CN102443773A - 涂层、具有该涂层的被覆件及该被覆件的制造方法 - Google Patents

涂层、具有该涂层的被覆件及该被覆件的制造方法 Download PDF

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CN102443773A
CN102443773A CN2010102990258A CN201010299025A CN102443773A CN 102443773 A CN102443773 A CN 102443773A CN 2010102990258 A CN2010102990258 A CN 2010102990258A CN 201010299025 A CN201010299025 A CN 201010299025A CN 102443773 A CN102443773 A CN 102443773A
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张新倍
陈文荣
蒋焕梧
陈正士
马闯
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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Hon Hai Precision Industry Co Ltd
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Abstract

本发明提供一种涂层，该涂层包括纳米复合层，该纳米复合层包括若干ZrN层和若干ZrYN层，所述若干ZrN层和若干ZrYN层交替排布。该涂层具有良好的硬度、韧性及耐磨性。本发明还提供一种具有上述涂层的被覆件，该被覆件包括基体、形成于该基体的结合层及形成于该结合层上的所述涂层。该结合层为ZrY层。另外，本发明还提供了上述被覆件的制造方法。

Description

涂层、具有该涂层的被覆件及该被覆件的制造方法
技术领域
本发明涉及一种涂层、具有该涂层的被覆件及该被覆件的制造方法，特别涉及一种以真空镀膜的方式形成的涂层、具有该涂层的被覆件及该被覆件的制造方法。
背景技术
真空镀膜工艺在工业领域有着广泛的应用，其中，TiN薄膜镀覆在刀具或模具表面能大幅提高刀具和模具的使用寿命。然而，随着金属切削加工朝高切削速度、高进给速度、高可靠性、长寿命、高精度和良好的切削控制性方面发展，对表面涂层的性能提出了更高的要求。传统的TiN涂层在硬度、韧性等方面已经不能满足要求。
ZrN薄膜由于其硬度与韧性均优于TiN薄膜而受到人们的广泛关注。但单一的ZrN薄膜在硬度、韧性及耐磨性等方面几乎已经没有提高的空间，很难满足现代工业的需求。
发明内容
有鉴于此，提供一种具有良好硬度、韧性及耐磨性的涂层。
另外，还提供一种应用上述涂层的被覆件。
另外，还提供一种上述被覆件的制造方法。
一种涂层，该涂层包括纳米复合层，该纳米复合层包括若干ZrN层和若干ZrYN层，所述若干ZrN层和若干ZrYN层交替排布。
一种被覆件，该被覆件包括基体、形成于该基体的结合层及形成于该结合层上的涂层，该结合层为ZrY层，该涂层包括纳米复合层，该纳米复合层包括若干ZrN层和若干ZrYN层，所述若干ZrN层和若干ZrYN层交替排布。
一种被覆件的制造方法，包括以下步骤：
提供基体；
于该基体的表面磁控溅射结合层，该结合层为ZrY层；
于该结合层的表面磁控溅射纳米复合层，该纳米复合层包括若干ZrN层和若干ZrYN层，所述若干ZrN层和若干ZrYN层交替排布。
在形成所述ZrYN层时，N原子优先与Zr原子形成ZrN晶粒，Y原子则以独立形式偏聚在晶界上形成Y相，其可抑制ZrN晶粒的长大，因而使得ZrYN层中的ZrN晶粒的粒径维持在纳米级，该纳米级的ZrN晶粒可有效提高所述纳米复合层的硬度和韧性。更重要的是，由于纳米级氮化物ZrN与ZrYN之间剪切模量的差异，交替沉积的每一ZrN层与每一ZrYN层之间的位错运动在二膜层的界面处而停止，位错的塞积可产生硬化现象及抑制膜层的变形，从而使得所述纳米复合层的硬度及韧性进一步得到显著的提高。所述的被覆件在基体与纳米复合层之间设置ZrY结合层，可有效提高涂层与基体之间的结合力。所述涂层的硬度、韧性的提高及涂层与基体之间结合力的增强，可显著地提高所述涂层的耐磨性。
附图说明
图1为本发明一较佳实施例的涂层的剖视图；
图2为本发明一较佳实施例的被覆件的剖视图。
主要元件符号说明
基体          10
结合层        20
涂层          30
纳米复合层    31
ZrN层         311
ZrYN层        313
颜色层        33
被覆件        40
具体实施方式
