CN108048785A - 一种热喷涂氮化物增强高熵合金涂层的制备方法 - Google Patents
一种热喷涂氮化物增强高熵合金涂层的制备方法 Download PDFInfo
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Abstract
本发明公开了一种热喷涂制备氮化物增强高熵合金涂层的方法,采用等离子喷涂设备在低碳钢表面喷涂由一定比例的Al粉、Fe‑Cr‑B‑Si、Mn粉、Ni‑Cr‑B‑Si组成的混合粉末,在喷涂过程中由活性元素Cr、Al等与活化的N反应形成氮化物,该氮化物细小、弥散,然后沉积于碳钢表面制备氮化物增强的AlCrFeMnNi高熵合金涂层,涂层具有基本致密、空隙率小、耐磨性高的优点。
Description
技术领域
本发明属于高能束表面处理领域,特别涉及采用在低碳钢表面热喷涂制备耐磨复合涂层的方法。
背景技术
低碳钢的含碳量较低,具有较好塑性和韧性,冷成形性能良好,可采用卷边、折弯、冲压等方法进行冷成形,同时具有较低的强度和硬度,并且具有良好的焊接性,获得了广泛的应用。但因其表面硬度较低,耐磨性差,使低碳钢应用受到了一定的限制。通过提高其表面性能能够获得较好的耐磨性。高熵合金是由五个以上的元素组元按照等原子比或接近于等原子比合金化的合金,具有一些传统合金所无法比拟的优异机械性能,如高耐磨耐腐蚀性、高强度、高硬度、高韧性等,从而使其成为制作涂层的选择之一。采用等离子喷涂是将粉末材料送入等离子弧中,使粉末颗粒在其中加速、熔化或部分熔化后,利用冲击力的作用在基底上铺展并凝固形成层片,进而通过层片叠层形成涂层的一类加工工艺。它具有生产效率高、制备的涂层质量好、喷涂的材料范围广,成本低等优点。在喷涂过程中多使用便宜的氮气作为保护气,其具有成本低、热焓高、传热快等优点,利于喷涂粉末的加热和熔化,同时等离子有利于生成活化的N。本申请通过在喷涂粉中添加易于形成氮化物的合金元素,如Cr、Al,使其在喷涂过程中与活性的N元素反应,有利于进一步提高涂层的硬度。考虑到Ni、Cr的熔点较高,采用Ni-Cr-B-Si、Fe-Cr-B-Si合金粉作为Ni、Cr、Fe元素的替代物加入合金粉中,也有利于避免氧化及降低成本。而Al、Mn的熔点较低,采用等离子加热完全可以熔化,球磨混合后制备混合粉,经喷涂制备AlN、CrN增强的AlCrFeMnNi高熵合金涂层。
发明内容
本发明设计了由低熔点的自熔合金和单质金属粉组成的合金粉,在喷涂过程中不仅实现合金化,形成高熵合金,而且在喷涂过程中采用N2作为电离的气体,可以使其中的Cr、Al发生氮化物反应形成氮化物,并且由于时间短和熔融液滴的运动,该氮化物增强相细小,有利于进一步提高高熵合金基涂层的耐磨性。该工艺具备粉末制备简单、成本较低的优点。
本发明解决其技术问题所采用的制作方法包括下述工艺步骤:
步骤一、将Al粉、Fe-Cr-B-Si、Mn粉、Ni-Cr-B-Si合金粉按一定比例进行球磨混合制作喷涂粉,制作的粉末粒径20-50μm;其中Al粉、Fe-Cr-B-Si、Mn粉、Ni-Cr-B-Si合金粉的质量比为:10~20:26~30:26~30:26~30; Fe-Cr-B-Si成分的质量含量为Cr:16~18%,B:2.5~4.5%,Si:3~4.5%,其余为Fe;Ni-Cr-B-Si成分的质量含量为Cr:16~18%,B:2.5~4.5%,Si:3~4.5%,其余为Ni;Al、Mn粉的纯度高于99.5%,粒径在30-80μm。将上述金属粉末采用钢制球磨罐进行球磨混合,其中的磨球与金属粉质量比为2.7~3.2∶1,密封后打开真空阀抽真空20~30分钟,将球磨罐放入行星式球磨机,转速为 260~300 r/min,倒向频率 30~45 Hz,进行球磨混料时间为60~80分钟。
步骤二、选取将要强化的碳钢工件表面作为基体,对工件表面清除铁锈和油污,然后喷砂处理,粗化工件表面;最后采用外热方式对工件表面进行预热,预热温度控制在250~300℃;
步骤三、采用热喷涂的方式对工件表面预喷涂Ni-Al粘结层,粘结层厚度控制在30-100μm;Ni-Al合金粉末的粒度为80-240μm,其成分中含Al的质量为8~20%,其余为Ni。
