2.8A，占空比为50％，控制ZrB2靶起辉，开始正对靶材沉积Zr-B-N涂层，靶基距为75mm，基体偏压仍为-150V；连续镀膜60min。
Zr-B-N涂层的表面形貌和截面形貌如图1和图2所示，从图1可以看出，涂层表面组织结构均匀致密，无大颗粒和液滴出现。根据Zr-B-N涂层的截面形貌(图2)，可知涂层内部组织无明显柱状晶存在，涂层/过渡层/基体间界面结合良好。图3为采用本实施例工艺制备的Zr-B-N涂层的X射线衍射分析结果，涂层主要由多晶ZrB2相组成，其中(001)晶面的ZrB2相衍射峰最强，为涂层的择优生长方向。未发现与N元素相关的衍射峰，根据元素化合价态分析，N元素主要以非晶BN相存在，形成非晶层包裹纳米晶的复合结构，并且两相(非晶和纳米晶)界面的存在可以阻挡微裂纹的萌生和拓展，从而提高涂层的韧性。
实施例2
本实施例为在镜面抛光的YG8硬质合金基片上沉积Zr-B-N涂层，基片尺寸为30mm×30mm×3mm。基片先经金相砂纸研磨、抛光后，再依次用丙酮、脱脂剂、超纯水和酒精溶液超声清洗，用高纯氮气吹干后，正对靶材放置于真空室内试样架上。沉积过程及工艺参数同实施例1。
图4为硬质合金基体上沉积Zr-B-N涂层的硬度测试结果。可以看出涂层硬度测试值波动较小，在39～43GPa范围内变化，5次测量的平均值为41.9±1.2GPa，涂层硬度较高。涂层与基体的结合强度采用划痕法进行测试，金刚石划头的针尖半径为200μm，法向载荷以2.67N/s的速率由0N逐渐增加到80N，划痕长度为15mm，测试速度0.5mm/s。选取不同位置测试5次取平均值，Zr-B-N涂层临界载荷为41.3±0.7N，图5为划痕测试后Zr-B-N涂层上的划痕形貌，从图中可以识别涂层完全从基体上剥离的位置，经能谱分析确认，灰色区域为残余的涂层，白色区域为硬质合金基体。图6为Zr-B-N涂层与直径为6mm的氧化铝陶瓷球对摩后的摩擦系数曲线，测试条件：法向载荷2N，滑动速度0.1m/s，采用干摩擦旋转式运动，磨痕轨道半径为9mm。根据摩擦系数曲线，经计算稳定摩擦阶段的平均摩擦系数为0.69，Zr-B-N涂层的平均磨损率为1.12×10-14m3/N·m，利用本发明制备的涂层具有良好的摩擦磨损性能。
Claims (10)
1.一种兼具高硬度和高韧性Zr-B-N纳米复合涂层，其特征在于：所述Zr-B-N纳米复合涂层制备于金属、合金或陶瓷材料基体上，所述Zr-B-N纳米复合涂层与基体之间沉积有CrN过渡层；其中，所述Zr-B-N纳米复合涂层包括非晶BN相和ZrB2晶相。
2.根据权利要求1所述的Zr-B-N纳米复合涂层，其特征在于：所述Zr-B-N纳米复合涂层中，ZrB2相沿(001)晶面择优生长。
3.根据权利要求1所述的Zr-B-N纳米复合涂层，其特征在于：所述Zr-B-N纳米复合涂层与基体间的临界载荷大于41N，涂层硬度大于41GPa，涂层平均摩擦系数小于0.69，涂层的磨损率小于1.2×10-14m3/N·m。
4.根据权利要求1-3任一所述的Zr-B-N纳米复合涂层的制备方法，其特征在于：该方法是利用脉冲直流磁控溅射技术在基体上沉积Zr-B-N涂层，具体包括如下步骤：
(1)利用电弧离子镀技术蒸发金属Cr靶，对基体表面进行离子轰击清洗；
(2)通入高纯Ar、N2和H2的混合气体，沉积CrN过渡层，沉积完成后关闭Cr靶电源；
(3)在高纯Ar、N2和H2的混合气氛中，利用脉冲直流磁控溅射技术溅射ZrB2靶，反应沉积Zr-B-N纳米复合涂层。
5.根据权利要求4所述的Zr-B-N纳米复合涂层的制备方法，其特征在于：步骤(1)离子轰击清洗前，先进行辉光放电清洗，具体过程如下：将真空室的本底真空抽至3.0×10-3Pa或以下，然后通入高纯氩气并加载-800V直流偏压对基体表面进行辉光放电清洗，工作压强保持在1.5Pa，辉光放电清洗时间15min。
6.根据权利要求4所述的Zr-B-N纳米复合涂层的制备方法，其特征在于：步骤(1)中，所述离子轰击清洗过程为：向真空室内通入氩气流量100sccm，工作压强保持在6.0×10-1Pa，开启电弧离子镀电源，调节平均输出电流至90A，控制金属Cr靶起弧，输出电压为18～25V，偏压仍保持在-800V，进行离子轰击清洗8min。
7.根据权利要求4所述的Zr-B-N纳米复合涂层的制备方法，其特征在于：步骤(2)中，沉积CrN过渡层的过程为：将偏压调至-150V，真空室内通入高纯Ar、N2和H2的混合气体，保持气体流量比(N2+H2)/(Ar+N2+H2)＝4/5，控制工作压强为9.0×10-1Pa，沉积CrN过渡层10min，之后关闭Cr靶电源。
8.根据权利要求7所述的Zr-B-N纳米复合涂层的制备方法，其特征在于：步骤(3)中，沉积Zr-B-N涂层的过程为：真空室内通入高纯Ar、N2和H2的混合气体，保持气体流量比(N2+H2)/(Ar+N2+H2)＝1/11，工作压强调至6.0×10-1Pa，开启脉冲直流磁控溅射电源，控制ZrB2靶起辉，输出功率0.8kW，靶电流为2.5～2.8A，占空比为50％，基体偏压保持为-150V，开始正对靶材沉积Zr-B-N涂层；沉积时间根据涂层厚度要求而定。
9.根据权利要求8所述的Zr-B-N纳米复合涂层的制备方法，其特征在于：步骤(2)沉积CrN过渡层过程中，靶基距保持在280mm，沉积温度400℃；步骤(3)沉积Zr-B-N涂层过程中，靶基距为75mm，沉积温度400℃。
10.根据权利要求4所述的Zr-B-N纳米复合涂层的制备方法，其特征在于：步骤(2)和步骤(3)沉积涂层过程中，真空室内N2与H2的气体体积比为9:1。
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Application publication date: 20200911 Assignee: TIANJIN HUIZHU PETROLEUM EQUIPMENT TECHNOLOGY Co.,Ltd. Assignor: TIANJIN University OF TECHNOLOGY AND EDUCATION (CHINA VOCATIONAL TRAINING INSTRUCTOR TRAINING CENTER) Contract record no.: X2024980004373 Denomination of invention: Zr-B-N nanocomposite coating with high hardness and toughness and its preparation method Granted publication date: 20220719 License type: Common License Record date: 20240412 |