请参阅图1，本发明一较佳实施例的涂层30包括纳米复合层31。该纳米复合层31包括若干氮化锆(ZrN)层311和若干氮化锆钇(ZrYN)层313，所述若干ZrN层311和若干ZrYN层313交替排布。所述若干ZrN层311及若干ZrYN层313通过磁控溅射的方法形成。该若干ZrN层311及若干ZrYN层313的层数分别为20～50层。
每一ZrN层311的厚度为10～20nm，每一ZrYN层313的厚度为10～20nm。所述涂层30的总厚度为1～4μm。
可以理解的，所述涂层30还可包括于该纳米复合层31的表面上镀覆的颜色层33，以增强该涂层30的美观性。
请参阅图2，本发明一较佳实施例的被覆件40包括基体10、形成于该基体10的结合层20及形成于该结合层20上的所述涂层30。该基体10的材质可以为高速钢、硬质合金及不锈钢等。该被覆件40可以为各类切削刀具、精密量具、模具、3C电子产品外壳及各种建筑装饰件等。
该结合层20为锆钇(ZrY)层，其厚度为0.05～0.2μm。该结合层20通过磁控溅射法沉积形成。该结合层20的化学稳定性与热膨胀系数介于基体10与涂层30之间，因而可有效提高涂层30与基体10之间的结合力。所述涂层30与基体11直接结合的为ZrN层311。
所述被覆件40的制造方法主要包括如下步骤：
提供基体10，该基体10的材质可以为高速钢、硬质合金、金属陶瓷及烧结金刚石等。将基体10放入盛装有乙醇及/或丙酮溶液的超声波清洗器中进行震动清洗，以除去基体10表面的杂质和油污等。清洗完毕后烘干备用。
对经上述处理后的基体10的表面进行氩气等离子体清洗，以进一步去除基体10表面的油污，以及改善基体10表面与后续涂层的结合力。该等离子体清洗的具体操作及工艺参数为：将基体10固定于磁控溅射镀膜机的镀膜室的工件架上，抽真空该镀膜室至真空度为8.0×10-3Pa，以300～600sccm(标准状态毫升/分钟)的流量向镀膜室内通入纯度为99.999％的氩气，并施加-300～-800V的偏压于基体10，对基体10表面进行等离子体清洗，清洗时间为3～10min。
在对基体10进行等离子体清洗后，于该基体10上形成结合层20。该结合层20为ZrY层。形成该结合层20的具体操作方法及工艺参数如下：调节氩气(工作气体)流量至150～300sccm，加热该镀膜室至150～300℃(即溅射温度为150～300℃)，设置所述工件架的公转速度为1.0～3.0rpm(revolution per minute，转/分钟)；开启分别安装于所述镀膜室两侧的锆靶及锆钇合金靶的电源，并设置所述锆靶及锆钇合金靶的电流均为20～100A；于基体10上施加-100～-300V的偏压，沉积结合层20。沉积该结合层20的时间为5～15min。所述锆钇合金靶中Zr的质量百分含量为70～90％。
形成所述结合层20后，于该结合层20上形成纳米复合层31。该纳米复合层31由若干ZrN层311和若干ZrYN层313交替沉积形成。形成所述纳米复合层31的具体操作方法及工艺参数如下：向镀膜室中通入流量为10～200sccm的纯度为99.999％的氮气，以沉积所述纳米复合层31。沉积该纳米复合层31时，交替开启分别安装于所述磁控溅射镀膜机的锆钇合金靶及锆靶，以于结合层20上交替沉积若干ZrN层311和若干ZrYN层313。沉积该纳米复合层31的时间为60～120min。
关闭负偏压、锆钇合金靶及锆靶电源，停止通入氩气及氮气，待所述纳米复合层31冷却后，向镀膜内通入空气，打开镀膜室门，取出镀覆有结合层20及纳米复合层31的基体10。
可以理解的，制造所述被覆件40的方法还可包括在该纳米复合层31的表面镀覆颜色层33，以增强被覆件40的美观性。
在形成ZrYN层313时，由于Y与Zr不能形成固溶体，且Y不易与氮气反应，沉积过程中氮气中的N原子优先与Zr原子形成ZrN晶粒，Y原子则以独立形式偏聚在晶界上形成Y相，其可抑制ZrN晶粒的长大，因而使得ZrYN层313中的ZrN晶粒的粒径维持在纳米级，该纳米级的ZrN晶粒可显著地提高所述纳米复合层31的硬度和韧性。更重要的是，由于纳米级氮化物ZrN与ZrYN之间剪切模量的差异，交替沉积的每一ZrN层311与每一ZrYN层313之间的位错运动在二膜层的界面处而停止，位错的塞积可产生硬化现象及抑制膜层的变形，从而使得所述纳米复合层31的硬度及韧性进一步得到显著的提高。
所述的被覆件40在基体10与纳米复合层31之间设置ZrY结合层20，由于该结合层20的化学稳定性与热膨胀系数介于基体10与纳米复合层31之间，因而可有效提高纳米复合层31与基体10之间的结合力。所述纳米复合层31的硬度、韧性的提高及纳米复合层31与基体10之间结合力的增强，可显著地提高所述涂层30的耐磨性。
此外，所述涂层30在磨损过程中，涂层30表层的Y可与膜层外界的O、S等元素结合，形成含有对应的氧化物或/和硫化物的膜层，该膜层致密且硬度较高，在工作过程中对所述被覆件40起到较好的保护作用，间接地提高了被覆件40的硬度及耐磨性。

