CN113969392A - 一种可调控的Ti-Al-C系MAX相涂层的制备方法 - Google Patents
一种可调控的Ti-Al-C系MAX相涂层的制备方法 Download PDFInfo
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Abstract
本发明公开了一种可调控的Ti‑Al‑C系MAX相涂层的制备方法，包括：以Ti‑Al复合靶作为溅射靶，以碳氢气体作为反应气源，所述的碳氢气体的流量为5‑12sccm，采用直流磁控溅射，对清洁后的基体表面溅射得到Ti‑Al‑C涂层，将所述的Ti‑Al‑C涂层加热到600‑700℃，保温60‑180min得到Ti‑Al‑C系MAX相涂层。该方法能够简单、高效的调控不同的Ti‑Al‑C系MAX相，同时能够降低热处理温度。
Description
技术领域
本发明涉及表面处理技术领域，具体为一种可调控的Ti-Al-C系MAX相涂层的制备方法。
背景技术
MAX相材料是一大类热力学稳定、具有密排六方结构的层状高性能陶瓷金属材料，通式为Mn+1AXn，其中M位为早期过渡金属元素，包括Ti、Cr等，A位通常为元素周期表中ⅢA或ⅣA族元素，像Al、Si等，X位元素为C或N，可以理解为由单层A原子分割的金属碳化物或金属氮化物纳米层状化合物。
一般来说，M-X以强的共价键和离子键结合，而M-A依靠相对较弱的金属键结合。这种独特的层状结构和成键方式，使MAX相兼具金属和陶瓷的优异性能，如优异的机械稳定性、高硬度，热震耐受好，强的耐蚀性和高温抗氧化性，良好的电导率和热导率，以及自愈合特性和可加工性等，在核能、海洋、航空航天、汽车、生物医药等高技术领域具有广泛的应用。
在通式Mn+1AXn中，n值表示MAX相晶体结构中每两层A原子之间M原子的层数为n+1，目前大多数已知的MAX相材料n值主要有1、2、3，根据n值的不同将MAX相分为211，312，413相。其中典型的含Al的MAX相材料通过形成保护性Al2O3层而表现出显著的抗高温氧化和抗腐蚀性能，最具代表的Ti-Al-C体系和Cr-Al-C体系中又以Ti-Al-C化合物与Al2O3的热膨胀系数相近成为不锈钢、钛合金、镍基高温合金等基体的合适的防护涂层。
Ti-Al-C系MAX相包括211相的Ti2AlC和312相的Ti3AlC2两种，两者具有相似的成键特征和能带结构，性能相近。目前，Ti2AlC和Ti3AlC2的主要制备方法为物理气相沉积(PVD)技术中的阴极电弧溅射或者磁控溅射，由于相对复杂的MAX相长c轴晶体结构的合成需要足够的扩散率来划分元素，所以两者的成相需要高的热处理温度(800-1000℃)，Ti3AlC2因为更长的c轴，成相温度要更高。
如何在较低温度下实现211相和312相的制备，使得Ti-Al-C系MAX相对于不同类型基材有更强的适应性，以及基于需求如何调控Ti-Al-C系MAX的不同相是亟需解决的问题。
发明内容
本发明提供一种可调控的Ti-Al-C系MAX相涂层的制备方法，该方法能够简单、高效的调控不同的Ti-Al-C系MAX相，同时能够降低热处理温度。
一种可调控的Ti-Al-C系MAX相涂层的制备方法，包括：
以Ti-Al复合靶作为溅射靶，以碳氢气体作为反应气源，所述的碳氢气体的流量为5-12sccm，持续通入惰性气体，采用直流磁控溅射，对清洁后的基体表面溅射得到Ti-Al-C涂层，将所述的Ti-Al-C涂层加热到600-700℃，保温60-180min得到Ti-Al-C系MAX相涂层。
进一步的，所述的碳氢气体的流量为5-8sccm，得到Ti-Al-C系MAX相为211相。
进一步的，所述的碳氢气体的流量为9-12sccm，得到Ti-Al-C系MAX相为312相。
