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中国 发明授权 有效

一种低摩擦系数MoS 【EN】A kind of low-friction coefficient MoS

申请(专利)号:CN201710972599.9国省代码:吉林 22
申请(专利权)人:【中文】吉林大学【EN】Jilin University
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摘要:
【中文】本发明公开了一种低摩擦系数MoS2基金属复合固体润滑膜,由下述原子百分比的成分组成:Cu 2at%~38at%,Al 0~12at%,MoS2余量;制备方法包括以下步骤:在磁控溅射镀膜前,在基底表面预沉积Ti或Al预结合层;金属靶材和MoS2靶材进行磁控溅射,得到低摩擦系数MoS2基金属复合固体润滑膜。本发明改良了二硫化钼固体润滑膜与金属添加剂结合的成分体系,解决了二硫化钼基固体润滑膜在使用中耐磨性较差及使用环境苛刻的问题,提供了二硫化钼基薄膜多场合使用的可能性,并延长了薄膜的使用寿命。 【EN】Paragraph:The invention discloses a kind of low-friction coefficient MoS2Base Metal composite solid lubricant film, by following atomic percents at being grouped as: Cu 2at%~38at%, Al 0~12at%, MoS2Surplus;Preparation method is the following steps are included: before magnetron sputtering plating, in the pre- binder course of substrate surface pre-deposition Ti or Al;Metal targets and MoS2Target carries out magnetron sputtering, obtains low-friction coefficient MoS2Base Metal composite solid lubricant film.The present invention improves component system of the molybdenum disulfide solid lubricant film in conjunction with metallic addition, solve the problems, such as that molybdenum-disulfide radical solid lubricant film wearability in use is poor and use environment is harsh, a possibility that more occasions of molybdenum disulfide base film use is provided, and extends the service life of film.Image:201710972599.GIF

主权项:
【中文】1.一种低摩擦系数MoS基金属复合固体润滑膜,其特征在于,由下述原子百分比的成分组成:Cu 25at%~30at%,Al 5at%~10at%,MoS余量;所述低摩擦系数MoS基金属复合固体润滑膜的制备方法,包括以下步骤: 步骤A1,预结合层溅射:在磁控溅射镀膜前,采用射频电源,在预溅射功率为120W的条件下在基底表面预沉积Ti或Al结合层10min;所述预结合层的厚度为28nm~35nm; 步骤A2,磁控溅射镀膜:本底真空度为5×10Pa~5×10Pa,保护气体采用氩气,工作气压为1Pa,基底温度为常温,衬底旋转速度为3r/min~5r/min,靶基距为15cm~17cm;设置金属靶材的溅射条件:5W~60W直流溅射靶电源;设置MoS靶材的溅射条件:100W射频溅射靶电源;溅射时间为2.5h~3.5h,得到所述低摩擦系数MoS基金属复合固体润滑膜;还包括对制得的所述低摩擦系数MoS基金属复合固体润滑膜在600℃ ~800℃的温度下进行退火热处理的步骤;所述低摩擦系数MoS2基金属复合固体润滑膜的厚度为0.3μm~3μm。 【EN】1. a kind of low-friction coefficient MoSBase Metal composite solid lubricant film, which is characterized in that by the ingredient of following atomic percents Composition: Cu 25at% ~ 30at%, Al 5at% ~ 10at%, MoSSurplus;The low-friction coefficient MoSBase Metal complex solid profit The preparation method of synovial membrane, comprising the following steps: Step A1, pre- binder course sputtering: before magnetron sputtering plating, using radio-frequency power supply, in the item that pre-sputtering power is 120W In substrate surface pre-deposition Ti or Al binder course 10min under part;The pre- binder course with a thickness of 28nm ~ 35nm; Step A2, magnetron sputtering plating: background vacuum is 5 × 10Pa~5×10Pa, protective gas use argon gas, work gas Pressure is 1Pa, and base reservoir temperature is room temperature, and substrate rotation speed is 3r/min ~ 5r/min, and target-substrate distance is 15cm ~ 17cm;Metal is set The sputtering condition of target: 5W ~ 60W d.c. sputtering target power supply;MoS is setThe sputtering condition of target: 100W radio-frequency sputtering target electricity Source;Sputtering time is 2.5h ~ 3.5h, obtains the low-friction coefficient MoSBase Metal composite solid lubricant film;It further include to system The low-friction coefficient MoS obtainedBase Metal composite solid lubricant film 600 DEG C ~ 800 DEG C at a temperature of anneal at heat The step of reason;The low-friction coefficient MoS2 Base Metal composite solid lubricant film with a thickness of 0.3 μm ~ 3 μm.


说明书

【中文】

一种低摩擦系数MoS2基金属复合固体润滑膜

技术领域

本发明涉及对金属的涂覆领域,具体涉及一种低摩擦系数MoS2基金属复合固体润滑膜。

背景技术

为防止与保护摩擦表面在作相对运动时免于损坏及减少其摩擦和磨损而在表面上使用的粉末状或薄膜状固体称为固体润滑剂。固体润滑膜用于不能使用润滑油脂的地方、环境恶劣及无需维护的场合下,常见应用于空间技术、电气工程及汽车工程等领域。固体润滑剂的种类按原料可分为硫化物、石墨、软金属、金属氧化物、金属氟化物等几类。

二硫化钼具有良好的各向异性与较低的摩擦因数,且S对金属的粘附力很强,使二硫化钼能很好地附着在金属表面并始终发挥润滑功能,是一种性能良好的金属硫化物固体润滑剂。但大气环境下的二硫化钼在400℃左右时就开始逐渐氧化,其摩擦系数逐渐升高,而且二硫化钼的耐潮湿氧化性差,随大气中湿度的增加其摩擦系数也增高。

为提高二硫化钼的耐氧化和耐湿性,扩大其使用范围,研究人员通过添加单质金属、树脂材料、金属氧化物、金属硫化物或金属氟化物等与二硫化钼形成二组份或多组份固体润滑材料以改善固体润滑薄膜的润滑、耐磨损以及抗湿抗氧化性能。

