CN110424003A - 一种碳强化金属-陶瓷复合材料及其制备方法和用途 - Google Patents

一种碳强化金属-陶瓷复合材料及其制备方法和用途 Download PDF

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CN110424003A
CN110424003A CN201910696786.8A CN201910696786A CN110424003A CN 110424003 A CN110424003 A CN 110424003A CN 201910696786 A CN201910696786 A CN 201910696786A CN 110424003 A CN110424003 A CN 110424003A
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曾和平
黄延伟
贺嘉杨
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East China Normal University
Chongqing Institute of East China Normal University
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Abstract

本发明公开了一种碳强化金属‑陶瓷复合材料，其由按重量百分数计的如下原料制备而成：碳：5％～8％；铜：10％～15％；锌：10％～18％；钛：20％～33％；氧化铜：5％～8％；氧化钙：18％～35％；余量为二氧化钛。本发明本发明采用激光熔覆技术，在金属或合金基体上熔覆一层碳强化的金属‑陶瓷复合涂层，利用激光的快速冲击产生高热环境使部分氧化物还原为金属，进一步生成合金，同时与陶瓷成分共同作用，生成复合涂层，该激光熔覆涂层与基体呈冶金状结合，涂层的显微硬度提高，耐蚀耐磨性增强，同时涂层生成工艺过程简单、原料利用率高、无污染，适合作为防腐耐磨涂层。