步骤四、采用等离子设备按一定喷涂工艺参数加热混合的喷涂粉对工件表面进行热喷涂,冷却后即为耐磨涂层。喷涂的工艺参数分别为,喷涂距离:90-120mm,工作电流:500-700A,工作电压:50-70V,N2气速度:30-50 升/min,H2速度:5-10 升/min,送粉量:38±42g/min,冷却气压力:0.3-0.5MPa,喷枪移动速度:30-80mm/s。
本发明的有益效果是:
(1)本发明的工艺方法采用高熵合金作为耐磨涂层的基体,能够充分利用其特有的扩散速度慢、对成分变化不敏感的特性,使涂层具有更高的韧性、强度、耐磨性。
(2)本发明利用高温等离子使N2气分解活化,在喷涂过程中与Cr、Al等元素进行反应,由于氮化物反应时间短且反应物在运动,因此可以得到弥散细小的氮化物,与原先少量的硼化物等、高熵合金共同沉积于低碳钢表面,形成氮化物、硼化物增强的高熵合金涂层,该涂层呈层状结构,韧性高,耐磨性好。
具体实施方式
实施例1:
步骤一、将Al粉、Fe-Cr-B-Si、Mn粉、Ni-Cr-B-Si合金粉按一定比例混合,并用球磨机进行球磨混合制作喷涂粉,制作的粉末粒径20-30μm;其中Al粉、Fe-Cr-B-Si、Mn粉、Ni-Cr-B-Si合金粉的质量比为:20:27:27:26;Fe-Cr-B-Si成分的质量含量为Cr:16~18%,B:2.5~4.5%,Si:3~4.5%,其余为Fe; Ni-Cr-B-Si成分的质量含量为Cr:16~18%,B:2.5~4.5%,Si:3~4.5%,其余为Ni; Al、Mn粉的纯度高于99.5%,粒径在60-80μm。将上述金属粉末采用钢制球磨罐进行球磨混合,其中的磨球与金属粉质量比为2.7∶1,密封后打开真空阀抽真空20分钟,将球磨罐放入行星式球磨机,转速为300 r/min,倒向频率 30 Hz,进行球磨混料时间为80分钟。
步骤二、选取将要强化的Q235碳钢工件表面作为基体,对工件表面清除铁锈和油污,然后喷砂处理,粗化工件表面;最后采用外热方式对工件表面进行预热,预热温度控制在250℃;
步骤三、采用热喷涂的方式对工件表面预喷涂Ni-Al粘结层,粘结层厚度控制在50-80μm;Ni-Al合金粉末的粒度为80-240μm,其成分中含Al的质量为12%,其余为Ni。
步骤四、采用APS-2000A型大气等离子设备按一定喷涂工艺参数加热混合的喷涂粉对工件表面进行热喷涂,冷却后即为耐磨涂层。喷涂的工艺参数分别为,喷涂距离:90mm,工作电流:700A,工作电压: 70V,N2气速度:50 升/min,H2速度:10 升/min,送粉量:42g/min,冷却气压力:0.3MPa,喷枪移动速度:30mm/s。
经实验表明,等离子热喷涂涂层形貌基本致密、无裂纹等缺陷,涂层厚度大约为230μm,组织为氮化物、硼化物弥散分布的层状组织,涂层的耐磨性为Q235钢的4.3倍。
实施例2:
步骤一、将Al粉、Fe-Cr-B-Si、Mn粉、Ni-Cr-B-Si合金粉按一定比例混合,并用球磨机进行球磨混合制作喷涂粉,制作的粉末粒径35-50μm;其中Al粉、Fe-Cr-B-Si、Mn粉、Ni-Cr-B-Si合金粉的质量比为:10:30:30:30;Fe-Cr-B-Si成分的质量含量为Cr:16~18%,B:2.5~4.5%,Si:3~4.5%,其余为Fe; Ni-Cr-B-Si成分的质量含量为Cr:16~18%,B:2.5~4.5%,Si:3~4.5%,其余为Ni; Al、Mn粉的纯度高于99.5%,粒径在40-80μm。将上述金属粉末采用钢制球磨罐进行球磨混合,其中的磨球与金属粉质量比为3.2∶1,密封后打开真空阀抽真空30分钟,将球磨罐放入行星式球磨机,转速为 260 r/min,倒向频率45 Hz,进行球磨混料时间为60分钟。
步骤二、选取将要强化的Q275碳钢工件表面作为基体,对工件表面清除铁锈和油污,然后喷砂处理,粗化工件表面;最后采用外热方式对工件表面进行预热,预热温度控制在300℃;
步骤三、采用热喷涂的方式对工件表面预喷涂Ni-Al粘结层,粘结层厚度控制在70-100μm;Ni-Al合金粉末的粒度为80-240μm,其成分中含Al的质量为8%,其余为Ni。
步骤四、采用等离子设备按一定喷涂工艺参数加热混合的喷涂粉对工件表面进行热喷涂,冷却后即为耐磨涂层。喷涂的工艺参数分别为,喷涂距离: 120mm,工作电流:500A,工作电压:50V,N2气速度:30 升/min,H2速度:5 升/min,送粉量:38g/min,冷却气压力:0.5MPa,喷枪移动速度:80mm/s。
经实验表明,等离子热喷涂后涂层基本致密无气孔,涂层厚度大约为260μm,组织为氮化物、硼化物弥散分布的层状组织,其耐磨性为Q275钢的3.2倍。