Claims (10)

1.一种涂层，该涂层包括纳米复合层，其特征在于：该纳米复合层包括若干ZrN层和若干ZrYN层，所述若干ZrN层和若干ZrYN层交替排布。
2.如权利要求1所述的涂层，其特征在于：每一ZrN层的厚度为10～20nm，每一ZrYN层的厚度为10～20nm。
3.如权利要求1所述的涂层，其特征在于：该涂层的总厚度为1～4μm。
4.如权利要求1所述的涂层，其特征在于：该涂层还包括形成于该纳米复合层上的颜色层。
5.一种被覆件，该被覆件包括基体、形成于该基体的结合层及形成于该结合层上的涂层，该涂层包括纳米复合层，其特征在于：该结合层为ZrY层，该纳米复合层包括若干ZrN层和若干ZrYN层，所述若干ZrN层和若干ZrYN层交替排布。
6.如权利要求5所述的被覆件，其特征在于：该结合层为ZrY层，其厚度为0.05～0.2μm。
7.一种被覆件的制造方法，包括以下步骤：
提供基体；
于该基体的表面磁控溅射结合层，该结合层为ZrY层；
于该结合层的表面磁控溅射纳米复合层，该纳米复合层包括若干ZrN层和若干ZrYN层，所述若干ZrN层和若干ZrYN层交替排布。
8.如权利要求7所述的被覆件的制造方法，其特征在于：磁控溅射该结合层的步骤以如下方式进行：以锆靶及锆钇合金靶为靶材，设置所述锆靶及锆钇合金靶的电流均为20～100A，以氩气为工作气体，其流量为150～300sccm，对基体施加-100～-300V的偏压，溅射温度为150～300，溅射时间为5～15min。
9.如权利要求7所述的被覆件的制造方法，其特征在于：磁控溅射该纳米复合层的步骤以如下方式进行：以锆靶和锆钇合金靶为交替开启的靶材，以氮气为反应性气体，其流量为10～200sccm，溅射时间为60～120min。
10.如权利要求7或9所述的被覆件的制造方法，其特征在于：该锆钇合金靶中Zr的质量百分含量为70～90％。
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