Description

一种碳强化金属-陶瓷复合材料及其制备方法和用途
技术领域
本发明属于激光加工技术和无机功能涂层技术开发领域，具体涉及一种激光熔覆碳强化金属-陶瓷复合涂层。
背景技术
随着大功率激光器在工业工程上的应用越来越广泛，激光特种加工技术得到了迅猛发展，激光熔覆技术因其在表面工程领域中的突出优点而成为一种改善材料表面性能的有效手段。激光熔覆技术是以高能量密度激光束作用在放置于基体表面上的涂层材料，使之与基体表面薄层同时迅速熔化、扩展和快速凝固，最终在基体材料的表面上形成一层具有特殊物理、化学和力学性能并且与基体呈冶金状结合的熔覆层，具有耐磨、耐蚀、耐热、抗氧化、抗疲劳等特性，激光熔覆技术不仅实现了对基材进行表面改性和修复的目的，同时节约了成本，延长基材的使用寿命，具有稀释度小、组织致密、涂层与基体结合好、适合熔覆材料多、粒度及含量变化大等特点，应用前景十分广阔。近年来，随着激光熔覆技术的发展，激光熔覆材料也由原先的镍基、钴基、铁基合金材料向陶瓷材料乃至合金-陶瓷复合材料方向发展。金属-陶瓷复合涂层采用的原料粉末是一种介于合金粉末与陶瓷粉末之间的激光熔覆粉末材料，是指将具有特殊性能的陶瓷粉末和一定成分配比的金属或合金粉末进行比例混合，通过一系列复杂工艺得到的一种新型复合粉末。将新型功能复合粉末在基体材料上形成功能涂层，尤其是耐蚀耐磨涂层，常用的方法是涂装，即刷涂、刮涂、浸涂、喷涂，随着涂层的性能要求的不同、涂装环境不同选取的涂装方法也不同。将混合粉末利用粘结剂、分散剂混合后进行涂覆是最常见的简单易行的涂装方法，这种方法虽然操作灵活，对于小面积作业来说经济实用。但其缺点是耗费大量的人工成本，工作效率低下，不便于大面积作业，同时易造成开裂，脱落，翻卷等情况发生，尽管热喷涂技术进一步发展了涂层涂覆技术，但热喷涂厚度不均匀，与基体结合处容易萌生裂纹，原料消耗严重，污染空气，且不适合于以陶瓷成分为主的功能涂层。
发明内容
本发明的目的在于提出一种碳强化金属-陶瓷复合材料及其制备方法和用途，以解决现有技术中所存在的上述问题。
本发明是通过以下技术方案实现的：
一种碳强化金属-陶瓷复合材料，其由按重量百分数计的如下原料制备而成：
余量为二氧化钛。
一种如前述的碳强化金属-陶瓷复合材料的制备方法，其包括如下步骤：
将碳、铜粉、锌粉、钛粉、氧化铜、二氧化钛和氧化钙混合，进行球磨后，烘干、得到球磨料；
将所述球磨料在激光的辐照下进行反应后，控制在5min之内冷却至室温，得到所述碳强化金属-陶瓷复合材料。
作为优选方案，所述球磨的媒质为氧化锆球，球磨转速为400rpm，烘干温度为60～80℃。
作为优选方案，所述碳的来源为蔗糖、葡萄糖、有机溶剂碳、石墨粉、碳纳米材料、石墨烯中的至少一种。
作为优选方案，所述激光辐照的功率不低于100W。
作为优选方案，所述快速冷却是通过喷涂液氨或液氮实现的。
一种如权前述的碳强化金属-陶瓷复合材料在防护涂层中的用途。
本发明的实现原理为：
所述涂层是碳强化的金属-陶瓷复合涂层，金属成分指的是CuTi、Zn-Cu-Ti-Ca合金、 TiC等合金相，在复合涂层中充当粘结相，陶瓷成分指的是CuO、TiO2、CaTiO3、Zn2TiO4的复合材料，在涂层中充当硬质相，两相共同作用使涂层不仅具有金属材料的韧性，而且具有陶瓷材料的耐蚀耐磨的性质。
复合涂层体系为C-CuTi/Zn-Cu-Ti-Ca/TiC/-CuO-TiO2-CaTiO3-Zn2TiO4，在激光熔覆过程中，由于激光的快速热冲击，部分的金属氧化物发生了还原反应，如铜、钛从CuO、TiO2中还原析出，发生类似如下反应：3Cu2+→2Cu1++TiCu 4++Cu↑，由Ti4+离子占据原来铜离子的位置，同时高热的环境也使Cu+重新氧化成Cu2+，Ti4+还原成Ti的低价离子，如Ti3+，析出的金属成分在高温下发生合金化过程，形成了涂层的金属相。
与现有技术相比，本发明具有如下的有益效果：
本发明采用激光熔覆技术，在金属或合金基体上熔覆一层碳强化的金属-陶瓷复合涂层，利用激光的快速冲击产生高热环境使部分氧化物还原为金属，进一步生成合金，同时与陶瓷成分共同作用，生成复合涂层，该激光熔覆涂层与基体呈冶金状结合，涂层的显微硬度提高，耐蚀耐磨性增强，同时涂层生成工艺过程简单、原料利用率高、无污染，适合作为防腐耐磨涂层。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述，本发明的其它特征、目的和优点将会变得更明显：
图1激光熔覆金属-陶瓷复合涂层的流程图；
图2在铜基体上激光熔覆金属-陶瓷复合涂层材料。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
采用半导体激光器，波长980nm，功率350W，在铜基体表面激光熔覆碳强化的金属-陶瓷复合涂层，以石墨粉、铜粉、锌粉、钛粉、氧化铜(CuO)、纳米氧化钛(TiO2)、氧化钙(CaO)为激光熔覆原材料粉末，按原料质量百分比配比进行混合，石墨：8％，Cu: 10％,Zn:18％,Ti:25％,CuO:6％,CaO:25％,余量为TiO2，放入氧化锆球磨罐，进行高能湿法球磨混合，以无水乙醇为媒质，球磨转速为每分钟400转，球磨时间在24小时，取出后置于75℃的干燥箱里干燥得混合粉末，并将混合粉末进一步研磨均匀备用，将均匀打磨抛光的铜基体放置于激光熔覆设备上，采用预制原料法将球磨混合的原料粉末均匀覆盖于铜基体，控制激光输出功率350W，熔覆时间5min，然后冷却至室温，生成成分为C-CuTi/Zn-Cu-Ti-Ca/TiC/-CuO-TiO2-CaTiO3-Zn2TiO4的金属-陶瓷复合涂层。图1为激光熔覆金属-陶瓷复合涂层的流程图。该碳强化的金属-陶瓷复合涂层在5％H2SO4和在 20％的NaCl溶液中的耐腐蚀性能较传统的T10钢防腐材料提高了10倍。
实施例2
采用半导体激光器，波长980nm，功率500W，在铜基体表面激光熔覆碳强化的金属-陶瓷复合涂层，以蔗糖、铜粉、锌粉、钛粉、氧化铜(CuO)、纳米氧化钛(TiO2)、氧化钙(CaO)为激光熔覆原材料粉末，按原料质量百分比配比进行混合，蔗糖：8％，Cu: 12％,Zn:18％,Ti:25％,CuO:8％,CaO:25％,余量为TiO2，放入氧化锆球磨罐，进行高能湿法球磨混合，以无水乙醇为媒质，球磨转速为每分钟400转，球磨时间在12小时，取出后置于70℃的干燥箱里干燥得混合粉末，并将混合粉末进一步研磨均匀备用，将均匀打磨抛光的铜基体放置于激光熔覆设备上，采用预制原料法将球磨混合的原料粉末均匀覆盖于铜基体，控制激光输出功率500W，熔覆时间8min，然后冷却至室温，生成成分为C-CuTi/Zn-Cu-Ti-Ca/TiC/-CuO-TiO2-CaTiO3-Zn2TiO4的金属-陶瓷复合涂层。该碳强化的金属-陶瓷复合涂层在10％H2SO4溶液中的耐腐蚀性能较传统的T10钢防腐材料提高了10倍以上。
实施例3
采用CO2激光器，波长1060nm，功率105W，在铜基体表面激光熔覆碳强化的金属-陶瓷复合涂层，以石墨粉、铜粉、锌粉、钛粉、氧化铜(CuO)、纳米氧化钛(TiO2)、氧化钙(CaO)为激光熔覆原材料粉末，按原料质量百分比配比进行混合，石墨：5％，Cu: 12％,Zn:18％,Ti:25％,CuO:6％,CaO:25％,余量为TiO2，放入氧化锆球磨罐，进行高能湿法球磨混合，以无水乙醇为媒质，球磨转速为每分钟400转，球磨时间在24小时，取出后置于75℃的干燥箱里干燥得混合粉末，并将混合粉末进一步研磨均匀备用，将均匀打磨抛光的铜基体放置于激光熔覆设备上，采用预制原料法将球磨混合的原料粉末均匀覆盖于铜基体，控制激光输出功率105W，熔覆时间5min，然后冷却至室温，生成成分为C-CuTi/Zn-Cu-Ti-Ca/TiC/-CuO-TiO2-CaTiO3-Zn2TiO4的金属-陶瓷复合涂层。图2为在铜基体上激光熔覆金属-陶瓷复合涂层材料。该碳强化的金属-陶瓷复合涂层在 5％H2SO4和在20％的NaOH溶液中的耐腐蚀性能较传统的T10钢防腐材料提高了10倍。
实施例4
采用CO2激光器，波长1060nm，功率300W，在铜基体表面激光熔覆碳强化的金属-陶瓷复合涂层，以石墨粉、铜粉、锌粉、钛粉、氧化铜(CuO)、纳米氧化钛(TiO2)、氧化钙(CaO)为激光熔覆原材料粉末，按原料质量百分比配比进行混合，石墨：5％，Cu: 10％,Zn:18％,Ti:25％,CuO:6％,CaO:25％,余量为TiO2，放入氧化锆球磨罐，进行高能湿法球磨混合，以无水乙醇为媒质，球磨转速为每分钟400转，球磨时间在24小时，取出后置于75℃的干燥箱里干燥得混合粉末，并将混合粉末进一步研磨均匀备用，将均匀打磨抛光的铜基体放置于激光熔覆设备上，采用预制原料法将球磨混合的原料粉末均匀覆盖于铜基体，控制激光输出功率300W，熔覆时间5min，然后冷却至室温，生成成分为C-CuTi/Zn-Cu-Ti-Ca/TiC/-CuO-TiO2-CaTiO3-Zn2TiO4的金属-陶瓷复合涂层。该碳强化的金属-陶瓷复合涂层在10％H2SO4和在20％的NaCl溶液中的耐腐蚀性能较传统的 T10钢防腐材料提高了10倍。
实施例5
采用半导体激光器，波长980nm，功率200W，在铜基体表面激光熔覆碳强化的金属-陶瓷复合涂层，以石墨粉、铜粉、锌粉、钛粉、氧化铜(CuO)、纳米氧化钛(TiO2)、氧化钙(CaO)为激光熔覆原材料粉末，按原料质量百分比配比进行混合，葡萄糖：5％， Cu:10％,Zn:18％,Ti:25％,CuO:6％,CaO:25％,余量为TiO2，放入氧化锆球磨罐，进行高能湿法球磨混合，以无水乙醇为媒质，球磨转速为每分钟400转，球磨时间在24小时，取出后置于75℃的干燥箱里干燥得混合粉末，并将混合粉末进一步研磨均匀备用，将均匀打磨抛光的铜基体放置于激光熔覆设备上，采用预制原料法将球磨混合的原料粉末均匀覆盖于铝合金基体，控制激光输出功率200W，熔覆时间5min，然后冷却至室温，生成成分为C-CuTi/Zn-Cu-Ti-Ca/TiC/-CuO-TiO2-CaTiO3-Zn2TiO4的金属-陶瓷复合涂层。该碳强化的金属-陶瓷复合涂层在5％H2SO4和在10％的NaOH溶液中的耐腐蚀性能较传统的T10钢防腐材料提高了10倍。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。