固体润滑膜通常采用的制备方法以及存在的问题有:(1)浸涂、喷涂、刷涂,但这些涂覆方式形成的润滑膜的结合力不好、外观性差、耐特种介质差、膜的均匀性难以保证,如中国专利CN03127698.9公开的一种应用于汽车花键轴类零件的固体润滑膜的制备方法;(2)电沉积法,这种方法多存在沉积速率过慢的问题;(3)离子镀法,但是离子镀会在工件表面沉积大量大颗粒导致膜层表面粗糙度较大,内部包裹的颗粒易导致膜层剥离失效,使得膜层的耐磨性能受到影响,不能完全满足长寿命固体润滑设备仪器的需要;(4)物理气相沉积法,该方法制得的润滑膜具有结合力好、膜层均匀、沉积速率适中、膜层致密等优点,但仍存在多次重复使用后固体润滑膜与基底之间内应力增加,固体润滑膜仍然较好的情况下基底已经氧化的问题,如中国专利94107544.3公开的一种共溅射固体润滑薄膜。

物理气相沉积法主要有真空蒸镀、溅射镀膜、电弧等离子体镀、离子镀膜,及分子束外延等方法。相对于真空蒸镀,磁控镀膜过程中靶材无相变,化学成分稳定,工艺重复性好,便于自动化生产,且所镀膜层沉积均匀,不会出现熔滴等缺陷现象,适合固体润滑薄膜等制备。

因此,针对上述问题,需要改良二硫化钼固体润滑膜与金属添加剂结合的成分体系,解决二硫化钼基固体润滑膜在使用中耐磨性较差及使用环境苛刻的问题,提供二硫化钼基薄膜多场合使用的可能性,并延长薄膜的使用寿命。

发明内容

本发明针对上述问题,提供一种低摩擦系数MoS2基金属复合固体润滑膜。

本发明解决上述问题所采用的技术方案是:一种低摩擦系数MoS2基金属复合固体润滑膜,由下述原子百分比的成分组成:Cu 2at%~38at%,Al 0~12at%, MoS2余量;低摩擦系数MoS2基金属复合固体润滑膜的制备方法,包括以下步骤:

步骤A1,预结合层溅射:在磁控溅射镀膜前,采用射频电源,在预溅射功率为120W的条件下在基底表面预沉积Ti或Al结合层10min;其中,在磁控溅射镀膜前预沉积结合层,能够减少薄膜与基体之间的内应力,同时在高温条件下形成氧化物保护膜,阻止基体进一步氧化。

步骤A2,磁控溅射镀膜:本底真空度为5×10-4Pa~5×10-5Pa,保护气体采用氩气,工作气压为1Pa,基底温度为常温,衬底旋转速度为3r/min~5r/min,靶基距为15cm~17cm;设置金属靶材的溅射条件:5W~60W直流溅射靶电源;设置MoS2靶材的溅射条件:100W射频溅射靶电源;溅射时间为2.5h~3.5h,得到低摩擦系数MoS2基金属复合固体润滑膜。

进一步的,低摩擦系数MoS2基金属复合固体润滑膜由下述原子百分比的成分组成:Cu 3at%~14at%,MoS2余量。

进一步的,低摩擦系数MoS2基金属复合固体润滑膜由下述原子百分比的成分组成:Cu 25at%~30at%,MoS2余量。

进一步的,低摩擦系数MoS2基金属复合固体润滑膜由下述原子百分比的成分组成:Cu 25at%~30at%,Al 5at%~10at%,MoS2余量。

进一步的,步骤A1中,基底为:单晶硅或不锈钢。

进一步的,步骤A1中,预结合层的厚度为28nm~35nm。

进一步的,步骤A1进行前还包括对基底进行表面抛光、丙酮和酒精超声清洗、烘干的步骤。

更进一步的,还包括对制得的所述低摩擦系数MoS2基金属复合固体润滑膜在600℃~800℃的温度下进行退火热处理的步骤。其中,选用Cu-Al共溅射靶材,通过退火热处理后获取固溶体相,从而强化薄膜整体机械性能,总体耐磨损性能和抗湿性能均有所提高;而且Cu和Al在退火处理和基材加热镀膜的过程中,出现明显的Al2O3氧化快于CuO,有助于提高薄膜的抗氧化性能。

进一步的,低摩擦系数MoS2基金属复合固体润滑膜的厚度为0.3μm~3μm。

本发明的优点是:

1.本发明选用常见软金属铜作为主要添加剂,以二硫化钼作为固体润滑膜的主要成分,或辅以第二种金属形成中间相固溶体,以提高固体润滑膜的综合性能,工艺加工成本低,并辅以热处理工艺,工艺流程不繁杂,所制备的薄膜综合性能达到要求,具有工业化生产的可行性,总体性价比较高;

2.本发明在磁控溅射镀膜前预沉积结合层,能够减少薄膜与基体之间的内应力,同时在高温条件下形成氧化物保护膜,阻止基体进一步氧化;

3.本发明选用的Cu-Al共溅射靶材,通过退火热处理后获取固溶体相,从而强化薄膜整体机械性能,总体耐磨损性能和抗湿性能均有所提高;而且Cu和Al在退火处理和基材加热镀膜的过程中,出现明显的Al2O3氧化快于CuO,有助于提高薄膜的抗氧化性能。

附图说明

构成本说明书的一部分、用于进一步理解本发明的附图示出了本发明的实施方案,并与说明书一起用来说明本发明的制备流程。在附图中:

图1是本发明实施例1制得的低摩擦系数MoS2基金属复合固体润滑膜的 SEM图;

图2是本发明实施例1制得的低摩擦系数MoS2基金属复合固体润滑膜截面的SEM图;

图3是本发明实施例1制得的低摩擦系数MoS2基金属复合固体润滑膜经磨损后的磨损形貌;

图4是本发明实施例1制得的低摩擦系数MoS2基金属复合固体润滑膜经磨损后的磨痕截面轮廓;

图5是本发明实施例1~4制得的低摩擦系数MoS2基金属复合固体润滑膜的XRD图;

图6是本发明实施例9制得的低摩擦系数MoS2基金属复合固体润滑膜在不同基底温度薄膜的XRD图;

