CN109467437A - 一种金属陶瓷复合耐磨材料及其制备方法 - Google Patents

一种金属陶瓷复合耐磨材料及其制备方法 Download PDF

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CN109467437A
CN109467437A CN201811312689.6A CN201811312689A CN109467437A CN 109467437 A CN109467437 A CN 109467437A CN 201811312689 A CN201811312689 A CN 201811312689A CN 109467437 A CN109467437 A CN 109467437A
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李秋南
王惠民
黄涛
夏志强
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HANJIANG HONGYUAN XIANGYANG SILICON CARBIDE SPECIAL CERAMICS Co Ltd
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Abstract

本发明属于耐磨材料技术领域,特别涉及一种金属陶瓷复合耐磨材料及其制备方法。一种金属陶瓷复合耐磨材料,首先将碳化硅颗粒、高岭土、金属硅粉、助剂与结合剂一起制备多孔碳化硅陶瓷基板,然后将高温熔融金属材料浇注到多孔碳化硅陶瓷基板上制得,本发明将金属的韧性、抗弯性,与陶瓷的高硬度、高耐磨、耐腐蚀和抗氧化性能有机结合,其整体的强度、抗冲击韧性和耐磨性均有极大地提高,耐磨性一致性好,使用寿命远超于现有产品。

Description

一种金属陶瓷复合耐磨材料及其制备方法
技术领域
本发明属于耐磨材料技术领域,特别涉及一种金属陶瓷复合耐磨材料及其制备方法。
背景技术
金属陶瓷复合耐磨材料既具有陶瓷的高强度、高硬度、高磨损、耐高温、抗氧化和化学稳定性等特点,又具有较好的金属韧性和可塑性,广泛应用于火电、钢铁、冶炼、机械、煤炭、矿山、化工、水泥、港口码头等企业的输煤、输料系统、制粉系统、排灰、除尘系统等一切磨损大的机械设备上。在烧结时,金属与陶瓷颗粒不能充分的混匀,导致耐磨复合材料的金属相和陶瓷相分布不均,导致耐磨性产生较大差异。
申请号为201220097663.6,授权公告号为CN202461486U的中国专利公开了一种金属陶瓷增强体,在增强体上下两个端面上设有多个通孔,并设有安装槽,使用时将通过相互配合的安装槽将多个增强体拼接后形成整体,然后在通孔中浇注钢水,冷却后得到产品,从而完整的将易磨损部位保护起来。然而,该申请的金属陶瓷增强体内部致密,钢水在浇注时不能够有效渗透到增强体的内部,因而实际起到耐磨损作用的是碳化硅陶瓷,无法实现金属与陶瓷的有机结合。
申请号为201310667449.9,公开号为CN103611922A的中国专利公开了一种耐磨复合材料的制备方法,将陶瓷颗粒与高温易熔化有机颗粒通过无机粘合剂进行混合制备预制件,并在浇铸前高温去除所述高温易熔化有机颗粒后,将陶瓷颗粒与高温易熔化有机颗粒按比例混合,然后使用高温熔融金属材料进行浇铸,得到耐磨复合材料。其中,预制件在制备时包括以下流程:a.将高温易熔化有机颗粒(以下简称有机颗粒)、ZTA陶瓷颗粒和无机粘合剂混合均匀,制得混合料一;b.按不同的比例依次制得混合料二、混合料三,将混合料一、混合料二和混合料三依次倒入模具中形成梯度混合料后,震实;c.高温去除有机颗粒;d.固化陶瓷颗粒。