Claims (7)

1.一种碳强化金属-陶瓷复合材料，其特征在于，由按重量百分数计的如下原料制备而成：
余量为二氧化钛。
2.一种如权利要求1所述的碳强化金属-陶瓷复合材料的制备方法，其特征在于，包括如下步骤：
将碳、铜粉、锌粉、钛粉、氧化铜、二氧化钛和氧化钙混合，进行球磨后，烘干、得到球磨料；
将所述球磨料在激光的辐照下进行反应后，控制在5min之内冷却至室温，得到所述碳强化金属-陶瓷复合材料。
3.如权利要求2所述的碳强化金属-陶瓷复合材料的制备方法，其特征在于，所述球磨的磨球为氧化锆球，媒质为无水乙醇，球磨转速为400rpm，烘干温度为60～80℃。
4.如权利要求2所述的碳强化金属-陶瓷复合材料的制备方法，其特征在于，所述碳的来源为蔗糖、葡萄糖、有机溶剂碳、石墨粉、碳纳米材料、石墨烯中的至少一种。
5.如权利要求2所述的碳强化金属-陶瓷复合材料的制备方法，其特征在于，所述激光辐照的功率不低于100W，波长为980nm。
6.如权利要求2所述的碳强化金属-陶瓷复合材料的制备方法，其特征在于，所述快速冷却是通过喷涂液氨或液氮实现的。
7.一种如权利要求1所述的碳强化金属-陶瓷复合材料在防护涂层中的用途。
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