CN106222726B - 一种钛及其合金表面耐磨、低摩擦复合涂层及其制备方法 - Google Patents
一种钛及其合金表面耐磨、低摩擦复合涂层及其制备方法 Download PDFInfo
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- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 22
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- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 4
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 4
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
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- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
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Abstract
本发明涉及一种钛及其合金表面耐磨、低摩擦复合涂层及其制备方法,包括以下步骤:采用微弧氧化技术在钛或其合金试件表面制得含有石墨的前驱体氧化涂层;对前驱体氧化涂层进行等离子渗氮处理。本发明提供的一种复合涂层不仅可以提高钛及其合金的耐磨性能,而且具有较低的摩擦系数,有效减缓了摩擦副的磨损失效,扩大了钛及其合金的应用范围。
Description
技术领域
本发明涉及表面防护涂层材料领域,具体涉及一种钛及其合金表面耐磨、低摩擦复合涂层及其制备方法。
背景技术
钛及其合金是优异的轻型结构材料,拥有高比强度、无磁性以及突出的耐海水和海洋大气腐蚀等优势,因而在各类海洋工程具有广泛的适用性,被誉为海洋“奇材”。尽管钛材作为海洋工程用材料拥有很多优异的性能,但也并非全然美好,在应用过程中存在的耐磨性能不足等问题,因而,制约了钛材的应用。目前提高钛及其合金耐磨性的方法有微弧氧化、激光熔覆等。尽管采用上述方法所制备的硬质陶瓷涂层具有优异的耐蚀性能,但是涂层的摩擦系数较高,易加快摩擦副磨损失效。为此,中国专利号CN201310025662.X,公开了名称为一种钛合金自润滑复合膜及其制备方法的专利,其通过微弧氧化和反复涂覆的方法制备出陶瓷氧化膜与环氧树脂复合自润滑膜层,有效提高了钛材耐磨性,减小了涂层的摩擦系数,但树脂基膜层易发生老化。E.E.Sukuroglu等采用磁控溅射在微弧氧化膜表面沉积了一层低摩擦系数的DLC膜,有效改善了涂层摩擦性能(E.E.Sukuroglu,Y.Totik,E.Arslan,I.Efeoglu.Analysis of tribo-corrosion properties of MAO/DLC coatings using aduplex process on Ti6Al4V alloys[J].J.Bio.Tribo.Corros.,2015,1:22),但DLC与氧化陶瓷层之间存在突变界面,在剧烈摩擦环境下,易导致顶部膜层脱落。
发明内容
本发明的目的是针对现有技术中存在的这些问题,提供一种钛及其合金表面耐磨、低摩擦复合涂层,既不存在膜层老化,膜层之间也不存在突变界面。
为达到上述目的,本发明提供的技术方案是:
一种钛及其合金表面耐磨、低摩擦复合涂层及其制备方法,其特征在于:包括以下步骤:
(1)采用微弧氧化技术在钛或其合金试件表面制得含有石墨的前驱体氧化涂层;
(2)对前驱体氧化涂层进行等离子渗氮处理。
所述的含有石墨的前驱体氧化涂层的微弧氧化工艺中电压380~420V,处理时间20~30min,频率50~100Hz,占空比10~20%;电解液成分为10~15g/L Na2SiO4、2~6g/LKOH、2~5g/L纳米石墨、40~60mL/L无水乙醇以及1~2g/L羟甲基纤维素钠。
所述的纳米石墨厚度≤40nm,片径≤400nm。
所述的等离子渗氮处理,其中电压400~500V,处理时间2~4h,Ar/N2=0~0.5,真空度30~60Pa。
微弧氧化:石墨添入电解液中,在微弧氧化过程中,将被吸附于TiO2表面孔隙中,并随着氧化层增厚,不断堆积,形成前驱体氧化涂层。
等离子渗氮:一方面,氮气气氛里,在等离子作用下,含有石墨的前驱体氧化涂层会发生反应:TiO2+2C+1/2N2→TiN+2CO↑,生成的TiN硬度高,具有较高的承载能力,耐磨性强;另一方面,等离子具有表面清洁能力,可以轰击、溅射前驱体氧化膜层的粗糙表面,改善涂层的表面质量。
