CN116397189B - 基于dlc的硬密封球阀用高耐磨低摩擦涂层材料及制备方法 - Google Patents
基于dlc的硬密封球阀用高耐磨低摩擦涂层材料及制备方法 Download PDFInfo
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Abstract
本发明公开了一种基于DLC的硬密封球阀用高耐磨低摩擦涂层材料及制备方法，涉及涂层材料技术领域，其特征是先在涂层的硬质相颗粒表面电沉积类金刚石（DLC）功能层作为自润滑相，通过表面包覆隔离形成固溶体界面相(Ti，Mo)C，提高其喷涂和服役过程中的耐高温性能，抑制DLC分解，最终在硬密封球阀表面制备出非层状高耐磨低摩擦系数涂层。本发明克服了现有技术工艺复杂、对设备依赖大，成本高，而且形成的多层状结构容易剥落等问题，本涂层工作温度范围为‑196~660℃的宽温域，最大工作压力45MPa，硬度1200~2200HV，涂层结合强度85~95MPa。可用于石油化工、硅行业（多晶硅、有机硅等）、冶金、水电等领域的高性能硬密封球阀。
Description
技术领域
本发明涉及一种涂层材料及制备方法，特别涉及一种基于DLC的硬密封球阀用高耐磨低摩擦涂层材料及制备方法，属于新材料、装备制造、表面工程与硬密封球阀制造技术领域。
背景技术
硬密封球阀是依靠金属球体与金属阀座硬对硬接触，紧密贴合来实现密封的效果。为了提高密封面的抗摩擦磨损性能，通常采用堆焊、表面涂层技术等对阀球和阀座表面进行硬化处理。CN115261854A提供了一种复配防护涂层及制备方法。该复配防护涂层依次包括Cr3C2-NiCr金属陶瓷支撑层、NiCr过渡层、Cr粘接层、Cr→C梯度过渡层和DLC薄膜，能够避免苛刻环境下腐蚀性成分中通过DLC薄膜的柱状结构间隙或DLC薄膜表面缺陷如针孔等直接接触金属基体形成微观闭塞电池而导致的涂层剥落和工件的服役寿命降低。
现有的硬密封球阀用涂层的摩擦系数比较大，特别是在无外部润滑的情况下，球阀在启闭过程中密封面承受着非常大的接触应力，容易产生磨损失效。为了降低摩擦系数而引入DLC涂层，但是，直接DLC喷涂则容易发生分解和石墨化；而且需要运用热喷涂结合气相沉积、离子注渗等方式，不仅工艺复杂、对设备依赖大，成本高，形成的多层状涂层结构不利于涂层结合，容易剥落。因此，开发出新的硬密封球阀用高耐磨低摩擦系数涂层材料及制备方法非常重要。
发明内容
针对目前在硬密封球阀表面制备高耐磨性和低摩擦系数涂层存在的问题。本发明提出在涂层的硬质相颗粒表面电沉积类金刚石（DLC）功能层作为自润滑相，并且通过表面包覆隔离提高其喷涂过程和服役过程中的耐高温性能，抑制类金刚石的分解，最终制备出基于DLC的硬密封球阀用高耐磨低摩擦涂层。
本发明的基于DLC的硬密封球阀用高耐磨低摩擦涂层材料，其特征在于该涂层材料的原料组成为含有TiO2保护层和DLC功能层的硬质相粉末占65~80wt.%，Co粉占0~20%wt.%，Ni粉占0~20%wt.%，Cr粉占0~10wt.%，Mo2C粉占4~6wt.%；超音速火焰喷涂后涂层的物相组成为硬质相+自润滑相+金属相+界面相，其中硬质相为WC或Cr3C2，自润滑相为DLC，金属相为金属固溶体，界面相为(Ti，Mo)C固溶体相，界面相位于硬质相与金属相界面，DLC的sp2/sp3=0.3~0.5，该值在喷涂前后保持不变；本涂层的工作温度范围为-196~660℃，最大工作压力45MPa；涂层硬度1200~2200HV，涂层结合强度85~95MPa。