图7是本发明实施例9制得的低摩擦系数MoS2基金属复合固体润滑膜在基底加热至200℃时的SEM图;

图8是本发明实施例9制得的低摩擦系数MoS2基金属复合固体润滑膜在基底加热至200℃时的截面形貌图;

图9是本发明实施例10制得的低摩擦系数MoS2基金属复合固体润滑膜的 SEM图;

图10是本发明实施例10制得的低摩擦系数MoS2基金属复合固体润滑膜截面的SEM图;

图11是本发明实施例10制得的低摩擦系数MoS2基金属复合固体润滑膜经磨损后的磨损形貌;

图12是本发明实施例10制得的低摩擦系数MoS2基金属复合固体润滑膜经磨损后的磨痕截面轮廓;

图13是本发明实施例10制得的低摩擦系数MoS2基金属复合固体润滑膜在不同基底温度薄膜的XRD图;

图14是本发明实施例11所制的低摩擦系数MoS2基金属复合固体润滑膜的XRD图;

图15是本发明实施例1、实施例10制得的低摩擦系数MoS2基金属复合固体润滑膜和对比例1制得的纯MoS2固体润滑膜进行摩擦性能测试的结果对比图。

具体实施方式

以下结合附图对本发明的实施例进行详细说明,但是本发明可以由权利要求限定和覆盖的多种不同方式实施。

实施例1

一种低摩擦系数MoS2基金属复合固体润滑膜,其成分组成为:Cu 13.74at%,MoS2余量。薄膜厚度为2.6μm。

制得的复合固体润滑膜结构致密,肉眼观察呈镜面。薄膜的微观形貌如图 1所示,薄膜表面呈10-100nm左右的颗粒状,无裂纹;所制薄膜的截面形貌如图2所示,截面呈紧密的片柱状,有一定的生长方向。

该薄膜通过Cu金属靶与MoS2靶材共溅射,制备方法为:

(1)对单晶硅基底进行表面抛光、丙酮和酒精超声清洗、烘干;

(2)设置工艺参数,本底真空度为5×10-4Pa,保护气体采用氩气,工作气压为1Pa,基底温度是常温,衬底旋转速度为3r/min,靶基距为17cm;采用射频电源,在预溅射功率为120W的条件下在基底表面预沉积Ti预结合层 10min,预结合层的厚度为30nm;

(3)磁控溅射镀膜:Cu金属靶采用10W直流溅射靶电源,MoS2靶采用 100W射频溅射靶电源,溅射3h,得低摩擦系数MoS2基金属复合固体润滑膜。

采用中国科学院兰州化学物理研究所MFT-R4000高速往复摩擦磨损试验仪对该薄膜进行了摩擦性能检测。测试条件为:室温,RH50%。摩擦副材料为Φ4mm钢珠,划痕实验采用锥角120°、尖端半径0.2mm的金刚石压头,往复摩擦速度为240mm/min。测试结果为:薄膜失效临界载荷(LC2)为12.6N, 10N载荷下摩擦系数为0.07,线磨损强度为2.08×10-7

该复合固体润滑膜在摩擦磨损过程中形成一定的粉状磨屑,在摩擦的划痕中起到润滑的作用,薄膜表现出粘着磨损和疲劳磨损结合的磨损机制。该薄膜磨损形貌及磨痕截面轮廓如图3、图4所示,耐磨损性能佳,结合力偏低,在 SEM电镜下观察薄膜形貌呈致密排列,截面呈明显的片层状,有明显的方向性。

实施例2

一种低摩擦系数MoS2基金属复合固体润滑膜,其成分与实施例1相同,薄膜厚度为0.3μm。

制备方法除步骤(3)中Cu金属靶采用20W直流溅射靶电源,预结合层厚度为29nm,其他与实施例1相同。

实施例3

一种低摩擦系数MoS2基金属复合固体润滑膜,其成分与实施例1相同,薄膜厚度为2μm。

制备方法除步骤(3)中Cu金属靶采用40W直流溅射靶电源,预结合层厚度为31nm,其他与实施例1相同。

实施例4

一种低摩擦系数MoS2基金属复合固体润滑膜,其成分与实施例1相同,薄膜厚度为1.5μm。

制备方法除步骤(3)中Cu金属靶采用60W直流溅射靶电源,预结合层厚度为32nm,其他与实施例1相同。

实验例1

对实施例1~4制得的低摩擦系数MoS2基金属复合固体润滑膜的物相进行 X射线衍射分析,测试结果如图5所示。

结果显示,Cu金属靶采用不同功率直流溅射电源与MoS2靶共溅射所得的复合固体润滑膜的物相呈现为非晶态,说明所制薄膜的均匀性很好。

实施例5

一种低摩擦系数MoS2基金属复合固体润滑膜,其成分组成为:Cu 3at%, MoS2余量,薄膜厚度为2.5μm。

制备方法除基底为不锈钢,采用Al预结合层,厚度为28nm,其余与实施例1相同。

实施例6

一种低摩擦系数MoS2基金属复合固体润滑膜,其成分组成为:Cu14at%, MoS2余量,薄膜厚度为2μm。

制备方法除衬底旋转速度为5r/min,靶基距为15cm,采用Al预结合层,厚度为35nm,其余与实施例1相同。

实施例7

一种低摩擦系数MoS2基金属复合固体润滑膜,其成分组成为:Cu 25at%, MoS2余量,薄膜厚度为2.2μm。

制备方法除衬底旋转速度为4r/min,预结合层厚度为33nm,其余与实施例1相同。

实施例8

一种低摩擦系数MoS2基金属复合固体润滑膜,其成分组成为:Cu 30at%, MoS2余量,薄膜厚度为1.5μm。

制备方法除靶基距为16cm,预结合层厚度为30nm,其余与实施例1相同。

实施例9

一种低摩擦系数MoS2基金属复合固体润滑膜,其成分组成为:Cu 35at%, MoS2余量,薄膜厚度为1.5μm。

制备方法除预结合层厚度为30nm,其余与实施例1相同。

采用实施例1的摩擦性能测试方法,测得该薄膜在10N载荷下摩擦系数为0.08。

实验例2

将实施例9所制的低摩擦系数MoS2基金属复合固体润滑膜的物相进行X 射线衍射分析;再将该薄膜基底加热至100℃,对薄膜的物相进行X射线衍射分析;再将该薄膜基底继续加热至200℃。对薄膜的物相进行X射线衍射分析,测试结果如图6所示。对该薄膜表面的微观形貌进行测试,结果如图7所示。对该薄膜截面形貌进行测试,结果如图8所示。