该发明的技术方案具有以下不足:1、在步骤b中,由于有机颗粒与ZTA陶瓷、无机粘接剂直接混合,有机颗粒有极可能被在ZTA陶瓷和无机粘接剂包覆,导致在步骤c中,高温去除有机颗粒时,有机颗粒不能够从梯度混合料中熔化流出,而不能够形成具有多孔、梯度的预制件;2、在步骤c中,高温去除有机颗粒时,有机物会部分残留在预制件的内部,后续在露天环境用钢水浇注预制件时,有机物会挥发到环境中,严重影响操作工人的身体健康;3、由于预制件的内部不能够有效形成多孔、梯度结构,因此在浇注钢水时,钢水不能够渗透到预制件的某些位置,钢水与预制件不能有效结合在一起,导致该耐磨复合材料的耐磨性和韧性达不到预期。
发明内容
本发明为了解决上述问题,提供一种金属陶瓷复合耐磨材料的制备方法,将金属的韧性、抗弯性,与陶瓷的高硬度、高耐磨、耐腐蚀和抗氧化性能有机结合,制得的金属陶瓷复合耐磨材料整体的强度、抗冲击韧性和耐磨性均有极大地提高,耐磨性一致性好,使用寿命远超于现有产品。
本发明采用以下技术方案来实现:
一种金属陶瓷复合耐磨材料的制备方法,包括以下步骤:
S1,将高岭土、金属硅粉和助剂进行干法球磨,球磨至粒径不大于20μm,得到小料;
S2,将碳化硅颗粒、结合剂与小料混合均匀后,在25~35℃条件下进行困料,困料时间为18~72h,困料结束后混合均匀,得到颗粒料;
S3,将颗粒料放入模具中,采用半干压成型法压制成型,放入烘干炉中,在100~180℃条件下烘干,得到干坯;
S4,将干坯放入氮化炉内,以30~100℃/h的速率进行升温,升温至1000~1200℃,保温1.5~2.5小时,接着升温至1400~1500℃,继续保温1.5~2.5小时,再自然冷却至室温,得到多孔碳化硅陶瓷基板;
S5,将高温熔融金属材料浇注到多孔碳化硅陶瓷基板中,自然冷却后,制得金属陶瓷复合耐磨材料。
制得的金属陶瓷复合耐磨材料,金属相和陶瓷相分布均匀,将金属的韧性、抗弯性,与陶瓷的高硬度、高耐磨、耐腐蚀和抗氧化性能有机结合,整体的强度、抗冲击韧性和耐磨性均有极大地提高,耐磨性一致性好,使用寿命远超于现有产品。
优选的方案,步骤S1中,所述助剂包括氮化铝、氮化硼、氧化硅、氧化铝、氧化钇、氧化锆中的至少一种。
优选的方案,步骤S1中,所述助剂还包括颗粒状金属铝。铝即使有一定的残余,高温熔融金属材浇注时也会对钢水形成脱氧效果,反而提高了金属陶瓷复合耐磨材料的金属相的品质。
优选的方案,步骤S2中,所述碳化硅颗粒的粒径为0.5~10mm。此粒径大小范围的碳化硅颗粒,大颗粒碳化硅烧结时,其内部能够形成多孔通道,扩大了其应用范围,且烧结制得的多孔碳化硅陶瓷基板,浇注钢水后的整体强度、硬度、耐磨损性能远高于小颗粒的碳化硅颗粒制备的多孔碳化硅陶瓷基板。
优选的方案,步骤S2中,所述结合剂通过如下方法制备而成:以质量份计,将结合剂原料1份、水10~20份混合,再用水浴法进行溶解。
优选的方案,所述结合剂原料包括聚乙烯醇、黄糊精、硅酸钠、三聚磷酸钠、羧甲基纤维素、硅溶胶中的至少一种。
优选的方案,步骤S5中,所述高温熔融金属材料选自高钒钢、高锰钢、高铬铸铁、球墨铸铁中的至少一种。
优选的方案,步骤S5中,高温熔融金属材料从预热至800~1000℃的多孔碳化硅陶瓷基板的底部向上浇注,浇注压力为0.01~0.08MPa。采用自下而上的浇注方式,能够起到保证浇注的钢水在多孔碳化硅陶瓷基板内部填充密实、浇注通道稳定可靠的效果。
一种金属陶瓷复合耐磨材料,通过上述方法制备而成。
优选的方案,所述金属陶瓷复合耐磨材料包括金属底板和碳化硅耐磨板,所述碳化硅耐磨板设于金属底板的上方,所述碳化硅和耐磨板一体成型。
本发明的有益效果是:
1、本发明的金属陶瓷复合耐磨材料,金属相和陶瓷相分布均匀,将金属的韧性、抗弯性,与陶瓷的高硬度、高耐磨、耐腐蚀和抗氧化性能有机结合,整体的强度、抗冲击韧性和耐磨性均有极大地提高,耐磨性一致性好,使用寿命远超于现有产品。
2、本发明选用大颗粒碳化硅颗粒作为原料,烧结时其内部能够自动形成多孔通道,无需通过其他手段辅助形成多孔通道,制备过程简单,浇注钢水后的整体强度、硬度、耐磨损性能远高于小颗粒的碳化硅颗粒制备的多孔碳化硅陶瓷基板。