进一步的，所述碳氢气体为乙炔或甲烷。
本发明利用直流磁控溅射技术与碳氢气体流量相结合，为基体表面单位面积内提供足够量的碳原子，降低了211和312相的热处理温度，并且通过控制碳氢气体流量能够根据需要获得211相和312相，实现对制备211相和312相的调控，并且结合直流磁控溅射技术，在较大的碳氢气体流量的情况下，得到结构致密，表面光滑，晶粒均匀细小的Ti-Al-C系MAX相为211相。
所述的惰性气体为氩气或氮气，所述惰性气体的流量为150-200sccm。
所述的直流磁控溅射的参数为：溅射靶功率为1500-2500W，基体负偏压为0-100V，腔体气压为0.6-1.2Pa，沉积时间为60-180min，真空度低于1-3×10-5Pa。
所述的Ti-Al复合靶的Ti-Al元素比为2:1.2～1.5。
对所述的基体表面进行清洁的步骤为：
对基体表面用400#～2000#的SiC砂纸打磨，然后抛光预处理后在丙酮中超声清洗10-15min。
所述的基体为不锈钢或钛基合金。
对所述的基体表面进行清洁后，进行等离子体辉光刻蚀处理，所述的等离子体辉光刻蚀处理的参数为：等离子流量为30-35sccm，离子源电压为1000～1200V，基体施加负偏压150-250V，刻蚀时间为20-40min。通过等离子体辉光刻蚀处理使得基体与溅射涂层结合更加紧密。
所述的等离子体为氩气，氮气中的任意一种。
在所述的对基体进行等离子体辉光刻蚀处理之后，在所述的基体表面溅射一层过渡层。
所述的基体表面溅射一层过渡层的步骤为：关闭所述的反应源，并通入保护性气体，开起所述的Ti-Al复合靶对基体进行直流溅射。
进一步的，所述的过渡层为TiAl间化合物。
进一步的，所述的溅射参数为：溅射功率1800～2400W，基体偏压为-100～0V。
进一步的，所述的保护性气体的流量为150～250sccm，腔体气压为0.6～1.2Pa。
进一步的，将所述的Ti-Al-C涂层加热之前，控制真空度低于1-3×10-3Pa。
与现有技术相比，本发明的有益效果为：
(1)采用Ti-Al复合靶和碳氢气体的反应磁控溅射沉积制备，能够通过对反应气体的流量调节轻松实现对热处理后涂层中211相和312相成分的控制和相纯度的调控；从而有利于根据成分性能优势满足不同领域的应用需求。
(2)通过对反应气体碳氢气体流量的调控，改善了312相成相对于退火温度的依赖，在一定程度上降低了312相的退火温度，即单纯通过流量调控，实现了较低温度下211相或312相的制备。
附图说明
图1为实施例1～3制得的Ti-Al-C系MAX相涂层涂层的XRD谱图。
图2为实施例1～3制得的Ti-Al-C系MAX相涂层涂层的表面形貌图，其中，2(a)为实施例1制得的Ti-Al-C系MAX相涂层涂层的表面形貌图，2(b)为实施例2制得的Ti-Al-C系MAX相涂层涂层的表面形貌图，2(c)为实施例3制得的Ti-Al-C系MAX相涂层涂层的表面形貌图。
具体实施方式
本发明实施例主要在保护性气体中，以Ti-Al复合靶为溅射靶，以碳氢气体作为反应气体，通过对反应气体碳氢气体的流量调节，实现对涂层中Ti-Al-C系MAX相成分的控制和调控。
下面结合优选实施例及附图对本发明的技术方案做进一步的详细说明，本实施例在以发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例1：
本实施例中，基体材料为1Cr11Ni2W2MoV不锈钢，基体表面涂层的具体制备步骤如下：
步骤1：使用400#～2000#的SiC砂纸依次对1Cr11Ni2W2MoV不锈钢表面进行打磨，再使用金刚石研磨膏进行抛光20min。
步骤2：将打磨抛光后的1Cr11Ni2W2MoV不锈钢基体置于丙酮中超声清洗10min，而后冷风吹干用导电胶粘贴于样品架上备用。