本发明的基于DLC的硬密封球阀用高耐磨低摩擦涂层材料，其进一步特征在于，所述含有TiO2保护层和DLC功能层的硬质相粉末中，硬质相粉末为WC或Cr3C2，涂层原料中WC粒度为1~6μm，Cr3C2粒度为2~8μm，其余原料的粒度为1~5μm，DLC功能层包覆于硬质相粉末表面，DLC功能层的sp2/sp3 =0.3~0.5，DLC含量占硬质相粉末颗粒总重量的1~2%，TiO2保护层包覆于DLC功能层表面，TiO2含量占硬质相粉末颗粒总重量的3~6%；超音速火焰喷涂后涂层孔隙率0.1~0.5%，涂层的厚度为150~350μm，涂层的摩擦系数为0.1~0.15。
本发明的基于DLC的硬密封球阀用高耐磨低摩擦涂层材料的制备方法，其特征在于依次包含以下步骤：
（1）硬质相粉体分散系配制：将乙醇与去离子水按体积比10:1配置成混合液，然后将WC或Cr3C2硬质相粉末加入其中，硬质相粉体占10~20wt.%，进行超声分散处理30~60min从而配制出硬质相粉体分散系；
（2）硬质相粉体沉降控制：将超声分散处理后硬质相粉体分散系倒入电沉积槽中，电沉积槽中阳极为高纯石墨板并固定于电沉积槽的上部，阴极为钛合金板并固定在电沉积槽的底部，阳极与阴极之间平行且距离为5~15mm；加入HCOOH调节pH值到3~5，溶液Zeta电位控制在-5~-20mv,静置后使硬质相粉体沉降于阴极板上方，沉降层厚度≤1cm；
（3）硬质相粉体颗粒表面DLC功能层制备：接通电沉积槽中阴极和阳极的高压直流电源，控制电压500V~1000V，使乙醇发生极化，其甲基基团阳离子作为碳源并向阴极靠近，在阴极发生放电反应形成DLC并沉积在硬质相粉体颗粒表面；沉积时恒温水浴温度控制在30~50℃，按“沉积DLC 2~4 min—搅拌1 min—粉体沉降5~10min”的循环周期变化的方式进行间歇沉降沉积，沉降和搅拌时切断高压直流电源，接通高压直流电源时不搅拌，沉积总时间6~8h；沉积结束后的粉末在90℃~100℃进行真空干燥，即在硬质相粉末颗粒表面制备出了sp2/sp3=0.3~0.5的DLC功能层；
（4）含DLC功能层的硬质相粉末颗粒表面TiO2保护层制备：按体积比1:（5~6）将钛酸丁脂和无水乙醇混合并搅拌10min形成溶液A；按体积比将1:1将无水乙醇和去离子水混合，并滴加HNO3至pH值为3~4，搅拌10min后形成溶液B；按体积比(2~3):1分别量取A液和B液，并在室温下将A液滴加到B液中，搅拌3~4h形成Ti(OH)4溶胶；称取表面包覆了DLC功能层的硬质相粉末颗粒并加入到Ti(OH)4溶胶中形成混合物，按重量百分比表面包覆了DLC功能层的硬质相粉末颗粒占20~30%，将混合物进行搅拌2~3h，使硬质相粉末颗粒表面包覆一层Ti(OH)4，将混合物进行真空干燥，干燥温度为150～200℃，保温时间1～3h，从而在含DLC功能层的硬质相粉末颗粒表面制备出TiO2保护层，其DLC功能层和TiO2保护层含量分别占硬质相粉末颗粒总重量的1~2wt.%和3~6wt.%；
