CN105524547B - 一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层及其制备方法 - Google Patents

一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层及其制备方法 Download PDF

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CN105524547B
CN105524547B CN201510988493.9A CN201510988493A CN105524547B CN 105524547 B CN105524547 B CN 105524547B CN 201510988493 A CN201510988493 A CN 201510988493A CN 105524547 B CN105524547 B CN 105524547B
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王金清
叶相元
杨生荣
方治文
刘超
张敏
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

本发明一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层及其制备方法,包括金属基底和涂覆于金属基底上的复合耐磨涂层,金属基底为通过机械加工的铁基材料,复合耐磨涂层组成成分按重量百分含量包括:聚酰亚胺99%~99.9%;固体润滑剂0.1%~1%;固体润滑剂是氟化石墨烯片;制备方法包括以下步骤:(ⅰ)复合耐磨涂料的制备;(ⅱ)复合耐磨涂层的涂覆;(ⅲ)复合耐磨涂层的烧结。本发明复合耐磨涂层以聚酰亚胺为基体,添加氟化石墨烯制成自润滑合耐磨涂层后,在三种工况条件下其抗磨损性能远优于纯的聚酰亚胺涂层;所使用固体润滑剂氟化石墨烯片的添加量很少,有效节约了资源,避免团聚现象的发生;制备工艺简单,经济实用,适用于工业化推广。

