CN110205178A - 金属钛改性二硒化钨纳米润滑材料、其制备方法及其用途 - Google Patents
金属钛改性二硒化钨纳米润滑材料、其制备方法及其用途 Download PDFInfo
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Abstract
本发明涉及金属钛改性二硒化钨纳米润滑材料、其制备方法及其用途,该材料是尺寸为100~500nm的纳米片,包括金属钛或钛的硒化物和二硒化钨,金属钛的掺杂含量为1‑8%。制备方法是将钨粉、钛粉及硒粉混合均匀,乙醇作助剂,球磨干燥后,与卤化物在500‑800℃,隔绝空气的条件下保温2‑4h既得。使用是将包含该润滑材料的质量分数为75‑85%的固体润滑复合材料分散至15‑25%的改性粘结剂胶液中后喷涂在金属基材表面,然后低温固化、高温烘烤固化形成复合涂层,该涂层具有优异的摩擦性能,能起到防腐与降低磨损的能效。
Description
技术领域
本发明属于纳米润滑材料领域,具体地,是涉及一种金属钛改性二硒化钨纳米润滑材料、其制备方法及其用于铜基纳米复合涂料的涂覆工艺。
背景技术
过渡金属硫硒化物因其独特的层状结构和优异的理化性能而被广泛应用于摩擦与润滑领域。自20世纪50年代起,二硫化钼作为固体润滑、润滑涂层、润滑油及润滑脂添加剂等应用于机械加工于极端工科下的应用。寻找和发展高性能的纳米润滑材料是当前摩擦学领域发展的重点,也是满足实际生产生活的需求。
目前,已有人研究将过渡金属硫硒化物润滑材料用于基材的涂覆或薄膜主要成分。本申请的发明人在之前的国家发明专利CN 104087033 B和CN 104087154 B提供硫化钼和硫化钨应用于自润滑涂层的涂覆工艺,而涂层的减摩抗磨性能一直是润滑材料研发关注的热点,也是符合绿色环保的发展理念。因此,本发明提供了一种金属钛改性二硒化钨纳米润滑材料的制备方法,并将其应用于润滑涂层的涂覆。
发明内容
针对现有技术的不足,本发明的目的之一在于提供一种金属钛改性二硒化钨纳米润滑材料,具有优异的摩擦学性能,在常温和较高温度下,具有更低的摩擦系数和更低的磨损率。
本发明的另一个目的在于提供一种金属钛改性二硒化钨纳米润滑材料的制备方法,工艺简单及产率高。
本发明的再一个目的在于提供一种金属钛改性二硒化钨纳米润滑材料的应用于铜基纳米复合涂料的合成及涂覆。
上述目的是通过如下技术方案实现的:
一种金属钛改性二硒化钨纳米润滑材料,是尺寸为100~500nm的纳米片,成分包括金属钛或钛的硒化物和二硒化钨,金属钛或二硒化钛的掺杂含量为1-8%。
金属钛改性二硒化钨纳米润滑材料的制备方法,步骤如下:
(1)将钨粉、钛粉及硒粉按比例混合均匀后,乙醇作助剂,球磨1-3h干燥得前驱体粉末;
W:Se物质的量之比为1:2.2-2.4,钛粉的添加量是钨粉和硒粉总质量的1-8%。
高能球磨的时候加入液体作为球磨的介质,本发明选择乙醇作助剂,高能球磨会使混合稳定有一定升高,部分原料会发生初步的反应。
(2)前驱体粉末与卤化物混合均匀转入固相反应釜中,在500-800℃,隔绝空气的条件下保温2-4h,冷却至室温后经干燥洗涤得金属钛改性二硒化钨纳米润滑材料。
所述卤化物为氯化钠、氯化钾及氯化镁的混合物,其中氯化钾为8-16%、氯化镁为2-6%,余量为氯化钠。
在反应过程中适量的钛会转化为二硒化钛,而添加过多的钛复合材料中就会出现单质钛,因此在该复合材料中,成分包括金属钛或二硒化钛和二硒化钨。
基于金属钛改性二硒化钨纳米材料的铜基纳米复合涂料,是由质量分数为75-85%的固体润滑复合材料分散至15-25%的改性粘结剂胶液中得到(所述的铜基纳米复合材料是以铜粉为主,本发明制备的金属钛改性二硒化钨纳米材料作为增强相)。
所述固体润滑复合材料包括金属钛改性二硒化钨纳米颗粒、超细石墨、二硫化钼和铜粉,质量分数分别为15-25%,35%-50%,10%-20%,30%-40%;超细石墨的颗粒尺寸为200-300目,二硫化钼的颗粒尺寸为150-250目,铜粉的颗粒尺寸为300-500目;
所述改性粘结剂胶液为无机纳米颗粒掺杂有机粘结剂胶液,无机纳米颗粒为Al2O3、SiO2或Ag,有机粘接剂为聚酰亚胺或环氧粘接剂胶液,具体地将质量分数为1-5%无机纳米颗粒超声分散至有机粘接剂中形成均一的改性粘接剂胶液。