（5）基于DLC的球形粉末喂料制备：按含有TiO2保护层和DLC功能层的硬质相粉末占65~80wt.%，Co粉占0~20%wt.%，Ni粉占0~20%wt.%，Cr粉占0~10wt.%，Mo2C粉占4~6wt.%称取原料粉末，加入无水乙醇和熔化后的石蜡成型剂，并在行星球磨机中混合12h；然后采用喷雾干燥制粒形成球形粉末团聚体，将球形粉末团聚体放入石墨盒中并在真空烧结炉中1100~1200℃保温1~2h完成固相烧结，烧结后的粉末中sp2/sp3比不变；经过破碎和气流分级，制得粒度为40~55μm的基于DLC的球形粉末喂料，喂料的物相组成为硬质相+自润滑相+金属相+保护相+第二相，其中硬质相为WC或Cr3C2，自润滑相为DLC，保护相为TiO2，第二相为Mo2C；
（6）基于DLC的硬密封球阀用高耐磨低摩擦涂层材料制备：基于DLC的球形粉末喂料在硬密封球阀的球体和阀座表面进行超音速火焰喷涂，喷涂时氧气流量900~1000L/min，煤油流量0.35~0.4L/min，喷距300~400mm，送粉率65~85g/min；喷涂后包覆在DLC表面的TiO2层与Mo2C发生固溶反应形成(Ti，Mo)C固溶体界面相，提高了涂层中的硬质相与金属相的界面润湿性和界面结合力，降低涂层孔隙，同时界面相对DLC层起到保护作用，DLC未发生石墨化和氧化，其sp2/sp3比不变，其余为硬质相和金属相；将球体和阀座进行对研后即完成基于DLC的硬密封球阀用高耐磨低摩擦涂层制备。
本发明的基于DLC的硬密封球阀用高耐磨低摩擦涂层材料的制备方法，其进一步的特征在于：
（1）硬质相粉体颗粒分散系配制中，超声分散处理时的超声频率和功率分别为40kHz和100W；
（2）硬质相粉体沉降控制中，静置时间30~60min；
（3）硬质相粉体颗粒表面DLC功能层制备时的搅拌速率为100~200r/min；干燥真空度为1~10Pa；
（4）硬质相粉末颗粒表面保护层制备时的搅拌速率为100~200r/min；干燥真空度为1~10Pa；
（5）基于DLC的球形粉末喂料制备时，行星球磨机中无水乙醇和石蜡成型剂的加量与原料粉末的质量比分别0.3:1和0.02:1，球磨机转速为250r/min；喷雾干燥时雾化盘转速4000~7000r/min，干燥温度为110~130℃；固相烧结时的真空度为1~5Pa；
（6）基于DLC的硬密封球阀用高耐磨低摩擦涂层材料制备中，对研后的阀球和阀座表面粗糙度为Ra0.1~0.2μm。
本发明的优点在于：
（1）本发明通过热喷涂控制直接制备出含DLC的硬密封球阀用高耐磨低摩擦涂层材料，解决了现有技术需要先进行热喷涂再进行物理气相沉积，工艺复杂，对设备要求高的问题。
（2）本发明制备的硬密封球阀用高耐磨低摩擦涂层是由DLC自润滑相与硬质相、粘结相共同组成的单层复合涂层，而现有技术是多层复合涂层，多层复合涂层存在着层间界面结合问题，表面的DLC层与过渡层及基体之间的热学和力学性质差异较大，涂层易剥落。
（3）本发明中DLC表面TiO2保护层在喷涂中形成(Ti，Mo)C相，既能提高硬质相与粘结相的润湿性，又能保护DLC层不发生石墨化和氧化。
（4）本发明中利用液相中间歇沉降沉积的模式在碳化物硬质相粉末表面沉积DLC，最终形成的涂层中DLC相位于(Ti，Mo)C相和碳化物相之间，与传统的DLC与金属或金属陶瓷接触形成的界面相比，相间结合力更好。
（5）本发明的硬密封球阀用高耐磨低摩擦涂层材料的使用温度范围为-196~660℃，最大工作压力45MPa，在恶劣工况中固体润滑相稳定，在宽温域具有高的耐磨性和低摩擦系数。
附图说明
图1本发明的基于DLC的硬密封球阀用高耐磨低摩擦涂层材料制备方法示意图。