步骤3：将粘贴有基体的样品架置于沉积腔体室中，待机械泵和分子泵抽真空至3×10-5Pa以下，设置腔体温度为100℃，向真空腔体中通入34sccm的高纯氩气，设置线性阳极离子源电流为0.2A，基体偏压为-200V，对1Cr11Ni2W2MoV不锈钢的表面刻蚀清洗30min。
步骤4：Ti-Al过渡层的沉积条件与以下步骤5中的一致，区别在于通入的气体不同，过渡层的沉积不通入碳氢反应气体，只通入200sccm的高纯氩气。
步骤5：以Ti-Al复合靶为溅射靶，腔体中通入高纯氩气，高纯甲烷气体为反应气体，进行反应磁控溅射沉积得到包含Cr，Al，C三种元素成分的涂层，其中高纯氩气的流量为200sccm，高纯甲烷的流量为5sccm，溅射靶的Ti、Al比为2:1.5，溅射功率为2000W，基体偏压为0V，腔体气压为1Pa，沉积时间为120min。
步骤6：将得到的沉积态Ti-Al-C涂层置于退火炉中，真空度低于2×10-3Pa，在700℃中保温90min。
步骤7：对上述制得的涂层的进行XRD和扫描电镜测试。
图1和图2分别是一定甲烷反应气体流量的所制备涂层的X射线衍射和扫描电镜测试图谱，由图1所示，实施例1中的涂层成分主要是TiAl间化合物和少量被检测到的Ti2AlC的峰。图2(a)所示的扫描电镜测试中，表面平整致密。
实施例2：
本实施例中，基体材料为1Cr11Ni2W2MoV不锈钢，基体表面涂层的具体制备步骤如下：
步骤1：使用400#～2000#的SiC砂纸依次对1Cr11Ni2W2MoV不锈钢表面进行打磨，再使用金刚石研磨膏进行抛光20min。
步骤2：将打磨抛光后的1Cr11Ni2W2MoV不锈钢基体置于丙酮中超声清洗10min，而后冷风吹干用导电胶粘贴于样品架上备用。
步骤3：将粘贴有基体的样品架置于沉积腔体室中，待机械泵和分子泵抽真空至3×10-5Pa以下，设置腔体温度为100℃，向真空腔体中通入34sccm的高纯氩气，设置线性阳极离子源电流为0.2A，基体偏压为-200V，对1Cr11Ni2W2MoV不锈钢的表面刻蚀清洗30min。
步骤4：Ti-Al过渡层的沉积条件与以下步骤5中的一致，区别在于通入的气体不同，过渡层的沉积不通入碳氢反应气体，只通入200sccm的高纯氩气。
步骤5：以Ti-Al复合靶为溅射靶，腔体中通入高纯氩气和高纯甲烷气体为反应气体进行反应磁控溅射沉积得到包含Cr，Al，C三种元素成分的涂层，其中高纯氩气的流量为200sccm，高纯甲烷的流量为7.5sccm，溅射靶的Ti、Al比为2:1.5，溅射功率为2000W，基体偏压为0V，腔体气压为1Pa，沉积时间为120min。
步骤6：将得到的沉积态Ti-Al-C涂层置于退火炉中，真空度低于2×10-3Pa，在700℃中保温90min。
步骤7：对上述制得的涂层的进行XRD和扫描电镜测试。
图1和图2分别是一定甲烷反应气体流量的所制备涂层的X射线衍射和扫描电镜测试图谱，由图1所示，实施例2中的涂层成分TiAl化合物消失，涂层的主要成分转变为了Ti2AlC。图2(b)所示的扫描电镜测试中，表面平整致密，有部分颗粒聚集，晶粒大小为0.24μm。
实施例3：
本实施例中，基体材料为1Cr11Ni2W2MoV不锈钢，基体表面涂层的具体制备步骤如下：
步骤1：使用400#～2000#的SiC砂纸依次对1Cr11Ni2W2MoV不锈钢表面进行打磨，再使用金刚石研磨膏进行抛光20min。
步骤2：将打磨抛光后的1Cr11Ni2W2MoV不锈钢基体置于丙酮中超声清洗10min，而后冷风吹干用导电胶粘贴于样品架上备用。