基于金属钛改性二硒化钨纳米材料的铜基纳米复合涂料的涂覆工艺,是以如45钢的金属基材,经表面除锈、脱脂、喷砂工艺处理后,将上述铜基纳米复合涂料喷涂在基材表面,200~350℃低温固化1.5~2.5h,再经950~1250℃高温烘烤固化1~3h,形成膜厚为10~15μm复合涂层。
本发明具有以下优点:
1、生产工艺简单易控,产物差率高,适合大规模的工业生产。
2、所得复合涂层具有优异的摩擦学性能,在常温与较高温度下,摩擦系数降低明显。与45钢相比,采用金属钛改性后,其摩擦系数降低50%,磨损率降低4倍,因此,能起到防腐与降低磨损的能效,延长其使用寿命。
附图说明
图1为本发明实施例1制得Ti@WSe2复合纳米材料的XRD谱图。表明主要的衍射峰与WSe2的标准衍射图谱(PDF:NO.038-1388)一致,在24.1°处有一微弱的峰为TiSe2的特征峰,说明金属Ti成功掺杂到WSe2中。
图2为本发明实施例1制得Ti@WSe2复合纳米材料的透射电镜(TEM)。可知TiSe2颗粒生长在WSe2纳米片表面,WSe2纳米片的尺寸为500nm左右,进一步证实复合材料的形成。
具体实施方式
以下通过具体实施方式进一步描述本发明,由技术常识可知,本发明也可通过其它的不脱离本发明技术特征的方案来描述,因此所有在本发明范围内或等同本发明范围内的改变均被本发明包含。
本发明所有试剂均为商业产品,不需要再制备。
实施例1:
(1)金属钛改性二硒化钨纳米润滑材料的制备方法
1.83g钨粉与1.74g硒粉(W:Se物质的量之比为1:2.2)超声混合均匀,再加入0.035g钛粉(1%),乙醇作助剂(20mL),球磨4h后干燥得前驱体粉末;
再将2g混合卤化物与上述前驱体粉末混合均匀,其中氯化钾为8%、氯化镁为2%,氯化钠为90%。然后转入到固相反应釜中,氮气作保护气,500℃条件下保温2h,自然冷却至室温得金属钛改性二硒化钨纳米润滑材料,产率为95%。
(2)金属钛改性二硒化钨纳米材料用作铜基纳米复合涂料用途
将制备得到的金属钛改性二硒化钨纳米颗粒与超细石墨、二硫化钼和铜粉按质量分数15%,35%,10%,40%置入混料机中混合12h得到复合固体润滑剂;将Al2O3纳米颗粒加入聚酰亚胺胶液中,Al2O3添加量为1%,超声分散2.5h后得改性粘接剂;再将质量分数85%的复合固体润滑剂分散于15%的改性聚酰亚胺胶液中得到改性铜基纳米复合涂料。
以45钢为基材,表面经除锈、脱脂、喷砂工艺处理后,将上述铜基纳米复合涂料喷涂在基材表面,200℃低温固化1.5h,再经950℃高温烘烤固化1h,形成膜厚为10μm复合涂层。
实施例2:
(1)金属钛改性二硒化钨纳米润滑材料的制备方法
1.83g钨粉与1.90g硒粉(W:Se物质的量之比为1:2.4)超声混合均匀,再加入0.28g钛粉(8%),乙醇作助剂(10mL),球磨6h后干燥得前驱体粉末;
再将4g混合卤化物与上述前驱体粉末混合均匀,其中氯化钾为12%、氯化镁为4%,氯化钠为84%。然后转入到固相反应釜中,氮气作保护气,800℃条件下保温4h,自然冷却至室温得金属钛改性二硒化钨纳米润滑材料,产率为92%。
(2)金属钛改性二硒化钨纳米材料用作铜基纳米复合涂料用途
将(1)所得金属钛改性二硒化钨纳米颗粒与超细石墨、二硫化钼和铜粉按质量分数25%,35%,10%,30%置入混料机中混合12h得到复合固体润滑剂;将Al2O3纳米颗粒加入聚酰亚胺胶液中,Al2O3添加量为5%,超声分散2h后得改性粘接剂;再将质量分数75%的复合固体润滑剂分散于25%的改性聚酰亚胺胶液中得到改性铜基纳米复合涂料。
以45钢为基材,表面经除锈、脱脂、喷砂工艺处理后,将上述铜基纳米复合涂料喷涂在基材表面,350℃低温固化2.5h,再经1250℃高温烘烤固化3h,形成膜厚为15μm复合涂层。
实施例3:
(1)金属钛改性二硒化钨纳米润滑材料的制备方法
1.83g钨粉与1.74g硒粉(W:Se物质的量之比为1:2.2)超声混合均匀,再加入0.175g钛粉(5%),乙醇作助剂(20mL),球磨4h后干燥得前驱体粉末;