具体实施方式
实施例1：
一种基于DLC的硬密封球阀用高耐磨低摩擦涂层材料，该涂层材料的原料组成为含有TiO2保护层和DLC功能层的WC硬质相粉末占80wt.%，Co粉占10%wt.%，Ni粉占2%wt.%，Cr粉占4wt.%，Mo2C粉占4wt.%；涂层原料中WC粒度为3μm，Co粒度为1.2μm，Ni粒度为1.5μm,Cr粒度为3μm，Mo2C粒度为2.5μm；DLC功能层包覆于硬质相粉末表面，DLC功能层的sp2/sp3 =0.3，DLC含量占硬质相粉末颗粒总重量的1.1%，TiO2保护层包覆于DLC功能层表面，TiO2含量占硬质相粉末颗粒总重量的3.4%；超音速火焰喷涂后涂层的物相组成为硬质相（WC或Cr3C2）+自润滑相（DLC）+金属相（Co-Ni-Cr固溶体）+界面相（即(Ti，Mo)C固溶体相），其中界面相位于硬质相与金属相界面，自润滑相DLC的sp2/sp3 =0.3；涂层孔隙率0.18%，涂层的厚度为260μm，涂层的摩擦系数为0.11；本涂层的工作温度范围为-196~660℃，最大工作压力45MPa；涂层硬度1720HV，涂层结合强度88MPa。
如图1所示，该涂层的制备方法和步骤如下：
（1）硬质相粉体分散系配制：将乙醇与去离子水按体积比10:1配置成混合液，然后将粒度为3μm的WC硬质相粉末加入其中，硬质相粉体占10~20wt.%，进行超声分散处理35min，超声分散处理时的超声频率和功率分别为40kHz和100W，从而配制出硬质相粉体分散系；
（2）硬质相粉体沉降控制：将超声分散处理后硬质相粉体分散系倒入电沉积槽中，电沉积槽中阳极为高纯石墨板并固定于电沉积槽的上部，阴极为钛合金板并固定在电沉积槽的底部，阳极与阴极之间平行且距离为8mm；加入HCOOH调节pH值到3，溶液Zeta电位控制在-6mv，静置35min后使硬质相粉体沉降于阴极板上方，沉降层厚度0.8cm；
（3）硬质相粉体颗粒表面DLC功能层制备：接通电沉积槽中阴极和阳极的高压直流电源，控制电压600V，使乙醇发生极化，其甲基基团阳离子作为碳源并向阴极靠近，在阴极发生放电反应形成DLC并沉积在硬质相粉体颗粒表面；沉积时恒温水浴温度控制在30℃，按“沉积DLC(2min)—搅拌(1min，搅拌速率为110r/min)—粉体沉降（5min)”的循环周期变化的方式进行间歇沉降沉积，沉降和搅拌时切断高压直流电源，接通高压直流电源时不搅拌，沉积总时间6h；沉积结束后的粉末在90℃进行真空干燥，干燥真空度为2Pa；即在硬质相粉末颗粒表面制备出了sp2/sp3 =0.3的DLC功能层；
（4）含DLC功能层的硬质相粉末颗粒表面TiO2保护层制备：按体积比1:5将钛酸丁脂和无水乙醇混合并搅拌10min形成溶液A；按体积比将1:1将无水乙醇和去离子水混合，并滴加HNO3至pH值为3，搅拌10min后形成溶液B；按体积比2:1分别量取A液和B液，并在室温下将A液滴加到B液中，搅拌3h形成Ti(OH)4溶胶；称取表面包覆了DLC功能层的硬质相粉末颗粒并加入到Ti(OH)4溶胶中形成混合物，按重量百分比表面包覆了DLC功能层的硬质相粉末颗粒占20%，将混合物进行搅拌2h，使硬质相粉末颗粒表面包覆一层Ti(OH)4；上述过程中的搅拌速率均为120r/min；将混合物进行真空干燥，干燥温度为150℃，保温时间1h，干燥真空度为2Pa；从而制备出了含有1.1wt.%的DLC功能层和3.4wt.%的TiO2保护层的硬质相粉末颗粒；