结果显示,所制薄膜随基底温度上升,其薄膜物相也发生变化,当基底温度升高到200℃时,Cu0.9Mo3O4物相的特征峰明显增多,峰值明显升高。这说明当基底温度加热至100℃时,薄膜出现少量结晶,出现初步集聚现象,这时薄膜仍具有相当强度,当薄膜基底加热至200℃时,薄膜结晶现象明显增多,薄膜不致密,失去强度。扫描该薄膜表面微观结构显示:薄膜表面出现了100nm 左右的长度蠕虫状结构,截面观察薄膜不致密。可知,在基底加热制备材料的过程中会加速薄膜表面的氧化速度。

实施例10

一种低摩擦系数MoS2基金属复合固体润滑膜,由下述原子百分比的成分组成:Cu25at%,Al 10at%,MoS2余量。薄膜厚度为0.367μm。

制得的复合固体润滑剂薄膜结构致密,肉眼观察呈镜面。薄膜的微观形貌如图9所示,薄膜表面呈10-20nm左右的颗粒状,几十个颗粒团聚在一起形成 60nm左右的大颗粒,并形成清晰的边界,偶有100-200nm左右的大颗粒凸起;截面形貌如图10所示,呈紧密的颗粒状生长,没有明显的生长方向。

该薄膜通过Cu金属靶、Al金属靶与MoS2靶材共溅射,制备方法为:

(1)对单晶硅基底进行表面抛光、丙酮和酒精超声清洗、烘干;

(2)设置工艺参数,本底真空度为5×10-5Pa,保护气体采用氩气,工作气压为1Pa,基底温度是常温,衬底旋转速度为5r/min,靶基距为17cm;采用射频电源,在预溅射功率为120W的条件下在基底表面预沉积Al结合层10min,预结合层的厚度为30nm;

(3)磁控溅射镀膜:Cu金属靶采用5W直流溅射靶电源,Al金属靶采用5W直流溅射靶电源,MoS2靶采用100W射频溅射靶电源,溅射3h,即得。

采用中国科学院兰州化学物理研究所MFT-R4000高速往复摩擦磨损试验仪对该薄膜进行了摩擦性能检测。测试条件为:室温,RH50%。摩擦副材料为Φ4mm钢珠,划痕实验采用锥角120°、尖端半径0.2mm的金刚石压头,往复摩擦速度为240mm/min。测试不同载荷(5N、10N、20N)下的薄膜摩擦系数,测试结果为:薄膜失效临界载荷(LC2)为50N,10N载荷下摩擦系数为 0.083,线磨损强度为4.1×10-8

该复合固体润滑膜表现出更强的磨损性能,在相同实验条件下,薄膜未出现磨穿的情形,没有形成膜层脱落的现象。该薄膜磨损形貌及磨痕截面轮廓如图11、图12所示,耐磨损性能佳,结合力明显改善,在SEM电镜下观察薄膜形貌呈致密排列,截面呈明显的柱状。

实验例3

将实施例10所制的低摩擦系数MoS2基金属复合固体润滑膜的物相进行X 射线衍射分析;再将该薄膜基底加热至100℃,对薄膜的物相进行X射线衍射分析;再将该薄膜基底继续加热至200℃。对薄膜的物相进行X射线衍射分析,测试结果如图13所示。

结果显示,所制薄膜随基底温度上升,其薄膜物相也发生变化,当基底温度升高到200℃时,出现Cu1.83Mo3S4、Cu1.47Mo3S4、Cu3Mo2O9等物质的特征峰,且Cu1.83Mo3S4的特征峰明显升高。这说明当基底温度加热至100℃时,薄膜仍致密,扫描截面呈非典型柱面,当薄膜基底加热至200℃时,薄膜结晶现象明显,扫描发现,薄膜表面集聚呈80nm左右的条状,截面呈松散状,薄膜强度下降。

实施例11

一种低摩擦系数MoS2基金属复合固体润滑膜,其成分与实施例10相同,薄膜厚度为0.5μm。

制备方法除在真空条件下,所得低摩擦系数MoS2基金属复合固体润滑膜在800℃下进行退火处理,其他与实施例1相同。测试退火后的薄膜物相,测试结果如图14所示。

实施例12

一种低摩擦系数MoS2基金属复合固体润滑膜,由下述原子百分比的成分组成:Cu30at%,Al 5at%,MoS2余量。薄膜厚度为1μm。

制备方法除衬底旋转速度为4r/min,靶基距为15cm,预结合层为Ti,厚度为33nm,所制成品在600℃下进行退火处理,其余与实施例10相同。

实施例13

一种低摩擦系数MoS2基金属复合固体润滑膜,由下述原子百分比的成分组成:Cu2at%,Al 12at%,MoS2余量。薄膜厚度为1.5μm。

制备方法除靶基距为16cm,预结合层为Ti,厚度为31nm,其余与实施例 10相同。

实施例14

一种低摩擦系数MoS2基金属复合固体润滑膜,由下述原子百分比的成分组成:Cu38at%,Al 3at%,MoS2余量。薄膜厚度为2μm。

制备方法除所制成品在700℃下进行退火处理,其余与实施例10相同。

对比例1

一种纯MoS2固体润滑膜,薄膜厚度为0.5μm,制备方法为:

(1)对单晶硅基底进行表面抛光、丙酮和酒精超声清洗、烘干;

(2)设置工艺参数,本底真空度为5×10-5Pa,保护气体采用氩气,工作气压为1Pa,基底温度是常温,衬底旋转速度为5r/min,靶基距为17cm;采用射频电源,在预溅射功率为120W的条件下在基底表面预沉积Al结合层10min,预结合层的厚度为30nm;

(3)磁控溅射镀膜:MoS2靶采用100W射频溅射靶电源,溅射3h,即得。

实验例5

采用中国科学院兰州化学物理研究所MFT-R4000高速往复摩擦磨损试验仪对实施例1、实施例10制得的低摩擦系数MoS2基金属复合固体润滑膜和对比例1制得的纯MoS2固体润滑膜进行摩擦性能测试,测试结果如图15所示。

测试条件为:室温,RH50%。摩擦副材料为Φ4mm钢珠,划痕实验采用锥角120°、尖端半径0.2mm的金刚石压头,往复摩擦速度为240mm/min。

以上仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。

【EN】

A kind of low-friction coefficient MoS2Base Metal composite solid lubricant film

Technical field

The present invention relates to the coating fields to metal, and in particular to a kind of low-friction coefficient MoS2Base Metal complex solid profit

Synovial membrane.

