CN106637093A - 多元多层纳米膜粉末冶金气门座及其制备方法 - Google Patents
多元多层纳米膜粉末冶金气门座及其制备方法 Download PDFInfo
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Abstract
多元多层纳米膜粉末冶金气门座，应用多弧离子镀（AIP）设备，将炉内温度控制在100‑300℃，采用多弧离子镀多层纳米膜制备工艺，在气门座工作表面生成单层膜（TiN、CrN）、复合膜（TiCr）N和多层膜（TiN－CrN）。制备方法：基础粉末采用高压水雾化制备的低合金粉末+配方量的高合金粉末，经过混料机混合均匀，在自动粉末成型机进行压制成型，之后置入推杆式烧结炉，在氨分解气氛中进行烧结。采用铜溶浸工艺，再将经过金加工的气门座（工件）置入多弧离子镀（AIP）设备进行涂层处理，产品薄膜多层化及添加其它元素。本发明制得的产品具有优良的结合强度，表面显微硬度、耐磨性和抗高温氧化性能，且可大幅度延长使用寿命。
Description
技术领域
本发明属于冶金技术领域，将予合金化粉末进行压制、烧结、机械加工和多弧离子镀膜，制得汽车零部件的冶金领域。
背景技术
气门座是汽车发动机配气机构中的重要部件，它与气门组成一对重要密封磨擦付，发动机工作时，气门座受到气门冲击，高温（530～870℃）燃烧气体的冲刷、腐蚀、以及燃烧产物、空气中灰尘的磨损，另外还受到热冷应力交替作用，它极易产生变形、烧损，甚至断裂，因此不但要求气门座材料耐磨、耐腐蚀、抗高温，还要求一定径向压溃强度。
发动机气门和气门座处于严酷的热力，化学和机械力状况下工作，其承受着高应力（发动机最高燃烧压力可达20MPa）、高工作温度（气门头低平面中心达870℃）和腐蚀环境（高温燃气侵蚀、硫化、V2O5）腐蚀和氧化作用。
根据上述气门座的工作环境，为保证其工作可靠性和使用寿命，在不同的工作环境和燃用不同燃料的情况下，必须尽快开发研究新材料和新工艺。
发明内容
本发明的目的是提供一种多元多层纳米膜粉末冶金气门座及其制备方法，本发明大大提高了基材的表面显微硬度，膜的致密度高，强度和耐磨性能好，且可大幅度延长使用寿命。
本发明的第一个目的是是通过以下技术方案实现的，实现本发明的技术解决方案：应用多弧离子镀（AIP）设备，将炉内温度限于小于300℃的工作条件下，采用《多弧离子镀多层纳米膜制备技术》，在气门座表面生成由氮化铬和氮化钛相间层叠而成的多元多层纳米膜（11-12层）形成的耐磨层。
本发明所应用的多弧离子镀（AIP）设备，为中科院力学所研制。该设备可制备单层膜（TiN、CrN）、复合膜（TiCr）N、（TiAI）N或多层膜（TiN-CrN），具有12个靶位，并采用计算机控制系统（PLC+I控机），转速可平衡调节的工件转动系统，以及过滤阴极电弧工作方式，以保证涂层细密、均匀，将“多弧离子镀多层纳米膜制备技术”应用到气门座上，系物理气相沉积技术：集电子物理、材料、真空控制技术于一体的高新技术。
本发明的第二个目的是通过以下技术方案实现的，多元多层纳米膜粉末冶金气门座的制备方法，包括以下步骤：
①首先选择经过高压水雾化低合金粉末为基础粉末，再添加合金粉，经过混料机40-50分钟混合均匀，在自动粉末成型机上进行压制成型；
②将压制成型的气门座生坯置入推杆式烧结炉，在氨分解气氛中进行烧结，烧结温度1100-1500℃，烧结时间50-60分钟；采用铜溶浸工艺，使烧结坯密度≥7.6g/㎝3，烧结坯硬度HRC≥35；所述烧结坯包括以下组分：C 0.8-1.2wt%，Cr 4.0-6.0wt%，Mo 5.0-7.0wt%，Ni1.0-2.0wt%，Co 0.2-0.5wt%，Cu 12-30wt%，纳米Fe 0.1-0.3wt%，余量为Fe；
③将经过金属切削加工气门座烧结坯置入多弧离子镀AIP设备进行涂层处理，将炉内温度控制在100-300℃，阴极材料采用钛、铬、钴或钒金属，反应气体为氮气和碳氢化合物气体，真空室接地作阳极，真空室内采用真空弧光放电，在阴极材料表面产生多弧光辉点，使阴极材料蒸发，形成原子和离子；在电场作用下，原子和离子高速轰击气门座工作表面，与此同时，高真空室通入反应气体，即可在气门座工作表面生成多元多层纳米膜涂层。
优选的，所述多元多层纳米膜粉末冶金气门座纳米膜表面显微硬度，即HV（0.050）为1100-2500，纳米膜总厚4-6um，纳米膜共计11-12层，纳米膜基结合力：≥30N。
与现有技术相比，本发明具有以下有益效果：
（1）涂层TiN和CrN膜层交替生成（至少11层，也可以为双数层），膜层总厚度可达4-6um,大大提高了基材的表面显微硬度，其磨损量在各种温度下，可远远低于现有技术的磨损量。
（2）涂层结构采用多元多层纳米级薄膜层—层间及膜—基间有很高的结合力。