Description

一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂 层及其制备方法
技术领域
本发明属于一种复合涂层及其制备方法,具体涉及一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层及其制备方法。
背景技术
作为一种超级工程材料,聚酰亚胺以其优异的机械性能、耐高温、耐化学腐蚀以及耐磨损等性能而被广泛的应用于航空工业和微电子等领域。近年来,为了进一步提升聚酰亚胺的耐磨损性能以满足市场的更高要求,各种固体润滑剂被添加到聚酰亚胺基体中以获得更加优异的减摩抗磨性能。如日本道康宁亚洲株式会社将聚四氟乙烯、二硫化钼、石墨和碳化硅等材料添加到热固性聚酰亚胺基体中,制备得到了用于滑动件的涂料复合物。浙江长盛滑动轴承有限公司也通过使用添加剂成功制得了热固性聚酰亚胺耐磨自润滑斜盘。
现有的术方案虽然有效地增强了聚酰亚胺的耐磨损性能,然而一个不容忽视的问题就是所添加的固体润滑填料量较大,大量的固体润滑填料的加入不可避免的会发生团聚,从而影响基体材料的力学性能,限制了材料的使用领域,同时也造成了大量的资源浪费。
氟化石墨烯作为石墨烯的新型衍生物,既保持了石墨烯高强度的性能,又因氟原子的引入带来了表面能降低、疏水性增强及带隙展宽等新颖的界面和物理化学性能。同时,氟化石墨烯耐高温、化学性质稳定,表现出类似聚四氟乙烯的性质,被称之为“二维特氟龙”。氟化石墨烯这些独特的性能使其在界面、新型纳米电子器件、润滑材料等领域具有广泛的应用前景。
发明内容
本发明是为了克服现有技术中存在的缺点而提出的,其目的是提供一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层及其制备方法。
本发明的技术方案是:
一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层,包括金属基底和涂覆于金属基底上的复合耐磨涂层,所述金属基底为通过机械加工的铁基材料,所述复合耐磨涂层组成成分按重量百分含量包括:
聚酰亚胺99%~99.9%;
固体润滑剂0.1%~1%;
所述固体润滑剂是氟化石墨烯片。
所述氟化石墨烯片的厚度为纳米级。
一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层的制备方法,包括以下步骤:
(ⅰ)复合耐磨涂料的制备
在低温下,将一定量的单体4,4’-二氨基二苯醚加入非质子极性溶剂中,待单体4,4’-二氨基二苯醚完全溶解后,加入氟化石墨烯片;再加入与单体4,4’-二氨基二苯醚等摩尔量的单体均苯四甲酸酐,搅拌,即得复合耐磨涂料;
(ⅱ)复合耐磨涂层的涂覆
将步骤(ⅰ)所得复合耐磨涂料按0.1~0.2mL/cm2的配比于室温环境下在金属基底上进行刷涂,涂层表面均匀无气泡;
(ⅲ)复合耐磨涂层的烧结
首先将步骤(ⅱ)所得复合耐磨涂层放入真空干燥箱内,于60℃~80℃下干燥6h;然后再放入烘箱中,于80℃下烧结2h;升温至135℃再烧结2h;再升温至300℃烧结2h,即得聚酰亚胺/氟化石墨烯复合耐磨涂层。
所述低温为-10℃~25℃。
所述非质子极性溶剂为N,N-二甲基乙酰胺。
所述步骤(ⅰ)加入氟化石墨烯片的质量为单体4,4’-二氨基二苯醚和单体均苯四甲酸酐质量之和的0.1%~1%。
所述步骤(ⅰ)非质子极性溶剂与单体4,4’-二氨基二苯醚以及单体均苯四甲酸酐的摩尔比为32:1:1。
所述步骤(ⅰ)搅拌时间为4~10h
所述步骤(ⅲ)中烧结时由80℃升温至135℃历时1h,由135℃升温至300℃历时1~2h。
本发明的有益效果是:
本发明复合耐磨涂层以聚酰亚胺为基体,添加氟化石墨烯制成自润滑复合耐磨涂层后,在三种工况条件下其抗磨损性能远优于纯的聚酰亚胺涂层;所使用固体润滑剂氟化石墨烯片的添加量很少,有效节约了资源,避免团聚现象的发生;制备工艺简单,经济实用,适用于工业化推广。
附图说明
图1是本发明复合耐磨涂层照片;
图2复合耐磨涂层干摩擦条件下的磨损表面照片;
图3复合耐磨涂层在水润滑条件下的磨损表面照片;
图4复合耐磨涂层在油润滑条件下的磨损表面照片。
其中:a为纯聚酰亚胺涂层,b~e依次氟化石墨烯含量为0.25%、0.5%、0.75%和1%的聚酰亚胺复合涂层。
具体实施方式
下面结合实施例对本发明聚酰亚胺/氟化石墨烯复合耐磨涂层及其制备方法进行详细说明:
实施例1
一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层的制备方法,包括以下步骤:
(ⅰ)复合耐磨涂料的制备
在0~5℃下,将一定量的单体4,4’-二氨基二苯醚加入N,N-二甲基乙酰胺中,待单体4,4’-二氨基二苯醚完全溶解后,加入氟化石墨烯片;再加入与单体4,4’-二氨基二苯醚等摩尔量的单体均苯四甲酸酐,搅拌,即得复合耐磨涂料,加入氟化石墨烯片的质量为单体4,4’-二氨基二苯醚和单体均苯四甲酸酐质量之和的0.25%,N,N-二甲基乙酰胺与单体4,4’-二氨基二苯醚以及单体均苯四甲酸酐的摩尔比为32:1:1;
(ⅱ)复合耐磨涂层的涂覆
将步骤(ⅰ)所得复合耐磨涂料按0.15mL/cm2的配比于室温环境下在金属基底上进行刷涂,涂层表面均匀无气泡;
(ⅲ)复合耐磨涂层的烧结
首先将步骤(ⅱ)所得复合耐磨涂层放入真空干燥箱内,于80℃下干燥6h;然后再放入烘箱中,于80℃下烧结2h;历时1h升温至135℃,于135℃下再烧结2h;再历时1h升温至300℃,于300℃下烧结2h,即得聚酰亚胺/氟化石墨烯复合耐磨涂层,如图1中b所示。