Background technique

To prevent and protecting friction surface when performing relative motion from damaging and reducing its friction and wear and on surface

On the powdered or film-form solid that uses be known as solid lubricant.Solid lubricant film is for that cannot use the ground of lubricant grease

It is common to be applied to the fields such as space technology, electrical engineering and automobile engineering under the occasion of side, bad environments and Maintenance free.Gu

The type of body lubricant can be divided into several classes such as sulfide, graphite, soft metal, metal oxide, metal fluoride by raw material.

Molybdenum disulfide has good anisotropy and lower friction factor, and S is very strong to the adhesion strength of metal, makes two

Molybdenum sulfide can be perfectly adhered to metal surface and play lubricating function always, be a kind of metal sulfide solid of good performance

Lubricant.But the molybdenum disulfide under atmospheric environment begins to gradually aoxidize at 400 DEG C or so, and coefficient of friction gradually rises,

And the humidity oxidisability of molybdenum disulfide is poor, and with the increase of humidity in atmosphere, its coefficient of friction also increases.

For the resistance to oxidation and moisture-proof for improving molybdenum disulfide, expand its use scope, researcher passes through addition elemental gold

Category, resin material, metal oxide, metal sulfide or metal fluoride etc. form two components with molybdenum disulfide or multiple groups part is solid

Body lubriation material is to improve the lubrication of solid lubricating film, wear-resistant and moisture-resistant antioxygenic property.

Preparation method that solid lubricant film generallys use and there are the problem of have: (1) dip-coating, spraying, brushing, but these

The binding force for the lubricating film that coating method is formed is bad, aesthetic appearance is poor, resistance to Special Medium is poor, film uniformity is difficult to ensure, such as

A kind of preparation method of the solid lubricant film applied to automobile spline axial workpiece disclosed in Chinese patent CN03127698.9;

(2) electrodeposition process, this method have that deposition rate is excessively slow more;(3) ion plating method, but ion plating can be in workpiece table

Face, which deposits a large amount of bulky grains, causes film surface roughness larger, and the particle of inside package easily leads to film layer removing failure, so that

The wear-resisting property of film layer is affected, and cannot fully meet the needs of long life solid lubricating utensil instrument;(4) physical vapor is heavy

Area method, lubricating film made from this method have many advantages, such as that good binding force, even film layer, deposition rate is moderate, film layer is fine and close, but still

Increase in the presence of internal stress between rear solid lubricant film and substrate is repeatedly used, base in the still preferable situation of solid lubricant film

The problem of bottom has aoxidized, a kind of common-sputtering solid lubricating film as disclosed in Chinese patent 94107544.3.

Physical vaporous deposition mainly has vacuum evaporation, sputter coating, arc-plasma plating, ion film plating and molecule

The methods of beam epitaxy.Relative to vacuum evaporation, during magnetic control film coating target without phase-change, chemical composition stability, process repeatability

Well, the defects of being convenient for automated production, and institute's film plating layer depositing homogeneous, being not in molten drop phenomenon, is suitble to solid lubricating film

Deng preparation.

Therefore, in view of the above-mentioned problems, need to improve molybdenum disulfide solid lubricant film in conjunction with metallic addition at seperated

System, solves the problems, such as that molybdenum-disulfide radical solid lubricant film wearability in use is poor and use environment is harsh, provides curing

A possibility that more occasions of molybdenum base film use, and extend the service life of film.

Summary of the invention

The present invention is in view of the above-mentioned problems, provide a kind of low-friction coefficient MoS2Base Metal composite solid lubricant film.

Technical solution used by the present invention solves the above problems is: a kind of low-friction coefficient MoS2Base Metal complex solid

Lubricating film, by following atomic percents at being grouped as: Cu 2at%~38at%, Al 0~12at%, MoS2Surplus;It is low

Coefficient of friction MoS2The preparation method of Base Metal composite solid lubricant film, comprising the following steps:

Step A1, pre- binder course sputtering: being 120W in pre-sputtering power using radio-frequency power supply before magnetron sputtering plating

Under conditions of in substrate surface pre-deposition Ti or Al binder course 10min;Wherein, the pre-deposition binder course before magnetron sputtering plating,

The internal stress between film and matrix can be reduced, while forming oxide film under the high temperature conditions, prevents matrix into one

Step oxidation.

Step A2, magnetron sputtering plating: background vacuum is 5 × 10-4Pa~5 × 10-5Pa, protective gas use argon gas,

Operating air pressure is 1Pa, and base reservoir temperature is room temperature, and substrate rotation speed is 3r/min~5r/min, and target-substrate distance is 15cm~17cm;

The sputtering condition of metal targets: 5W~60W d.c. sputtering target power supply is set;MoS is set2The sputtering condition of target: 100W radio frequency

Sputter target power supply;Sputtering time is 2.5h~3.5h, obtains low-friction coefficient MoS2Base Metal composite solid lubricant film.

Further, low-friction coefficient MoS2Base Metal composite solid lubricant film is by following atomic percents at grouping

At: Cu 3at%~14at%, MoS2Surplus.

Further, low-friction coefficient MoS2Base Metal composite solid lubricant film is by following atomic percents at grouping

At: Cu 25at%~30at%, MoS2Surplus.

Further, low-friction coefficient MoS2Base Metal composite solid lubricant film is by following atomic percents at grouping

At: Cu 25at%~30at%, Al 5at%~10at%, MoS2Surplus.