本发明提供的一种钛及其合金表面耐磨、低摩擦N-(TiO2/graphite)复合涂层及其制备方法,具有如下有益效果:
(1)该复合涂层中的TiO2、TiN等为硬质相,大大提高了涂层的硬度和耐磨性能;
(2)该复合涂层表面粗糙度较低,且石墨具有润滑作用,大大降低了涂层的摩擦系数;
(3)该复合涂层与基体结合力强,渗氮后的复合涂层之间不存在突变界面,有效降低涂层剥落倾向,延长了涂层的使用寿命,进一步扩大了钛材使用范围和空间;
(4)该复合涂层制备工艺简单,由工业化设备生产,易实现工业化生产。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
实施例1
以TA1纯钛为基体,耐磨、低摩擦复合涂层的制备方法主要包括:采用微弧氧化技术将前处理后的钛在石墨混合电解液中制得含有石墨的前驱体氧化涂层,其中微弧氧化工艺中电压380V,处理时间20min,频率50Hz,占空比20%;电解液成分为10g/L Na2SiO4、3g/LKOH、2g/L纳米石墨(厚度≤40nm,片径≤400nm)、40mL/L无水乙醇以及、1g/L羟甲基纤维素钠。然后对前驱体氧化涂层进行等离子渗氮处理,其中电压400V,处理时间2h,Ar/N2=0.5,真空度40Pa。
实施例2
以TA1纯钛为基体,复合涂层的制备过程与实施例1相同,不同的是微弧氧化工艺中电压400V,处理时间25min,频率100Hz,占空比10%;电解液成分为13g/L Na2SiO4、5g/LKOH、3g/L纳米石墨(厚度≤40nm,片径≤400nm)、50mL/L无水乙醇以及、1.5g/L羟甲基纤维素钠。等离子渗氮处理工艺中电压450V,处理时间2.5h,Ar/N2=0.1,真空度50Pa。
实施例3
以TA1钛合金为基体,复合涂层的制备过程与实施例1相同,不同的是微弧氧化工艺中电压410V,处理时间25min,频率100Hz,占空比10;电解液成分为12g/L Na2SiO4、2g/LKOH、3g/L纳米石墨(厚度≤40nm,片径≤400nm)、50mL/L无水乙醇以及、1g/L羟甲基纤维素钠。等离子渗氮处理工艺中电压450V,处理时间3h,N2气氛,真空度50Pa。
实施例4
以TC4钛合金为基体,复合涂层的制备过程与实施例1相同,不同的是微弧氧化工艺中电压400V,处理时间20min,频率80Hz,占空比15%;电解液成分为10g/L Na2SiO4、4g/LKOH、2g/L纳米石墨(厚度≤40nm,片径≤400nm)、40mL/L无水乙醇以及、1g/L羟甲基纤维素钠。等离子渗氮处理工艺中电压430V,处理时间2h,Ar/N2=0.25,真空度30Pa。
实施例5
以TC4钛合金为基体,复合涂层的制备过程与实施例1相同,不同的是微弧氧化工艺中电压420V,处理时间30min,频率100Hz,占空比20%;电解液成分为15g/L Na2SiO4、6g/LKOH、5g/L纳米石墨(厚度≤40nm,片径≤400nm)、60mL/L无水乙醇以及、2g/L羟甲基纤维素钠。等离子渗氮处理工艺中电压500V,处理时间4h,Ar/N2=0.5,真空度60Pa。
分别采用显微硬度计及摩擦磨损试验机对本发明的N-(TiO2/graphite)复合涂层的表面硬度和摩擦性能进行测试。显微硬度与摩擦磨损测试分别根据标准GB/T 4340.1-2009及标准GB/T 12444-2006执行,其测试结果如表1所示。
表1测试结果
以上所述,仅是本发明的较佳实施例,并非对本发明作任何形式上的限制,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,依据本发明的技术实质,对以上实施例所作的任何简单的修改、等同替换与改进等,均仍属于本发明技术方案的保护范围之内。
Claims (2)
1.一种钛及其合金表面耐磨、低摩擦复合涂层的制备方法,其特征在于:包括以下步骤:
(1)采用微弧氧化技术在钛或其合金试件表面制得含有石墨的前驱体氧化涂层;
(2)对前驱体氧化涂层进行等离子渗氮处理;
所述的含有石墨的前驱体氧化涂层的微弧氧化工艺中电压380~420V,处理时间20~30min,频率50~100Hz,占空比10~20%;电解液成分为10~15g/L Na2SiO4、2~6g/L KOH、2~5g/L纳米石墨、40~60mL/L无水乙醇以及1~2g/L羟甲基纤维素钠;
所述的等离子渗氮处理,其中电压400~500V,处理时间2~4h,Ar/N2=0~0.5,真空度30~60Pa;所述的纳米石墨厚度≤40nm,片径≤400nm。
2.权利要求1所述方法制备的钛及其合金表面耐磨、低摩擦复合涂层。
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