CN115449748A - 一种在镀锌板上的多层pvd复合镀膜钢板及其制备方法 - Google Patents
一种在镀锌板上的多层pvd复合镀膜钢板及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种在镀锌板上的多层PVD复合镀膜钢板及其制备方法，基板为镀锌钢板，镀膜层包括中间层和氮化钛层，所述中间层沉积在镀锌板基体上，所述氮化钛层沉积在所述中间层上。与现有技术相比，本发明的有益效果是：本发明提供了一种在镀锌板表面PVD复合镀层的制备方法，由于锌层与氮化钛层的热膨胀系数差别较大，二者结合时产生较大的残余应力，因此采用中间层过渡，使镀锌板表面与氮化钛镀层间具备更优秀的粘附性，使锌层与氮化钛层更有效的结合。这种复合镀层具有出色的镀层附着力，使其兼具备镀锌板的良好的耐蚀性和氮化钛涂层的金黄色的美观性和高硬度性能。
Description
技术领域
本发明涉及PVD镀层领域，尤其涉及一种在镀锌板上的多层PVD复合镀膜钢板及其制备方法。
背景技术
物理气相沉积(PVD)技术作为下一代的带钢镀层处理技术，其具有：生产过程更加环保、绝对均匀的涂层表面、出色的涂层粘附性、工艺在真空低温条件下完成、具有高度灵活性等特点。氮化钛膜层具有极好的装饰性，未来具有广阔的应用前景。但由于氮化钛涂层表面有较多的细微孔洞，大气中的氧气或其他易腐蚀物质会随这些孔洞进入基体内腐蚀基体，从而造成产品的使用寿命严重受影响。一些室内外装饰件对耐蚀性的要求越来越高，若采用不锈钢做基板，生产成本会显著增加，因此考虑选用兼顾良好耐蚀性和相对较低的生产成本的镀锌板作为基板。
现有的公开资料关于在钢板以及成型件上使用PVD技术制备复合涂层等方面研究较多，但关于使用PVD技术在镀锌板上沉积氮化钛的制备方法方面研究甚少。由于锌层和氮化钛涂层的硬度分别为55～65HV和1500～2500HV，锌层和氮化钛涂层的热膨胀系数分别为36×10-6/℃和6.81×10-6/℃，二者的硬度和热膨胀系数差异较大，给镀层技术带来一定的难度。
现有的关于PVD复合镀层的专利公开技术(CN 103436843 A)主要是在基体上镀锆再镀氮化钛的制备方法。专利公开文件(CN201621145486.9)是在球墨铸铁为基体上依次镀C、CrMeN/CrN混合过渡层和CrMe混合过渡层的复合镀层。但都没有涉及到以镀锌板作为基层镀膜氮化钛的技术。
发明内容
本发明提供了一种在镀锌板上的多层PVD复合镀膜钢板及其制备方法，在镀锌板上制备氮化钛膜层，氮化钛附着力较好，能够制造出具有高硬度、耐划伤、耐腐蚀且美观的钢板。
为了达到上述目的，本发明采用以下技术方案实现：
一种在镀锌板上的多层PVD复合镀膜钢板，基板为镀锌钢板，镀膜层包括中间层和氮化钛层，所述中间层沉积在镀锌板基体上，所述氮化钛层沉积在所述中间层上。
所述中间层元素包括Cr、Ni、Ti、Mg、Cu、Ag中的一种或多种作为组合进行沉积，其Cu、Ag具有抗菌效果。
所述中间层元素从下至上依次沉积Cu、Cr和Ag。
所述中间层元素从下至上依次沉积Cr、Ni和Ag。
所述镀锌钢板镀锌层的制备方式包括电镀、热浸镀和PVD镀锌。
所述镀锌层厚度为5～20μm。
所述中间层厚度为100～500nm。
所述氮化钛层厚度为700～1500nm。