Further, in step A1, substrate are as follows: monocrystalline silicon or stainless steel.

Further, in step A1, pre- binder course with a thickness of 28nm~35nm.

It further, further include that surface polishing, acetone and alcohol ultrasonic cleaning, drying are carried out to substrate before step A1 is carried out

The step of.

It further, further include to the low-friction coefficient MoS obtained2Base Metal composite solid lubricant film is 600

DEG C~800 DEG C at a temperature of carry out annealing heat-treatment the step of.Wherein, Cu-Al cosputtering target is selected, annealing heat-treatment is passed through

After obtain solid solution phase, to strengthen film overall mechanical properties, overall abrasion resistance properties and anti humility performance increase;And

And there is apparent Al during annealing and substrate heating film-coated in Cu and Al2O3Oxidation is faster than CuO, helps to improve

The antioxygenic property of film.

Further, low-friction coefficient MoS2Base Metal composite solid lubricant film with a thickness of 0.3 μm~3 μm.

The invention has the advantages that

1. the present invention selects common soft metal copper as main additive, using molybdenum disulfide as the main of solid lubricant film

Ingredient, or be aided with second of metal and form interphase solid solution, to improve the comprehensive performance of solid lubricant film, technique processing cost

It is low, and it is aided with heat treatment process, process flow is not many and diverse, and prepared film comprehensive performance reaches requirement, has industrial metaplasia

The feasibility of production, overall cost performance are higher;

2. present invention pre-deposition binder course before magnetron sputtering plating, can reduce the internal stress between film and matrix,

It forms oxide film under the high temperature conditions simultaneously, matrix is prevented further to aoxidize;

3. the Cu-Al cosputtering target that the present invention selects, by obtaining solid solution phase after annealing heat-treatment, to strengthen thin

Film overall mechanical properties, overall abrasion resistance properties and anti humility performance increase;And Cu and Al are in annealing and substrate

During heating film-coated, there is apparent Al2O3Oxidation is faster than CuO, helps to improve the antioxygenic property of film.

Detailed description of the invention

It forms part of this specification, show embodiment party of the invention for further understanding attached drawing of the invention

Case, and be used to illustrate preparation flow of the invention together with specification.In the accompanying drawings:

Fig. 1 is low-friction coefficient MoS made from the embodiment of the present invention 12The SEM of Base Metal composite solid lubricant film schemes;

Fig. 2 is low-friction coefficient MoS made from the embodiment of the present invention 12The SEM in Base Metal composite solid lubricant film section

Figure;

Fig. 3 is low-friction coefficient MoS made from the embodiment of the present invention 12After Base Metal composite solid lubricant film experience wear

Wear morphology;

Fig. 4 is low-friction coefficient MoS made from the embodiment of the present invention 12After Base Metal composite solid lubricant film experience wear

Polishing scratch cross section profile;

Fig. 5 is low-friction coefficient MoS made from the embodiment of the present invention 1~42The XRD diagram of Base Metal composite solid lubricant film;

Fig. 6 is low-friction coefficient MoS made from the embodiment of the present invention 92Base Metal composite solid lubricant film is in different base

The XRD diagram of temperature thin-film;

Fig. 7 is low-friction coefficient MoS made from the embodiment of the present invention 92Base Metal composite solid lubricant film is heated in substrate

SEM figure when to 200 DEG C;

Fig. 8 is low-friction coefficient MoS made from the embodiment of the present invention 92Base Metal composite solid lubricant film is heated in substrate

Cross Section Morphology figure when to 200 DEG C;

Fig. 9 is low-friction coefficient MoS made from the embodiment of the present invention 102The SEM of Base Metal composite solid lubricant film schemes;

Figure 10 is low-friction coefficient MoS made from the embodiment of the present invention 102The SEM in Base Metal composite solid lubricant film section

Figure;

Figure 11 is low-friction coefficient MoS made from the embodiment of the present invention 102After Base Metal composite solid lubricant film experience wear

Wear morphology;

Figure 12 is low-friction coefficient MoS made from the embodiment of the present invention 102After Base Metal composite solid lubricant film experience wear

Polishing scratch cross section profile;

Figure 13 is low-friction coefficient MoS made from the embodiment of the present invention 102Base Metal composite solid lubricant film is in different bases

The XRD diagram of bottom temperature thin-film;

Figure 14 is the made low-friction coefficient MoS of the embodiment of the present invention 112The XRD diagram of Base Metal composite solid lubricant film;

Figure 15 is the embodiment of the present invention 1, low-friction coefficient MoS made from embodiment 102Base Metal composite solid lubricant film

With pure MoS made from comparative example 12The comparative result figure of solid lubricant film progress frictional behaviour test.

Specific embodiment

The embodiment of the present invention is described in detail below in conjunction with attached drawing, but the present invention can be defined by the claims

Implement with the multitude of different ways of covering.

Embodiment 1

A kind of low-friction coefficient MoS2Base Metal composite solid lubricant film, at being grouped as are as follows: Cu 13.74at%, MoS2

Surplus.Film thickness is 2.6 μm.

Composite solid lubricant film compact structure obtained, visually observes in mirror surface.The microscopic appearance of film as shown in Figure 1,

Graininess of the film surface in 10-100nm or so, flawless;The Cross Section Morphology of institute's made membrane is as shown in Fig. 2, section is in close

Piece column, have certain direction of growth.

The film passes through Cu metallic target and MoS2Target cosputtering, the preparation method comprises the following steps:

(1) surface polishing, acetone and alcohol ultrasonic cleaning, drying are carried out to monocrystal silicon substrate;

(2) technological parameter is set, and background vacuum is 5 × 10-4Pa, protective gas use argon gas, operating air pressure 1Pa,

Base reservoir temperature is room temperature, and substrate rotation speed is 3r/min, target-substrate distance 17cm;Using radio-frequency power supply, it is in pre-sputtering power

In the pre- binder course 10min of substrate surface pre-deposition Ti under conditions of 120W, pre- binder course with a thickness of 30nm;

(3) magnetron sputtering plating: Cu metallic target uses 10W d.c. sputtering target power supply, MoS2Target uses 100W radio-frequency sputtering

Target power supply sputters 3h, obtains low-friction coefficient MoS2Base Metal composite solid lubricant film.