再将6g混合卤化物与上述前驱体粉末混合均匀,其中氯化钾为16%、氯化镁为6%,氯化钠为78%。然后转入到固相反应釜中,氮气作保护气,650℃条件下保温3h,自然冷却至室温得金属钛改性二硒化钨纳米润滑材料,产率为94%。
(2)金属钛改性二硒化钨纳米材料用作铜基纳米复合涂料用途
将(1)所得金属钛改性二硒化钨纳米颗粒与超细石墨、二硫化钼和铜粉按各组分的质量分数20%,40%,20%,20%置入混料机中混合12h得到复合固体润滑剂;将Al2O3纳米颗粒加入聚酰亚胺胶液中,Al2O3添加量为2%,超声分散2.5h后得改性粘接剂;再将质量分数85%的复合固体润滑剂分散于15%的改性聚酰亚胺胶液中得到改性铜基纳米复合涂料。
以45钢为基材,表面经除锈、脱脂、喷砂工艺处理后,将上述铜基纳米复合涂料喷涂在基材表面,250℃低温固化2h,再经1000℃高温烘烤固化1h,形成膜厚为12μm复合涂层。
实施例4
保持实施例1相同的条件下,以SiO2纳米颗粒改性环氧粘接剂为粘接材料,环氧牌号为SM6101,SiO2纳米颗粒添加量取1%、2%、5%,得改性粘接胶液,并应用于涂覆工艺,得到类似的润滑涂层,且具有良好的摩擦学性能。
复合涂料制备的过程中,以SiO2纳米颗粒改性环氧粘接剂为粘接材料,环氧牌号为SM6101是商品级的环氧粘接剂,其他条件均不变。
摩擦实验采用美国CETR公司的UMT-2型多用途摩擦磨损测试仪测定上述复合涂层。摩擦实验过程采用球盘式摩擦的方式,上试样采用直径为10mm的440C不锈钢球,材料硬度HRC 62;下试样为涂覆本发明涂料的45#钢圆盘摩擦实验条件:载荷为10–30N,转速100rpm,实验时间1h,结果见表1。
本申请所有实施例制备的润滑涂层均能起到减摩抗磨的作用,常温与高温的摩擦学性能明显改善,与45刚相比,涂覆了铜基纳米复合涂层,其摩擦系数降低50%,磨损率降低4倍,能有效增强及材料的强度,延长其使用寿命。
表1对比实施例摩擦学性能
Claims (6)
1.一种金属钛改性二硒化钨纳米润滑材料,其特征在于,是尺寸为100~500nm的纳米片,组分成分包括金属钛或钛的硒化物和二硒化钨,金属钛的掺杂含量为1-8%。
2.如权利要求1所述的金属钛改性二硒化钨纳米润滑材料的制备方法,其特征在于,步骤如下:
(1)将钨粉、钛粉及硒粉按比例混合均匀后,乙醇作助剂,球磨1-3h干燥得前驱体粉末;
(2)前驱体粉末与卤化物,混合均匀转入固相反应釜中,在500-800℃,隔绝空气的条件下保温2-4h,冷却至室温后经干燥洗涤得金属钛改性二硒化钨纳米润滑材料。
3.如权利要求2所述的金属钛改性二硒化钨纳米润滑材料的制备方法,其特征在于,步骤(2)中所述卤化物为氯化钠、氯化钾及氯化镁的混合物,其中氯化钾为8-16%、氯化镁为2-6%,余量为氯化钠。
4.如权利要求2所述的金属钛改性二硒化钨纳米润滑材料的制备方法,其特征在于,步骤(1)中W:Se物质的量之比为1:2.2-2.4,钛粉的添加量是钨粉和硒粉总质量的1-8%。
5.基于权利要求1所述的金属钛改性二硒化钨纳米润滑材料的铜基纳米复合涂料,其特征在于,是由质量分数为75-85%的固体润滑复合材料分散至15-25%的改性粘结剂胶液中得到;
所述固体润滑复合材料包括金属钛改性二硒化钨纳米颗粒、超细石墨、二硫化钼和铜粉,质量分数分别为15-25%,35%-50%,10%-20%,30%-40%;超细石墨的颗粒尺寸为200-300目,二硫化钼的颗粒尺寸为150-250目,铜粉的颗粒尺寸为300-500目;
所述改性粘结剂胶液为无机纳米颗粒掺杂有机粘结剂胶液,无机纳米颗粒为Al2O3、SiO2或Ag,有机粘接剂为聚酰亚胺或环氧粘接剂胶液,具体地将质量分数为1-5%无机纳米颗粒超声分散至有机粘接剂中形成均一的改性粘接剂胶液。
6.如权利要求5所述的铜基纳米复合涂料的使用方法,是将金属基材,经表面除锈、脱脂、喷砂工艺处理后,将铜基纳米复合涂料喷涂在金属基材表面,然后200~350℃低温固化1.5~2.5h,再经950~1250℃高温烘烤固化1~3h,形成膜厚为10~15μm复合涂层。
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