（5）基于DLC的球形粉末喂料制备：按含有TiO2保护层和DLC功能层的WC硬质相粉末占80wt.%，Co粉占10%wt.%，Ni粉占2%wt.%，Cr粉占4wt.%，Mo2C粉占4wt.%称取原料粉末，加入无水乙醇和熔化后的石蜡成型剂，并在行星球磨机中混合12h，球磨机转速为250r/min，行星球磨机中无水乙醇和石蜡成型剂的加量与原料粉末的质量比分别0.3:1和0.02:1；然后采用喷雾干燥制粒形成球形粉末团聚体，喷雾干燥时雾化盘转速6000r/min，干燥温度为120℃；固相烧结时的真空度为2Pa；将球形粉末团聚体放入石墨盒中并在真空烧结炉中1150℃保温2h完成固相烧结，烧结后的粉末中sp2/sp3比不变；经过破碎和气流分级，制得粒度为45μm的基于DLC的球形粉末喂料，喂料的物相组成为硬质相（WC）+自润滑相（DLC）+金属相（Co、Ni、Cr）+保护相（TiO2）+第二相（Mo2C）；
（6）基于DLC的硬密封球阀用高耐磨低摩擦涂层制备：基于DLC的球形粉末喂料在硬密封球阀的球体和阀座表面进行超音速火焰喷涂，喷涂时氧气流量900L/min，煤油流量0.35L/min，喷距320mm，送粉率65g/min；喷涂后Mo2C与包覆在DLC表面的TiO2层发生固溶反应形成(Ti，Mo)C固溶体界面相，提高了涂层中的硬质相与金属相的界面润湿性和界面结合力，降低涂层孔隙，涂层孔隙率0.18%，同时界面相对DLC层起到保护作用，喷涂后DLC未发生石墨化和氧化，其sp2/sp3比不变，仍为0.3；涂层的厚度为260μm，涂层中物相组成为硬质相（WC）+自润滑相（DLC）+金属相（Co-Ni-Cr固溶体）+固溶体界面相（即(Ti，Mo)C相），涂层的摩擦系数为0.11；将球体和阀座进行对研，对研后的阀球和阀座表面粗糙度为Ra0.1μm，即完成基于DLC的硬密封球阀用高耐磨低摩擦涂层制备。
实施例2：
一种基于DLC的硬密封球阀用高耐磨低摩擦涂层材料，该涂层材料的原料组成为Cr3C2硬质相粉末占69wt.%，Ni粉占20%wt.%，Cr粉占5wt.%，Mo2C粉占6wt.%；涂层原料中为Cr3C2粒度为5μm，Ni粒度为1.6μm,Cr粒度为3.2μm，Mo2C粒度为2.6μm，DLC功能层包覆于硬质相粉末表面，DLC功能层的sp2/sp3 =0.4，DLC含量占硬质相粉末颗粒总重量的1.7%，TiO2保护层包覆于DLC功能层表面，TiO2含量占硬质相粉末颗粒总重量的5.2%；超音速火焰喷涂后涂层的物相组成为硬质相（WC或Cr3C2）+自润滑相（DLC）+金属相（Ni-Cr固溶体）+界面相（即(Ti，Mo)C相固溶体），其中界面相位于硬质相与金属相界面，自润滑相DLC的sp2/sp3 =0.4；涂层孔隙率0.31%，涂层的厚度为190μm，涂层的摩擦系数为0.12；本涂层的工作温度范围为-196~660℃，最大工作压力45MPa；涂层硬度1350HV，涂层结合强度86MPa。
该涂层的制备方法和步骤如下：
（1）硬质相粉体分散系配制：将乙醇与去离子水按体积比10:1配置成混合液，然后将粒度为5μm的Cr3C2硬质相粉末加入其中，硬质相粉体占20wt.%，进行超声分散处理50min，超声分散处理时的超声频率和功率分别为40kHz和100W，从而配制出硬质相粉体分散系；