It is thin to this using Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences MFT-R4000 high speed reciprocating friction Wear Tester

Film has carried out frictional behaviour detection.Test condition are as follows: room temperature, RH50%.Friction pair material is Φ 4mm steel ball, and scratch experiment is adopted

With 120 ° of cone angle, the diamond penetrator of tip radius 0.2mm, reciprocating friction speed is 240mm/min.Test result are as follows: film

Critical load (LC2) is failed for 12.6N, and coefficient of friction is 0.07 under 10N load, and line tear strength is 2.08 × 10-7

The composite solid lubricant film forms certain powdery abrasive dust in process of friction and wear, plays in the scratch of friction

The effect of lubrication, film show the wear mechanism that adhesive wear and fatigue wear combine.The film wear morphology and polishing scratch are cut

Facial contour is as shown in Figure 3, Figure 4, and abrasion resistance properties are good, and binding force is relatively low, in SEM electricity microscopic observation film morphology in fine and close row

Column, section are in apparent sheet, there is apparent directionality.

Embodiment 2

A kind of low-friction coefficient MoS2Base Metal composite solid lubricant film, ingredient is same as Example 1, and film thickness is

0.3μm。

Preparation method removes Cu metallic target in step (3) and uses 20W d.c. sputtering target power supply, and pre- joint thickness is 29nm,

Other are same as Example 1.

Embodiment 3

A kind of low-friction coefficient MoS2Base Metal composite solid lubricant film, ingredient is same as Example 1, and film thickness is

2μm。

Preparation method removes Cu metallic target in step (3) and uses 40W d.c. sputtering target power supply, and pre- joint thickness is 31nm,

Other are same as Example 1.

Embodiment 4

A kind of low-friction coefficient MoS2Base Metal composite solid lubricant film, ingredient is same as Example 1, and film thickness is

1.5μm。

Preparation method removes Cu metallic target in step (3) and uses 60W d.c. sputtering target power supply, and pre- joint thickness is 32nm,

Other are same as Example 1.

Experimental example 1

To low-friction coefficient MoS made from Examples 1 to 42The object of Base Metal composite solid lubricant film mutually carries out X-ray

Diffraction analysis, test results are shown in figure 5.

The results show that Cu metallic target uses different capacity DC sputtering power and MoS2The resulting complex solid of target co-sputtering

The object of lubricating film is mutually rendered as amorphous state, illustrates that the uniformity of institute's made membrane is fine.

Embodiment 5

A kind of low-friction coefficient MoS2Base Metal composite solid lubricant film, at being grouped as are as follows: Cu 3at%, MoS2It is remaining

Amount, film thickness are 2.5 μm.

Preparation method is stainless steel except substrate, and using the pre- binder course of Al, with a thickness of 28nm, remaining is same as Example 1.

Embodiment 6

A kind of low-friction coefficient MoS2Base Metal composite solid lubricant film, at being grouped as are as follows: Cu14at%, MoS2It is remaining

Amount, film thickness are 2 μm.

Preparation method is 5r/min, target-substrate distance 15cm except substrate rotation speed, using the pre- binder course of Al, with a thickness of

35nm, remaining is same as Example 1.

Embodiment 7

A kind of low-friction coefficient MoS2Base Metal composite solid lubricant film, at being grouped as are as follows: Cu 25at%, MoS2It is remaining

Amount, film thickness are 2.2 μm.

Preparation method is 4r/min except substrate rotation speed, and pre- joint thickness is 33nm, remaining is same as Example 1.

Embodiment 8

A kind of low-friction coefficient MoS2Base Metal composite solid lubricant film, at being grouped as are as follows: Cu 30at%, MoS2It is remaining

Amount, film thickness are 1.5 μm.

Preparation method is 16cm except target-substrate distance, and pre- joint thickness is 30nm, remaining is same as Example 1.

Embodiment 9

A kind of low-friction coefficient MoS2Base Metal composite solid lubricant film, at being grouped as are as follows: Cu 35at%, MoS2It is remaining

Amount, film thickness are 1.5 μm.

Preparation method is 30nm except pre- joint thickness, remaining is same as Example 1.

Using the frictional behaviour test method of embodiment 1, measuring film coefficient of friction under 10N load is 0.08.

Experimental example 2

By the low-friction coefficient MoS that embodiment 9 is made2The object of Base Metal composite solid lubricant film mutually carries out X x ray diffraction

Analysis;The film substrate is heated to 100 DEG C again, X-ray diffraction analysis is mutually carried out to the object of film;Again by the film substrate after

It is continuous to be heated to 200 DEG C.X-ray diffraction analysis is mutually carried out to the object of film, test results are shown in figure 6.To the film surface

Microscopic appearance is tested, as a result as shown in Figure 7.The film sections pattern is tested, as a result as shown in Figure 8.

The results show that institute's made membrane rises with base reservoir temperature, film object mutually also changes, when base reservoir temperature is increased to

At 200 DEG C, Cu0.9Mo3O4The characteristic peak of object phase increased significantly, and peak value is significantly raised.This explanation is heated to 100 DEG C when base reservoir temperature

When, there is a small amount of crystallization in film, preliminary aggregation phenomenon occurs, at this moment film still has suitable intensity, when film substrate is heated to

At 200 DEG C, film crystalline polamer be increased significantly, and film is not fine and close, lose intensity.The film surface microstructure is scanned to show:

There is the length vermicular texture of 100nm or so in film surface, and cross-section observation film is not fine and close.It is made it is found that being heated in substrate

It can accelerate the oxidation rate of film surface during standby material.

Embodiment 10

A kind of low-friction coefficient MoS2Base Metal composite solid lubricant film, by following atomic percents at being grouped as: Cu

25at%, Al 10at%, MoS2Surplus.Film thickness is 0.367 μm.

Composite solid lubricating agent membrane structure obtained is fine and close, visually observes in mirror surface.The microscopic appearance of film such as Fig. 9 institute

Showing, film surface is in the graininess of 10-20nm or so, and tens particle agglomerations form the bulky grain of 60nm or so together, and

Clearly boundary is formed, occasionally there is the bulky grain protrusion of 100-200nm or so;Cross Section Morphology is as shown in Figure 10, is in close particle

Shape growth, without the apparent direction of growth.