步骤3：将粘贴有基体的样品架置于沉积腔体室中，待机械泵和分子泵抽真空至3×10-5Pa以下，设置腔体温度为100℃，向真空腔体中通入34sccm的高纯氩气，设置线性阳极离子源电流为0.2A，基体偏压为-200V，对1Cr11Ni2W2MoV不锈钢的表面刻蚀清洗30min。
步骤4：Ti-Al过渡层的沉积条件与以下步骤5中的一致，区别在于通入的气体不同，过渡层的沉积不通入碳氢反应气体，只通入200sccm的高纯氩气。
步骤5：以Ti-Al复合靶为溅射靶，腔体中通入高纯氩气和高纯甲烷气体为反应气体进行反应磁控溅射沉积得到包含Cr，Al，C三种元素成分的涂层，其中高纯氩气的流量为200sccm，高纯甲烷的流量为10sccm，溅射靶的Ti、Al比为2:1.5，溅射功率为2000W，基体偏压为0V，腔体气压为1Pa，沉积时间为120min。
步骤6：将得到的沉积态Ti-Al-C涂层置于退火炉中，真空度低于2×10-3Pa，在700℃中保温90min。
步骤7：对上述制得的涂层的进行XRD和扫描电镜测试。
图1和图2分别是一定甲烷反应气体流量的所制备涂层的X射线衍射和扫描电镜测试图谱，由图1所示，实施例3中的涂层成分由Ti2AlC转变为了Ti3AlC2。图2(c)所示的扫描电镜测试中，表面平整致密，颗粒变得细化，晶粒大小为0.13μm。
Claims (10)
1.一种可调控的Ti-Al-C系MAX相涂层的制备方法，其特征在于，包括：
以Ti-Al复合靶作为溅射靶，以碳氢气体作为反应气源，所述的碳氢气体的流量为5-12sccm，对清洁后的基体表面进行直流磁控溅射得到Ti-Al-C涂层，将所述的Ti-Al-C涂层加热到600-700℃，保温60-180min得到Ti-Al-C系MAX相涂层。
2.根据权利要求1所述的可调控的Ti-Al-C系MAX相涂层的制备方法，其特征在于，所述的碳氢气体的流量为5-8sccm，得到Ti-Al-C系MAX相为211相。
3.根据权利要求1所述的可调控的Ti-Al-C系MAX相涂层的制备方法，其特征在于，所述的碳氢气体的流量为9-12sccm，得到Ti-Al-C系MAX相为312相。
4.根据权利要求1-3任一项所述的可调控的Ti-Al-C系MAX相涂层的制备方法，其特征在于，所述碳氢气体为乙炔或甲烷。
5.根据权利要求1所述的可调控的Ti-Al-C系MAX相涂层的制备方法，其特征在于，所述的直流磁控溅射的参数为：溅射靶功率为1500-2500W，基体负偏压为0-100V，腔体气压为0.6-1.2Pa，沉积时间为60-180min，真空度低于1-3×10-5Pa。
6.根据权利要求1所述的可调控的Ti-Al-C系MAX相涂层的制备方法，其特征在于，所述的Ti-Al复合靶的Ti-Al元素比为2:1.2～1.5。
7.根据权利要求1所述的可调控的Ti-Al-C系MAX相涂层的制备方法，其特征在于，对所述的基体表面进行清洁，包括：
对基体表面用400#～2000#的SiC砂纸打磨，然后抛光预处理后在丙酮中超声清洗10-15min。
8.根据权利要求1所述的可调控的Ti-Al-C系MAX相涂层的制备方法，其特征在于，所述的基体为不锈钢或钛基合金。
9.根据权利要求7所述的可调控的Ti-Al-C系MAX相涂层的制备方法，其特征在于，对所述的基体表面进行清洁后，进行等离子体辉光刻蚀处理，所述的等离子体辉光刻蚀处理的参数为：等离子流量为30-35sccm，离子源电压为1000～1200V，基体施加负偏压150-250V，刻蚀时间为20-40min。
10.根据权利要求9所述的可调控的Ti-Al-C系MAX相涂层的制备方法，其特征在于，在所述的对基体进行等离子体辉光刻蚀处理之后，在所述的基体表面溅射一层过渡层，所述的过渡层为TiAl间化合物。
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