（2）硬质相粉体沉降控制：将超声分散处理后硬质相粉体分散系倒入电沉积槽中，电沉积槽中阳极为高纯石墨板并固定于电沉积槽的上部，阴极为钛合金板并固定在电沉积槽的底部，阳极与阴极之间平行且距离为12mm；加入HCOOH调节pH值到4，溶液Zeta电位控制在-20mv，静置50min后使硬质相粉体沉降于阴极板上方，沉降层厚度0.7cm；
（3）硬质相粉体颗粒表面DLC功能层制备：接通电沉积槽中阴极和阳极的高压直流电源，控制电压1000V，使乙醇发生极化，其甲基基团阳离子作为碳源并向阴极靠近，在阴极发生放电反应形成DLC并沉积在硬质相粉体颗粒表面；沉积时恒温水浴温度控制在50℃，按“沉积DLC(4min)—搅拌(1min，搅拌速率为180r/min)—粉体沉降（10min)”的循环周期变化的方式进行间歇沉降沉积，沉降和搅拌时切断高压直流电源，接通高压直流电源时不搅拌，沉积总时间7h；沉积结束后的粉末在95℃进行真空干燥，干燥真空度为8Pa；即在硬质相粉末颗粒表面制备出了sp2/sp3 =0.4的DLC功能层；
（4）含DLC功能层的硬质相粉末颗粒表面TiO2保护层制备：按体积比1:6将钛酸丁脂和无水乙醇混合并搅拌10min形成溶液A；按体积比将1:1将无水乙醇和去离子水混合，并滴加HNO3至pH值为4，搅拌10min后形成溶液B；按体积比3:1分别量取A液和B液，并在室温下将A液滴加到B液中，搅拌4h形成Ti(OH)4溶胶；称取表面包覆了DLC功能层的硬质相粉末颗粒并加入到Ti(OH)4溶胶中形成混合物，按重量百分比表面包覆了DLC功能层的硬质相粉末颗粒占25%，将混合物进行搅拌3h，使硬质相粉末颗粒表面包覆一层Ti(OH)4；上述过程中的搅拌速率均为200r/min；将混合物进行真空干燥，干燥温度为200℃，保温时间3h，干燥真空度为8Pa；从而制备出了含有1.7wt.%的DLC功能层和5.2wt.%的TiO2保护层的硬质相粉末颗粒；
（5）基于DLC的球形粉末喂料制备：按含有TiO2保护层和DLC功能层的Cr3C2硬质相粉末占69wt.%，Ni粉占20%wt.%，Cr粉占5wt.%，Mo2C粉占6wt.%称取原料粉末，加入无水乙醇和熔化后的石蜡成型剂，并在行星球磨机中混合12h，球磨机转速为250r/min，行星球磨机中无水乙醇和石蜡成型剂的加量与原料粉末的质量比分别0.3:1和0.02:1；然后采用喷雾干燥制粒形成球形粉末团聚体，喷雾干燥时雾化盘转速5000r/min，干燥温度为130℃；固相烧结时的真空度为2Pa；将球形粉末团聚体放入石墨盒中并在真空烧结炉中1200℃保温2h完成固相烧结，烧结后的粉末中sp2/sp3比不变；经过破碎和气流分级，制得粒度为50μm的基于DLC的球形粉末喂料，喂料的物相组成为硬质相（Cr3C2）+自润滑相（DLC）+金属相（Ni、Cr）+保护相（TiO2）+第二相（Mo2C）；
（6）基于DLC的硬密封球阀用高耐磨低摩擦涂层制备：基于DLC的球形粉末喂料在硬密封球阀的球体和阀座表面进行超音速火焰喷涂，喷涂时氧气流量1000L/min，煤油流量0.38L/min，喷距400mm，送粉率75g/min；喷涂后Mo2C与包覆在DLC表面的TiO2层发生固溶反应形成(Ti，Mo)C固溶体界面相，提高了涂层中的硬质相与金属相的界面润湿性和界面结合力，降低涂层孔隙，涂层孔隙率0.31%，同时界面相对DLC层起到保护作用，喷涂后DLC未发生石墨化和氧化，其sp2/sp3比不变，仍为0.4；涂层的厚度为190μm，涂层中物相组成为硬质相（Cr3C2）+自润滑相（DLC）+金属相（Ni-Cr固溶体）+界面相（即(Ti，Mo)C相固溶体）；涂层的摩擦系数为0.12，将球体和阀座进行对研，对研后的阀球和阀座表面粗糙度为Ra0.2μm，即完成基于DLC的硬密封球阀用高耐磨低摩擦涂层制备。