（3）设计多层纳米级薄膜最外层为氮化铬膜层。经研究和实验表明，其摩擦系数在低温时略高于现有技术的摩擦系数，而在高温下低于现有技术的摩擦系数，对于粉末冶金气门座所处工况条件，具有十分重要意义。
（4）多弧离子镀工作原理如下：有空室接地作阳极，弧电源是具有徒降伏—安特性的低电压，大电流电源。在真空室内采用真空弧光放电技术，在阴材料表面产生许多弧光辉点，使阴极材料蒸发，形成原子和离子。在电场作用下，原子和离子轰击表面，与此同时高真空室通入反应气体，即可在工作表面生成性能优良的涂层。阴极材料（也称靶材）一般采用钛、铬、锆、钴、铝、钒等金属，通常反应气体为氮气和碳氢化合物气体。多弧型离子沉积除具有离子沉积的特点外，还有其独特之处。电弧蒸发无熔池的特点，靶可任意放在真空室内任何位置，使其能量的粒子呈多方向运动，大大简化了夹具，涂层的均匀性得到保证。入射粒子能量高，膜的致密度高，强度和耐磨性能好。工件与膜面有原子扩散，因而膜的附着力高。离化率高，又高达80%以上。镀膜速率高。
附图说明
图1是多弧离子镀原理图；
图2是本发明制得的01号气门座11层多层膜形貌图；
图3是本发明制得的02号气门座11层多层膜形貌图；
图4是本发明制得的01号气门座12层多层膜形貌图；
图5是本发明制得的02号气门座12层多层膜形貌图。
具体实施方式
下面结合实施例对本发明做进一步详细描述：
实施例：
一种多元多层纳米膜粉末冶金气门座，将炉内温度限于小于300℃的工作条件下，应用多弧离子镀设备，采用《多弧离子镀多层纳米膜制备技术》，在粉末冶金气门座表面生成由氮化铬、氮化钛相间层叠而成的多元多层纳米膜（11-12层）形成的耐磨层。多弧离子镀设备工作原理见图1。
（1）本发明专利产品经扬州市产品质量监督所检测，技术指标符合企业标准Q/321081JQ19001和主品图样要求。
（2）本发明专利产品通过沈阳博龙汽车部件制造有限公司生产的4G6汽油发动机（额定转速5000r/min，最大功率99KW）配套使用，通过500小时全速全负荷台架试验。
用户意见如下：本发明专利技术生产的4G6粉末冶金气门座在我公司已通过各项性能试验，试验认可，性能指标达到设计要求，可以投入批量生产。
（3）本发明专利产品多元多层纳米膜的形貌和厚度采用（日）S-450型扫描电子显微镜观察多元多层纳米膜的形貌。图2-图5是CrN –TiN- CrN多元多层纳米膜的形貌图，分为11层和12层二种，其中11层的多元多层纳米膜存度为4-5.2μm，12层的多元多层纳米膜存度为4-6μm。由图2-5可见，膜层之间结合致密，涂层与基体间结合良好。采用X射线衍射仪测定多元多层纳米膜的组成相。相分析结果表明：在气门座生成多元多层纳米膜，其表面层的组成相相同。
产品薄膜多层化及添加其它合金元素，其特点为具有优良的结合强度、表面硬度、耐磨性和抗高温抗氧化性能。产品的主要用途：为汽车发动机（汽油机、柴油机）及摩托车、工程车发动机配套。与有技术产品相比，具有节能、环保等功能，且可大幅度延长使用寿命，是一种新型节能环保产品。
Claims (3)
1.多元多层纳米膜粉末冶金气门座，其特征在于：应用多弧离子金属AIP设备，将炉内温度控制在100-300℃，采用多弧离子镀多层纳米膜制备工艺，在气门座工作表面生成单层膜TiN或CrN、复合膜（TiCr）N或多层膜TiN－CrN，具有12个靶位。
2.权利要求1所述的多元多层纳米膜粉末冶金气门座的制备方法，其特征是，所述制备方法包括以下步骤：
①首先选择经过高压水雾化低合金粉末为基础粉末，再添加合金粉，经过混料机40-50分钟混合均匀，在自动粉末成型机上进行压制成型；
②将压制成型的气门座生坯置入推杆式烧结炉，在氨分解气氛中进行烧结，烧结温度1100-1500℃，烧结时间50-60分钟；采用铜溶浸工艺，使烧结坯密度≥7.6g/㎝3，烧结坯硬度HRC≥35；所述烧结坯包括以下组分：C 0.8-1.2wt%，Cr 4.0-6.0wt%，Mo 5.0-7.0wt%，Ni1.0-2.0wt%，Co 0.2-0.5wt%，Cu 12-30wt%，纳米Fe 0.1-0.3wt%，余量为Fe；
③将经过金属切削加工气门座烧结坯置入多弧离子镀AIP设备进行涂层处理，将炉内温度控制在100-300℃，阴极材料采用钛、铬、钴或钒金属，反应气体为氮气和碳氢化合物气体，真空室接地作阳极，真空室内采用真空弧光放电，在阴极材料表面产生多弧光辉点，使阴极材料蒸发，形成原子和离子；在电场作用下，原子和离子高速轰击气门座工作表面，与此同时，高真空室通入反应气体，即可在气门座工作表面生成多元多层纳米膜涂层。
3.根据权利要求2所述的多元多层纳米膜粉末冶金气门座的制备方法，其特征是，所述多元多层纳米膜粉末冶金气门座纳米膜表面显微硬度，即HV（0.050）为1100-2500，纳米膜总厚4-6um，纳米膜共计11-12层，纳米膜基结合力：≥30N。
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