The film passes through Cu metallic target, Al metallic target and MoS2Target cosputtering, the preparation method comprises the following steps:

(1) surface polishing, acetone and alcohol ultrasonic cleaning, drying are carried out to monocrystal silicon substrate;

(2) technological parameter is set, and background vacuum is 5 × 10-5Pa, protective gas use argon gas, operating air pressure 1Pa,

Base reservoir temperature is room temperature, and substrate rotation speed is 5r/min, target-substrate distance 17cm;Using radio-frequency power supply, it is in pre-sputtering power

In substrate surface pre-deposition Al binder course 10min under conditions of 120W, pre- binder course with a thickness of 30nm;

(3) magnetron sputtering plating: Cu metallic target uses 5W d.c. sputtering target power supply, and Al metallic target uses 5W d.c. sputtering target

Power supply, MoS2Target use 100W radio-frequency sputtering target power supply, sputter 3h to get.

It is thin to this using Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences MFT-R4000 high speed reciprocating friction Wear Tester

Film has carried out frictional behaviour detection.Test condition are as follows: room temperature, RH50%.Friction pair material is Φ 4mm steel ball, and scratch experiment is adopted

With 120 ° of cone angle, the diamond penetrator of tip radius 0.2mm, reciprocating friction speed is 240mm/min.Test different loads (5N,

10N, 20N) under film friction coefficient, test result are as follows: diaphragm failure critical load (LC2) is 50N, is rubbed under 10N load

Coefficient is 0.083, and line tear strength is 4.1 × 10-8

The composite solid lubricant film shows stronger polishing machine, and under same experimental conditions, film does not occur worn out

Situation, do not form the phenomenon that film layer falls off.The film wear morphology and polishing scratch cross section profile are resistance to as shown in Figure 11, Figure 12

Polishing machine is good, and binding force is obviously improved, and is in dense arrangement in SEM electricity microscopic observation film morphology, section is in apparent column.

Experimental example 3

By the low-friction coefficient MoS that embodiment 10 is made2The object of Base Metal composite solid lubricant film mutually carries out X ray and spreads out

Penetrate analysis;The film substrate is heated to 100 DEG C again, X-ray diffraction analysis is mutually carried out to the object of film;Again by the film substrate

Continue to be heated to 200 DEG C.X-ray diffraction analysis is mutually carried out to the object of film, test result is as shown in figure 13.

The results show that institute's made membrane rises with base reservoir temperature, film object mutually also changes, when base reservoir temperature is increased to

At 200 DEG C, there is Cu1.83Mo3S4、Cu1.47Mo3S4、Cu3Mo2O9The characteristic peak of equal substances, and Cu1.83Mo3S4Characteristic peak it is obvious

It increases.For this explanation when base reservoir temperature is heated to 100 DEG C, film is still fine and close, and scanning cross-section is in atypia cylinder, works as film substrate

When being heated to 200 DEG C, film crystalline polamer is obvious, scanning discovery, and film surface gathers the strip in 80nm or so, and section is in pine

Bulk, film strength decline.

Embodiment 11

A kind of low-friction coefficient MoS2Base Metal composite solid lubricant film, ingredient is same as in Example 10, film thickness

It is 0.5 μm.

Preparation method is removed under vacuum conditions, gained low-friction coefficient MoS2Base Metal composite solid lubricant film is at 800 DEG C

Under made annealing treatment, other are same as Example 1.Film object phase after test annealing, test result are as shown in figure 14.

Embodiment 12

A kind of low-friction coefficient MoS2Base Metal composite solid lubricant film, by following atomic percents at being grouped as: Cu

30at%, Al 5at%, MoS2Surplus.Film thickness is 1 μm.

Preparation method is 4r/min except substrate rotation speed, and target-substrate distance 15cm, pre- binder course is Ti, with a thickness of 33nm,

Made finished product is made annealing treatment at 600 DEG C, remaining is same as in Example 10.

Embodiment 13

A kind of low-friction coefficient MoS2Base Metal composite solid lubricant film, by following atomic percents at being grouped as: Cu

2at%, Al 12at%, MoS2Surplus.Film thickness is 1.5 μm.

Preparation method is 16cm except target-substrate distance, and pre- binder course is Ti, and with a thickness of 31nm, remaining is same as in Example 10.

Embodiment 14

A kind of low-friction coefficient MoS2Base Metal composite solid lubricant film, by following atomic percents at being grouped as: Cu

38at%, Al 3at%, MoS2Surplus.Film thickness is 2 μm.

Preparation method is made annealing treatment at 700 DEG C except made finished product, remaining is same as in Example 10.

Comparative example 1

A kind of pure MoS2Solid lubricant film, film thickness are 0.5 μm, the preparation method comprises the following steps:

(1) surface polishing, acetone and alcohol ultrasonic cleaning, drying are carried out to monocrystal silicon substrate;

(2) technological parameter is set, and background vacuum is 5 × 10-5Pa, protective gas use argon gas, operating air pressure 1Pa,

Base reservoir temperature is room temperature, and substrate rotation speed is 5r/min, target-substrate distance 17cm;Using radio-frequency power supply, it is in pre-sputtering power

In substrate surface pre-deposition Al binder course 10min under conditions of 120W, pre- binder course with a thickness of 30nm;

(3) magnetron sputtering plating: MoS2Target use 100W radio-frequency sputtering target power supply, sputter 3h to get.

Experimental example 5

Using Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences MFT-R4000 high speed reciprocating friction Wear Tester to implementation

Low-friction coefficient MoS made from example 1, embodiment 102Pure MoS made from Base Metal composite solid lubricant film and comparative example 12Solid

Lubricating film carries out frictional behaviour test, and test result is as shown in figure 15.

Test condition are as follows: room temperature, RH50%.Friction pair material is Φ 4mm steel ball, and scratch experiment is using 120 ° of cone angle, point

The diamond penetrator of radius 0.2mm is held, reciprocating friction speed is 240mm/min.

These are only the preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art

For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,

Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

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