实施例2
在0~5℃下,将一定量的单体4,4’-二氨基二苯醚加入N,N-二甲基乙酰胺中,待单体4,4’-二氨基二苯醚完全溶解后,加入氟化石墨烯片;再加入与单体4,4’-二氨基二苯醚等摩尔量的单体均苯四甲酸酐,搅拌,即得复合耐磨涂料,加入氟化石墨烯片的质量为单体4,4’-二氨基二苯醚和单体均苯四甲酸酐质量之和的0.5%,N,N-二甲基乙酰胺与单体4,4’-二氨基二苯醚以及单体均苯四甲酸酐的摩尔比为32:1:1;
(ⅱ)复合耐磨涂层的涂覆
将步骤(ⅰ)所得复合耐磨涂料按0.15mL/cm2的配比于室温环境下在金属基底上进行刷涂,涂层表面均匀无气泡;
(ⅲ)复合耐磨涂层的烧结
首先将步骤(ⅱ)所得复合耐磨涂层放入真空干燥箱内,于80℃下干燥6h;然后再放入烘箱中,于80℃下烧结2h;历时1h升温至135℃,于135℃下再烧结2h;再历时1h升温至300℃,于300℃下烧结2h,即得聚酰亚胺/氟化石墨烯复合耐磨涂层,如图1中c所示。
实施例3
在0~5℃下,将一定量的单体4,4’-二氨基二苯醚加入N,N-二甲基乙酰胺中,待单体4,4’-二氨基二苯醚完全溶解后,加入氟化石墨烯片;再加入与单体4,4’-二氨基二苯醚等摩尔量的单体均苯四甲酸酐,搅拌,即得复合耐磨涂料,加入氟化石墨烯片的质量为单体4,4’-二氨基二苯醚和单体均苯四甲酸酐质量之和的0.75%,N,N-二甲基乙酰胺与单体4,4’-二氨基二苯醚以及单体均苯四甲酸酐的摩尔比为32:1:1;
(ⅱ)复合耐磨涂层的涂覆
将步骤(ⅰ)所得复合耐磨涂料按0.15mL/cm2的配比于室温环境下在金属基底上进行刷涂,涂层表面均匀无气泡;
(ⅲ)复合耐磨涂层的烧结
首先将步骤(ⅱ)所得复合耐磨涂层放入真空干燥箱内,于80℃下干燥6h;然后再放入烘箱中,于80℃下烧结2h;历时1h升温至135℃,于135℃下再烧结2h;再历时1h升温至300℃,于300℃下烧结2h,即得聚酰亚胺/氟化石墨烯复合耐磨涂层,如图1中d所示。
实施例4
在0~5℃下,将一定量的单体4,4’-二氨基二苯醚加入N,N-二甲基乙酰胺中,待单体4,4’-二氨基二苯醚完全溶解后,加入氟化石墨烯片;再加入与单体4,4’-二氨基二苯醚等摩尔量的单体均苯四甲酸酐,搅拌,即得复合耐磨涂料,加入氟化石墨烯片的质量为单体4,4’-二氨基二苯醚和单体均苯四甲酸酐质量之和的1%,N,N-二甲基乙酰胺与单体4,4’-二氨基二苯醚以及单体均苯四甲酸酐的摩尔比为32:1:1;
(ⅱ)复合耐磨涂层的涂覆
将步骤(ⅰ)所得复合耐磨涂料按0.15mL/cm2的配比于室温环境下在金属基底上进行刷涂,涂层表面均匀无气泡;
(ⅲ)复合耐磨涂层的烧结
首先将步骤(ⅱ)所得复合耐磨涂层放入真空干燥箱内,于80℃下干燥6h;然后再放入烘箱中,于80℃下烧结2h;历时1h升温至135℃,于135℃下再烧结2h;再历时1h升温至300℃,于300℃下烧结2h,即得聚酰亚胺/氟化石墨烯复合耐磨涂层,如图1中e所示。
摩擦学测试实验方式及测试条件
(一)干摩擦实验
实验设备:UMT-2MT摩擦磨损试验机(USA,CETR)
测试条件:干摩擦
对摩钢球:级别G10,直径6mm,技术依据GB308-2002
载荷:20N
频率:3Hz
时间:30min
干摩擦实验的结果如图2所示,图中(a)为纯聚酰亚胺涂层,(b-e)依次为氟化石墨烯含量为0.25%(实施例1)、0.5%(实施例2)、0.75%(实施例3)和1%(实施例4)的聚酰亚胺复合涂层。
(二)水润滑摩擦实验
实验设备:UMT-2MT摩擦磨损试验机(USA,CETR)
测试条件:浸水润滑,超纯水
对磨钢球:级别G10,直径6mm,技术依据GB308-2002
载荷:20N
频率:3Hz
时间:30min
水润滑摩擦实验的结果如图3所示,图中(a)为纯聚酰亚胺涂层,(b-e)依次为氟化石墨烯含量为0.25%(实施例1)、0.5%(实施例2)、0.75%(实施例3)和1%(实施例4)的聚酰亚胺复合涂层。
(三)油润滑摩擦实验
实验设备:UMT-2MT摩擦磨损试验机(USA,CETR)
测试条件:浸油润滑,液体石蜡油
对磨钢球:级别G10,直径6mm,技术依据GB308-2002
载荷:20N
频率:3Hz
时间:30min
油润滑摩擦实验的结果如图4所示,图中(a)为纯聚酰亚胺涂层,(b-e)依次为氟化石墨烯含量为0.25%(实施例1)、0.5%(实施例2)、0.75%(实施例3)和1%(实施例4)的聚酰亚胺复合涂层。
摩擦学测试实验结果
本发明以聚酰亚胺为基体,以二维纳米材料氟化石墨烯片为填料制成自润滑复合耐磨涂层材料。该涂层在三种常见工况条件(干摩擦、水润滑以及油润滑)下的摩擦学测试表明:与纯聚酰亚胺涂层相比较,氟化石墨烯添加量为0.5%的聚酰亚胺复合耐磨涂层表现出了最佳的抗磨损性能。详细结果为:在干摩擦条件下,氟化石墨烯添加量为0.5%的聚酰亚胺复合耐磨涂层的磨损率(0.87×10-5mm3/N·m)较纯聚酰亚胺(1.39×10-5mm3/N·m)降低了37.4%;在水润滑条件下,氟化石墨烯添加量为0.5%的聚酰亚胺复合耐磨涂层的磨损率(1.51×10-4mm3/N·m)较纯聚酰亚胺(2.41×10-4mm3/N·m)降低了37.3%;在油润滑条件下,氟化石墨烯添加量为0.5%的聚酰亚胺复合耐磨涂层的磨损率(1.42×10-6mm3/N·m)较纯聚酰亚胺(3.65×10-6mm3/N·m)降低了61.1%。