实施例3:
步骤一、将Al粉、Fe-Cr-B-Si、Mn粉、Ni-Cr-B-Si合金粉按一定比例混合,并用球磨机进行球磨混合制作喷涂粉,制作的粉末粒径20-50μm;其中Al粉、Fe-Cr-B-Si、Mn粉、Ni-Cr-B-Si合金粉的质量比为:15:28:28:29;Fe-Cr-B-Si成分的质量含量为Cr:16~18%,B:2.5~4.5%,Si:3~4.5%,其余为Fe; Ni-Cr-B-Si成分的质量含量为Cr:16~18%,B:2.5~4.5%,Si:3~4.5%,其余为Ni;Al、Mn粉的纯度高于99.5%,粒径在40-60μm。将上述金属粉末采用钢制球磨罐进行球磨混合,其中的磨球与金属粉质量比为3∶1,密封后打开真空阀抽真空25分钟,将球磨罐放入行星式球磨机,转速为 280 r/min,倒向频率40Hz,进行球磨混料时间为70分钟。
步骤二、选取将要强化的Q195碳钢工件表面作为基体,对工件表面清除铁锈和油污,然后喷砂处理,粗化工件表面;最后采用外热方式对工件表面进行预热,预热温度控制在280℃;
步骤三、采用热喷涂的方式对工件表面预喷涂Ni-Al粘结层,粘结层厚度控制在60-80μm;Ni-Al合金粉末的粒度为80-240μm,其成分中含Al的质量为10%,其余为Ni。
步骤四、采用等离子设备按一定喷涂工艺参数加热混合的喷涂粉对工件表面进行热喷涂,冷却后即为耐磨涂层。喷涂的工艺参数分别为,喷涂距离:110mm,工作电流:600A,工作电压:60V,N2气速度:40 升/min,H2速度:7 升/min,送粉量:40g/min,冷却气压力:0.4MPa,喷枪移动速度:50mm/s。
经实验表明,等离子热喷涂后涂层基本致密无气孔,涂层厚度大约为220μm,组织基本均匀,分布有细小弥散的氮化物和片状硼化物的层状组织,其耐磨性为Q195钢的3.6倍。
Claims (5)
1.一种热喷涂氮化物增强高熵合金涂层的制备方法,其特征在于,所述的制作方法包括下述工艺步骤:
步骤一、将Al、Mn粉、Fe-Cr-B-Si、Ni-Cr-B-Si合金粉按一定比例混合,并用球磨机进行球磨混合制作喷涂粉,制作的粉末粒径20-50μm;
步骤二、选取将要强化的碳钢工件表面作为基体,对工件表面清除铁锈和油污,然后喷砂处理,粗化工件表面;最后采用外热方式对工件表面进行预热,预热温度控制在250~300℃;
步骤三、采用热喷涂的方式对工件表面预喷涂Ni-Al粘结层,粘结层厚度控制在30-100μm;
步骤四、采用等离子设备按一定喷涂工艺参数加热混合的喷涂粉对工件表面进行热喷涂,冷却后即为耐磨涂层。
2.根据权利要求1所述的一种热喷涂氮化物增强高熵合金涂层的制备方法,其特征在于:所述的Al粉、Fe-Cr-B-Si、Mn粉、Ni-Cr-B-Si合金粉的质量比为:10~20:26~30:26~30:26~30;所述的Fe-Cr-B-Si成分的质量含量为Cr:16~18%,B:2.5~4.5%,Si:3~4.5%,其余为Fe;所述的Ni-Cr-B-Si成分的质量含量为Cr:16~18%,B:2.5~4.5%,Si:3~4.5%,其余为Ni; Al、Mn粉的纯度高于99.5%,粒径在30-80μm。
3.根据权利要求1所述的一种热喷涂氮化物增强高熵合金涂层的制备方法,其特征在于:所述的球磨混合是采用钢制球磨罐进行球磨混合,其中的磨球与金属粉质量比为2.7~3.2∶1,密封后打开真空阀抽真空20~30分钟,将球磨罐放入行星式球磨机,转速为 260~300r/min,倒向频率 30~45 Hz,进行球磨混料时间为60~80分钟。
4.根据权利要求1所述的一种热喷涂氮化物增强高熵合金涂层的制备方法,其特征在于所述的Ni-Al粘结层,所用Ni-Al合金粉末的粒度为80-240μm,含Al的质量为8~20%,其余为Ni。
5.根据权利要求1所述的一种热喷涂氮化物增强高熵合金涂层的制备方法,其特征在于所述的一定喷涂工艺参数为:喷涂距离:90-120mm,工作电流:500-700A,工作电压:50-70V,N2气速度:30-50 升/min,H2速度:5-10 升/min,送粉量:38±42g/min,冷却气压力:0.3-0.5MPa,喷枪移动速度:30-80mm/s。
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