一种在镀锌板上的多层PVD复合镀膜钢板的制备方法，包括如下方法：
1)由于热浸镀锌板的生产效率高且成本低，因此本发明提供的基板优选为在钢板上热浸镀锌层，锌锅温度为445～450℃；
2)在真空室内，通入氩气，采用氩离子刻蚀清洗镀锌板表面使基板洁净清洗时间为10～20min；
3)由于锌层熔点较低，因此本发明优选沉积温度较低镀膜表面较均匀致密的磁控溅射的方式，中间层和氮化钛层利用磁控溅射镀，其工艺参数为：功率为50～200W，电压为100～300V，基体负偏压为60～120V，占空比为50％～80％，气压为0.4～0.6Pa，温度为200～500℃；
4)相关资料表明，氮化钛层硬度较大，其与镀锌板的结合力较差、易脱落，增加中间层作为过渡可有效增加镀层之间的结合力。在镀锌板上沉积Cr、Ni、Ti、Mg、Cu中的一种或多种组合作为中间层过渡，沉积时间8～30min；
5)在中间层上沉积氮化钛层，为了控制氮化钛膜层为明亮度金黄色，优选氮氩流量比为0.4～0.45，沉积时间50～80min；
6)为减少氮化钛表面细微空洞带来的易氧化危害，最后在氮化钛表面进行封孔处理。
工作原理说明：
1)PVD镀膜技术主要分真空蒸镀、磁控溅射镀和电弧离子镀等。真空蒸镀具有成膜方法简单，但膜层易脱落；磁控溅射镀的膜表面致密层度较高，可在低温下成膜；电弧离子镀的金属离化率较高，成膜速率快、膜与基体的结合力较强。本发明建议优先选择磁控溅射镀膜技术，原因如下：采用磁控溅射的镀膜技术在沉积过程中温度相对较低，可控制在锌层熔点以下，因此不会破坏锌层的完整性，从而保证了基板的耐腐蚀性能。且该技术制备出的膜层致密度较高，表面更加均匀。
2)由于锌层与氮化钛层的热膨胀系数和硬度相差较大，需增加中间层作为过渡。采用Cr、Ni、Ti作为中间层时，这种复合PVD镀层比直接在镀锌板上镀氮化钛表现出良好的结合强度、硬度和耐磨性能等，这可以充分发挥氮化钛涂层的优势；采用Mg作为中间层时，Mg在沉积过程中可与锌层发生反应生成MgZn2相，该相具有良好的耐腐蚀性能，可使其耐蚀性增强；采用Cu、Ag作为中间层时，由于Cu本身具有抗菌作用，含Cu的氮化钛膜层可以制备出具有兼备抗菌能力和色彩美观性的氮化钛膜层。
3)在完成PVD镀膜之后，需在样品表面进行封孔处理，其目的是将PVD膜层中的细微孔洞进行填补及密封，避免在运输、存储及使用时空气或腐蚀性物资通过细微孔洞进入基体，从而延长其使用寿命。
与现有技术相比，本发明的有益效果是：
本发明提供了一种在镀锌板上的多层PVD复合镀膜钢板及其制备方法，采用中间层过渡，使镀锌板表面与氮化钛膜层间具备更优秀的粘附性，使锌层与氮化钛层更有效的结合。这种复合镀层具有出色的附着力，使其兼具备镀锌板的良好的耐蚀性(盐雾试验板面无白锈时间可达48h以上)和氮化钛膜层的高硬度(1600～2300HV)、耐划伤且美观的金黄色表面。
附图说明
图1为本发明镀层结构。
图中：1-钢基体、2-锌层、3-中间层、4-氮化钛层、5-封孔处理层。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例工艺方法如下：
见图1，一种多层PVD复合镀膜钢板，基板为镀锌钢板，镀膜层包括中间层3和氮化钛层4，中间层3沉积在镀锌板基体上，氮化钛层沉积在所述中间层上，制备方法如下：
1)实施例提供的基板为在钢板上镀锌；