Claims (3)
1.一种基于DLC的硬密封球阀用高耐磨低摩擦涂层材料，其特征在于，该涂层材料的原料组成为含有TiO2保护层和DLC功能层的硬质相粉末占65~80wt.%，Co粉占0~20%wt.%，Ni粉占0~20%wt.%，Cr粉占0~10wt.%，Mo2C粉占4~6wt.%；含有TiO2保护层和DLC功能层的硬质相粉末中，硬质相粉末为WC或Cr3C2，涂层原料中WC粒度为1~6μm，Cr3C2粒度为2~8μm，其余原料的粒度为1~5μm，DLC功能层包覆于硬质相粉末表面，DLC功能层的sp2/sp3=0.3~0.5，DLC含量占硬质相粉末颗粒总重量的1~2%，TiO2保护层包覆于DLC功能层表面，TiO2含量占硬质相粉末颗粒总重量的3~6%；超音速火焰喷涂后涂层的物相组成为硬质相+自润滑相+金属相+界面相，其中硬质相为WC或Cr3C2，自润滑相为DLC，金属相为金属固溶体，界面相为(Ti，Mo)C固溶体相，界面相位于硬质相与金属相界面，DLC的sp2/sp3 =0.3~0.5，该值在喷涂前后保持不变；超音速火焰喷涂后涂层孔隙率0.1~0.5%，涂层的厚度为150~350μm，涂层的摩擦系数为0.1~0.15；本涂层的工作温度范围为-196~660℃，最大工作压力45MPa，涂层硬度1200~2200HV，涂层结合强度85~95MPa。
2.一种基于DLC的硬密封球阀用高耐磨低摩擦涂层材料的制备方法，用于制备如权利要求1所述的一种基于DLC的硬密封球阀用高耐磨低摩擦涂层材料，其特征在于，依次包含以下步骤：
（1）硬质相粉体分散系配制：将乙醇与去离子水按体积比10:1配置成混合液，然后将WC或Cr3C2硬质相粉末加入其中，硬质相粉体占10~20wt.%，进行超声分散处理30~60min从而配制出硬质相粉体分散系；
（2）硬质相粉体沉降控制：将超声分散处理后硬质相粉体分散系倒入电沉积槽中，电沉积槽中阳极为高纯石墨板并固定于电沉积槽的上部，阴极为钛合金板并固定在电沉积槽的底部，阳极与阴极之间平行且距离为5~15mm；加入HCOOH调节pH值到3~5，溶液Zeta电位控制在-5~-20mv,静置后使硬质相粉体沉降于阴极板上方，沉降层厚度≦1cm；
（3）硬质相粉体颗粒表面DLC功能层制备：接通电沉积槽中阴极和阳极的高压直流电源，控制电压500V~1000V，使乙醇发生极化，其甲基基团阳离子作为碳源并向阴极靠近，在阴极发生放电反应形成DLC并沉积在硬质相粉体颗粒表面；沉积时恒温水浴温度控制在30~50℃，按“沉积DLC 2~4 min—搅拌1 min—粉体沉降5~10min”的循环周期变化的方式进行间歇沉降沉积，沉降和搅拌时切断高压直流电源，接通高压直流电源时不搅拌，沉积总时间6~8h；沉积结束后的粉末在90℃~100℃进行真空干燥，即在硬质相粉末颗粒表面制备出了sp2/sp3 =0.3~0.5的DLC功能层；