3、本发明采用自下而上的浇注方式,能够起到保证浇注的钢水在多孔碳化硅陶瓷基板内部填充密实、浇注通道稳定可靠的效果。
附图说明
为了更清楚地说明本发明实施例中的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域一般技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是本发明的金属陶瓷复合耐磨材料的一个实施例中某一位置的剖视图。
图2是本发明的金属陶瓷复合耐磨材料的一个实施例中另一位置的剖视图。
图3是本发明的金属陶瓷复合耐磨材料的另外一个实施例的剖视图。
图中,1、陶瓷相;2、金属相。
具体实施方式
下面对实施例中的技术方案进行清楚、完整地描述。显然,所描述的实施例仅仅是本发明的一部分实施例,而不是全部的实施例。基于本发明的实施例,本领域一般技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
一种金属陶瓷复合耐磨材料的制备方法,包括以下步骤:
S1,将高岭土、金属硅粉、氮化铝和氮化硼进行干法球磨,球磨至粒径不大于20μm,得到小料;
S2,将碳化硅颗粒、结合剂与小料混合均匀后,在25~35℃条件下进行困料,困料时间为18h,困料结束后混合均匀,得到颗粒料;
S3,将颗粒料放入模具中,采用半干压成型法压制成型,放入烘干炉中,在100℃条件下烘干,得到干坯;
S4,将干坯放入氮化炉内,以100℃/h的速率进行升温,升温至1000℃,保温2.5小时,接着升温至1400℃,继续保温2.5小时,再自然冷却至室温,得到多孔碳化硅陶瓷基板;
S5,将高温熔融金属材料直接浇注到多孔碳化硅陶瓷基板中,自然冷却后,制得金属陶瓷复合耐磨材料,所述高温熔融金属材料为高铬铸铁。
其中,步骤S3中,所述碳化硅颗粒的粒径为8~10mm,所述碳化硅颗粒的形状不规则。
制备时,按质量份计,加入的物料占比为:
其中,所述碳化硅颗粒的粒径为8~10mm,按质量份计,结合剂原料包括:聚乙烯醇2份、硅酸钠1份、三聚磷酸钠2份,制备时,将结合剂原料与水按质量比1:10的比例混合,在60℃水浴中进行溶解得到结合剂。
实施例2
一种金属陶瓷复合耐磨材料的制备方法,包括以下步骤:
S1,将高岭土、金属硅粉和氧化硅进行干法球磨,球磨至粒径不大于20μm,得到小料;
S2,将碳化硅颗粒、结合剂、小料和粒径为400~500μm的颗粒状金属铝混合均匀后,在35℃条件下进行困料,困料时间为36h,困料结束后混合均匀,得到颗粒料;
S3,将颗粒料放入模具中,采用半干压成型法压制成型,放入烘干炉中,在150℃条件下烘干,得到干坯;
S4,将干坯放入氮化炉内,以30℃/h的速率进行升温,升温至800℃,保温1h,继续升温至1200℃,保温1.5小时,接着升温至1500℃,继续保温1.5小时,再自然冷却至室温,得到多孔碳化硅陶瓷基板;
S5,在0.05MPa压力条件下,将高温熔融金属材料从多孔碳化硅陶瓷基板的底部向上浇注到提前预热至800℃的多孔碳化硅陶瓷基板中,自然冷却后,制得金属陶瓷复合耐磨材料,所述高温熔融金属材料为高钒钢、高锰钢、高铬铸铁和球墨铸铁的混合物。
步骤S3中,所述碳化硅颗粒为球状,其粒径为5~7mm。
制备时,按质量份计,加入的物料占比为:
其中,所述碳化硅颗粒的粒径为5~7mm,按质量份计,结合剂原料包括:聚乙烯醇2份、黄糊精0.5份、硅酸钠1份、三聚磷酸钠2份、羧甲基纤维素0.5份、硅溶胶1份,制备时,将结合剂原料与水按质量比1:17的比例混合,在100℃水浴中进行溶解得到结合剂。
本实施例中,颗粒状金属铝会在碳化硅颗粒的缝隙之间形成被高岭土、金属硅粉和氧化硅包裹的、间隔细小的颗粒料,在步骤S4的中升温至800℃时,这些铝会融化,由于高岭土、金属硅粉和氧化硅之间仍然具有微小的缝隙,且铝在融化时体积会发生变化,助剂之间会贯穿连通,从而形成连续、形状基本一致的浇注通道。