Claims (8)

1.一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层,包括金属基底和涂覆于金属基底上的复合耐磨涂层,所述金属基底为通过机械加工的铁基材料,其特征在于:所述复合耐磨涂层组成成分按重量百分含量包括:
聚酰亚胺99%~99.9%;
固体润滑剂0.1%~1%;
所述固体润滑剂是氟化石墨烯片;
所述具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层的制备方法,包括以下步骤:
(ⅰ)复合耐磨涂料的制备
在低温下,将一定量的单体4,4’-二氨基二苯醚加入非质子极性溶剂中,待单体4,4’-二氨基二苯醚完全溶解后,加入氟化石墨烯片;再加入与单体4,4’-二氨基二苯醚等摩尔量的单体均苯四甲酸酐,搅拌,即得复合耐磨涂料;
(ⅱ)复合耐磨涂层的涂覆
将步骤(ⅰ)所得复合耐磨涂料按0.1~0.2 mL/cm2的配比于室温环境下在金属基底上进行刷涂,涂层表面均匀无气泡;
(ⅲ)复合耐磨涂层的烧结
首先将步骤(ⅱ)所得复合耐磨涂层放入真空干燥箱内,于60℃~80℃下干燥6h;然后再放入烘箱中,于80℃下烧结2h;升温至135℃再烧结2h;再升温至300℃烧结2h,即得聚酰亚胺/氟化石墨烯复合耐磨涂层。
2.根据权利要求1所述的一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层,其特征在于:所述氟化石墨烯片的厚度为纳米级。
3.根据权利要求1所述的一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层,其特征在于:所述低温为-10℃~ 25℃。
4.根据权利要求1所述的一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层,其特征在于:所述非质子极性溶剂为N,N-二甲基乙酰胺。
5.根据权利要求1所述的一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层,其特征在于:所述步骤(ⅰ)加入氟化石墨烯片的质量为单体4,4’-二氨基二苯醚和单体均苯四甲酸酐质量之和的0.1%~1%。
6.根据权利要求1所述的一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层,其特征在于:所述步骤(ⅰ)非质子极性溶剂与单体4,4’-二氨基二苯醚以及单体均苯四甲酸酐的摩尔比为32:1:1。
7.根据权利要求1所述的一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层,其特征在于:所述步骤(ⅰ)搅拌时间为4~10h。
8.根据权利要求1所述的一种具有优异抗磨性能的聚酰亚胺/氟化石墨烯复合耐磨涂层,其特征在于:所述步骤(ⅲ)中烧结时由80℃升温至135℃历时1h,由135℃升温至300℃历时1~2h。
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