（4）含DLC功能层的硬质相粉末颗粒表面TiO2保护层制备：按体积比1:（5~6）将钛酸丁脂和无水乙醇混合并搅拌10min形成溶液A；按体积比将1:1将无水乙醇和去离子水混合，并滴加HNO3至pH值为3~4，搅拌10min后形成溶液B；按体积比(2~3):1分别量取A液和B液，并在室温下将A液滴加到B液中，搅拌3~4h形成Ti(OH)4溶胶；称取表面包覆了DLC功能层的硬质相粉末颗粒并加入到Ti(OH)4溶胶中形成混合物，按重量百分比表面包覆了DLC功能层的硬质相粉末颗粒占20~30%，将混合物进行搅拌2~3h，使硬质相粉末颗粒表面包覆一层Ti(OH)4，将混合物进行真空干燥，干燥温度为150～200℃，保温时间1～3h，从而在含DLC功能层的硬质相粉末颗粒表面制备出TiO2保护层，其DLC功能层和TiO2保护层含量分别占硬质相粉末颗粒总重量的1~2wt.%和3~6wt.%；
（5）基于DLC的球形粉末喂料制备：按含有TiO2保护层和DLC功能层的硬质相粉末占65~80wt.%，Co粉占0~20%wt.%，Ni粉占0~20%wt.%，Cr粉占0~10wt.%，Mo2C粉占4~6wt.%称取原料粉末，加入无水乙醇和熔化后的石蜡成型剂，并在行星球磨机中混合12h；然后采用喷雾干燥制粒形成球形粉末团聚体，将球形粉末团聚体放入石墨盒中并在真空烧结炉中1100~1200℃保温1~2h完成固相烧结，烧结后的粉末中sp2/sp3比不变；经过破碎和气流分级，制得粒度为40~55μm的基于DLC的球形粉末喂料，喂料的物相组成为硬质相+自润滑相+金属相+保护相+第二相，其中硬质相为WC或Cr3C2，自润滑相为DLC，保护相为TiO2，第二相为Mo2C；
（6）基于DLC的硬密封球阀用高耐磨低摩擦涂层材料制备：基于DLC的球形粉末喂料在硬密封球阀的球体和阀座表面进行超音速火焰喷涂，喷涂时氧气流量900~1000L/min，煤油流量0.35~0.4L/min，喷距300~400mm，送粉率65~85g/min；喷涂后包覆在DLC表面的TiO2层与Mo2C发生固溶反应形成(Ti，Mo)C固溶体界面相，提高了涂层中的硬质相与金属相的界面润湿性和界面结合力，降低涂层孔隙，同时界面相对DLC层起到保护作用，DLC未发生石墨化和氧化，其sp2/sp3比不变，其余为硬质相和金属相；将球体和阀座进行对研后即完成基于DLC的硬密封球阀用高耐磨低摩擦涂层制备。
3.根据权利要求2所述的基于DLC的硬密封球阀用高耐磨低摩擦涂层材料的制备方法，其特征在于：
（1）硬质相粉体颗粒分散系配制中，超声分散处理时的超声频率和功率分别为40kHz和100W；
（2）硬质相粉体沉降控制中，静置时间30~60min；
（3）硬质相粉体颗粒表面DLC功能层制备时的搅拌速率为100~200r/min；干燥真空度为1~10Pa；
（4）硬质相粉末颗粒表面保护层制备时的搅拌速率为100~200r/min；干燥真空度为1~10Pa；
（5）基于DLC的球形粉末喂料制备时，行星球磨机中无水乙醇和石蜡成型剂的加量与原料粉末的质量比分别0.3:1和0.02:1，球磨机转速为250r/min；喷雾干燥时雾化盘转速4000~7000r/min，干燥温度为110~130℃；固相烧结时的真空度为1~5Pa；
（6）基于DLC的硬密封球阀用高耐磨低摩擦涂层材料制备中，对研后的阀球和阀座表面粗糙度为Ra0.1~0.2μm。
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