作为上述效果的进一步说明,在步骤S4过程中,铝即使有一定的残余,高温熔融金属材浇注时也会对钢水形成脱氧效果,反而提高了金属陶瓷复合耐磨材料的金属相的品质,且在步骤S4的升温至800℃的阶段,铝不会发生爆沸现象,能够防止制得的多孔碳化硅陶瓷基板内部结构疏松,提高金属陶瓷复合耐磨材料的品质。
实施例3
一种金属陶瓷复合耐磨材料的制备方法,包括以下步骤:
S1,将高岭土、金属硅粉、氧化钇和氧化锆进行干法球磨,球磨至粒径不大于20μm,得到小料;
S2,将碳化硅颗粒、结合剂与小料混合均匀后,在32℃条件下进行困料,困料时间为72h,困料结束后混合均匀,得到颗粒料;
S3,将颗粒料放入模具中,采用半干压成型法压制成型,放入烘干炉中,在180℃条件下烘干,得到干坯;
S4,将干坯放入氮化炉内,以50℃/h的速率进行升温,升温至1100℃,保温2小时,接着升温至1450℃,继续保温2小时,再自然冷却至室温,得到多孔碳化硅陶瓷基板;
S5,在0.01MPa压力条件下,将高温熔融金属材料从多孔碳化硅陶瓷基板的底部向上浇注到提前预热至900℃的多孔碳化硅陶瓷基板中,自然冷却后,制得金属陶瓷复合耐磨材料,所述高温熔融金属材料为高铬铸铁、球墨铸铁的混合物。
步骤S3中,所述碳化硅颗粒为球状,其粒径为3~5mm。
制备时,按质量份计,加入的物料占比为:
其中,所述碳化硅颗粒的粒径为3~5mm,按质量份计,结合剂原料包括:三聚磷酸钠2份、羧甲基纤维素1份、硅溶胶3份,制备时,将结合剂原料与水按质量比1:15的比例混合,在80℃水浴中进行溶解得到结合剂。
实施例4
一种金属陶瓷复合耐磨材料的制备方法,包括以下步骤:
S1,将高岭土、金属硅粉、碳化硼和氧化铝进行干法球磨,球磨至粒径不大于20μm,得到小料;
S2,将碳化硅颗粒、结合剂与小料混合均匀后,在28℃条件下进行困料,困料时间为48h,困料结束后混合均匀,得到颗粒料;
S3,将颗粒料放入模具中,采用半干压成型法压制成型,放入烘干炉中,在135℃条件下烘干,得到干坯;
S4,将干坯放入氮化炉内,以75℃/h的速率进行升温,升温至1000℃,保温2小时,接着升温至1400℃,继续保温2小时,再自然冷却至室温,得到多孔碳化硅陶瓷基板;
S5,在0.08MPa压力条件下,将高温熔融金属材料从多孔碳化硅陶瓷基板的底部向上浇注到提前预热至1000℃的多孔碳化硅陶瓷基板中,自然冷却后,制得金属陶瓷复合耐磨材料,所述高温熔融金属材料为高钒钢和高锰钢的混合物。
步骤S3中,所述碳化硅颗粒为不规则形状,其粒径为0.5~2mm。
制备时,按质量份计,加入的物料占比为:
其中,所述碳化硅颗粒的粒径为0.5~2mm,结合剂原料为聚乙烯醇,制备时,将结合剂原料与水按质量比1:20的比例混合,在80℃水浴中进行溶解得到结合剂。
参考GB/T 23294及相关标准,测试实施例1~4制得的多孔碳化硅陶瓷基板的常温抗折强度和1400℃条件下的高温抗折强度,并进行气孔率、中值孔径的测试,测试结果如表1:
表1多孔碳化硅陶瓷基板的性能测试结果
样品 实施例1 实施例2 实施例3 实施例4
常温抗折强度/MPa 6.12 6.54 7.53 14.32
高温抗折强度/MPa 6.23 6.82 7.86 15.16
气孔率 51% 58% 49% 41%
中值孔径/μm 800~850 750~800 400~450 250~300
采用如下方法测试金属陶瓷复合耐磨材料的耐磨性能:
将实施例1~4制得的金属陶瓷复合耐磨材料、对比例1(Cr26耐磨钢)、对比例2(体积密度2.68g/cm3的碳化硅陶瓷)和对比例3(实施例3制得的多孔碳化硅陶瓷基板)分别制成100*100*20mm大小的样块,安装于测试设备中,采用120-200目、固含量为50~55%的石英浆液,以1MPa的压力和90°的冲击角度直接冲刷样块,冲刷时间为7小时,采用浸水法测试体积损失量,测试结果如表2:
表2耐磨性能测试结果
样品 实施例1 实施例2 实施例3 实施例4 对比例1 对比例2 对比例3