2)在真空室内，通入氩气，采用氩离子刻蚀清洗镀锌板表面；
3)中间层和氮化钛层利用磁控溅射镀；
4)增加中间层作为过渡可有效增加镀层之间的结合力。其中实施例2和实施例3中在沉积中间层时是同时沉积两种元素，实施例6和实施例7中在沉积中间层时是分别依次沉积表1中所对应的三种元素。实施例6中在沉积中间层是分别依次沉积Cu、Cr和Ag这三种元素，把硬度最高的Cr层夹在Cu层和Ag层之间，当受外力时这种软硬相间的“三明治”复合结构的中间层有利于缓冲，该镀层产品既有抗菌功效又有增大了其韧性。实施例7中在沉积中间层是按照热膨胀系数升序分别依次沉积Cr、Ni和Ag这三种元素，其在温度有变化时镀层材料的几何形状受影响程度较微小，该镀层产品既有抗菌功效又有利于提高镀层之间结合力；
5)在中间层上沉积氮化钛层，为了控制氮化钛层为明亮度金黄色；
6)最后在氮化钛表面进行封孔处理；
实施例1～7：具体案例主要规格和性能见附表1，中间层主要工艺参数见附表2，氮化钛层主要工艺参数见附表3。
表1样品主要规格和性能
表2中间层主要工艺参数
表3氮化钛层主要工艺参数
Claims (9)
1.一种在镀锌板上的多层PVD复合镀膜钢板，其特征在于，基板为镀锌钢板，镀膜层包括中间层和氮化钛层，所述中间层沉积在镀锌板基体上，所述氮化钛层沉积在所述中间层上。
2.根据权利要求1所述的一种在镀锌板上的多层PVD复合镀膜钢板，其特征在于，所述中间层元素包括Cr、Ni、Ti、Mg、Cu、Ag中的一种或多种作为组合进行沉积。
3.根据权利要求2所述的一种在镀锌板上的多层PVD复合镀膜钢板，其特征在于，所述中间层元素从下至上依次沉积Cu、Cr和Ag。
4.根据权利要求2所述的一种在镀锌板上的多层PVD复合镀膜钢板，其特征在于，所述中间层元素从下至上依次沉积Cr、Ni和Ag。
5.根据权利要求1所述的一种在镀锌板上的多层PVD复合镀膜钢板，其特征在于，所述镀锌钢板镀锌层的制备方式包括电镀、热浸镀和PVD镀锌。
6.根据权利要求3所述的一种在镀锌板上的多层PVD复合镀膜钢板，其特征在于，所述镀锌层厚度为5～20μm。
7.根据权利要求1所述的一种在镀锌板上的多层PVD复合镀膜钢板，其特征在于，所述中间层厚度为100～500nm。
8.根据权利要求1所述的一种在镀锌板上的多层PVD复合镀膜钢板，其特征在于，所述氮化钛层厚度为700～1500nm。
9.一种如权利要求1-7其中任意一项所述的在镀锌板上的多层PVD复合镀膜钢板制备方法，其特征在于，包括如下方法：
1)在钢板上热浸镀锌层，锌锅温度为445～450℃；
2)在真空室内，通入氩气，采用氩离子刻蚀清洗镀锌板表面使基板洁净清洗时间为10～20min；
3)中间层和氮化钛层利用磁控溅射镀，其工艺参数为：功率为50～200W，电压为100～300V，基体负偏压为60～120V，占空比为50％～80％，气压为0.4～0.6Pa，温度为200～500℃；
4)在镀锌板上沉积Cr、Ni、Ti、Mg、Cu、Ag中的一种或多种组合作为中间层过渡，沉积时间为8～30min；
5)在中间层上沉积氮化钛层沉积时间50～80min，氮氩流量比为0.4～0.45；
6)最后在氮化钛表面进行封孔处理。
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