体积损失量(cm<sup>3</sup>) 0.036 0.034 0.031 0.034 0.114 0.032 2.92
采用浸水法测试体积的具体操作为:将一个样品缓慢放置到盛满水的容器中,测试溢出水的体积即为样品的体积。体积损失量=样品初始体积-样品冲刷后的体积。
由上述测试结果可以看出,本发明制得的金属陶瓷复合耐磨材料,抗磨蚀效果与致密的碳化硅陶瓷相差不大,是Cr26耐磨钢的三倍以上,具有广阔的应用前景。
实施例5
图1、图2为一种金属陶瓷复合耐磨材料的剖视图,陶瓷相1是指多孔碳化硅陶瓷基板的内部结构相,金属相2是指高温熔融金属材料浇注后固化形成的结构相,从图上可以看出,陶瓷相1互接触但具有空隙,而金属相2为形状基本规则的一体式结构。本实施例的产品,适合金属陶瓷复合耐磨材料直接作为耐磨件使用,将金属的韧性、抗弯性,与陶瓷的高耐磨、高强度和抗氧化性能有机结合,整体的强度、抗冲击韧性和耐磨性均有极大地提高。
实施例6
图3为另外一种金属陶瓷复合耐磨材料的剖视图,所述金属陶瓷复合耐磨材料包括金属底板和碳化硅耐磨板,所述碳化硅耐磨板设于金属底板的上方,所述碳化硅和耐磨板一体成型。
本实施例与实施例5不同的是,金属陶瓷复合耐磨材料的底部全部为金属相2,这个底部赋予了金属陶瓷复合耐磨材料优良的加工性能,便于该金属陶瓷复合耐磨材料的加工和安装,相比于实施例5的金属陶瓷复合耐磨材料,应用范围较广。

Claims (10)

1.一种金属陶瓷复合耐磨材料的制备方法,其特征在于,包括以下步骤:
S1,将高岭土、金属硅粉和助剂进行干法球磨,球磨至粒径不大于20μm,得到小料;
S2,将碳化硅颗粒、结合剂与小料混合均匀后,在25~35℃条件下进行困料,困料时间为18~72h,困料结束后混合均匀,得到颗粒料;
S3,将颗粒料放入模具中,采用半干压成型法压制成型,放入烘干炉中,在100~180℃条件下烘干,得到干坯;
S4,将干坯放入氮化炉内,以30~100℃/h的速率进行升温,升温至1000~1200℃,保温1.5~2.5小时,接着升温至1400~1500℃,继续保温1.5~2.5小时,再自然冷却至室温,得到多孔碳化硅陶瓷基板;
S5,将高温熔融金属材料浇注到多孔碳化硅陶瓷基板中,自然冷却后,制得金属陶瓷复合耐磨材料。
2.如权利要求1所述的金属陶瓷复合耐磨材料的制备方法,其特征在于,步骤S1中,所述助剂包括氮化铝、氮化硼、氧化硅、氧化铝、氧化钇、氧化锆中的至少一种。
3.如权利要求1所述的金属陶瓷复合耐磨材料的制备方法,其特征在于,步骤S1中,所述助剂还包括颗粒状金属铝。
4.如权利要求1所述的金属陶瓷复合耐磨材料的制备方法,其特征在于,步骤S2中,所述碳化硅颗粒的粒径为0.5~10mm。
5.如权利要求1所述的金属陶瓷复合耐磨材料的制备方法,其特征在于,步骤S2中,所述结合剂通过如下方法制备而成:以质量份计,将结合剂原料1份、水10~20份混合,再用水浴法进行溶解。
6.如权利要求5所述的金属陶瓷复合耐磨材料的制备方法,其特征在于,所述结合剂原料包括聚乙烯醇、黄糊精、硅酸钠、三聚磷酸钠、羧甲基纤维素、硅溶胶中的至少一种。
7.如权利要求1所述的金属陶瓷复合耐磨材料的制备方法,其特征在于,步骤S5中,所述高温熔融金属材料选自高钒钢、高锰钢、高铬铸铁、球墨铸铁中的至少一种。
8.如权利要求1所述的金属陶瓷复合耐磨材料的制备方法,其特征在于,步骤S5中,高温熔融金属材料从预热至800~1000℃的多孔碳化硅陶瓷基板的底部向上浇注,浇注压力为0.01~0.08MPa。
9.一种金属陶瓷复合耐磨材料,其特征在于,通过如权利要求1所述的方法制备而成。
10.如权利要求9所述的金属陶瓷复合耐磨材料,其特征在于,包括金属底板和碳化硅耐磨板,所述碳化硅耐磨板设于金属底板的上方,所述碳化硅和耐磨板一体成型。
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