CN109824363A - 韧性陶瓷材料 - Google Patents

韧性陶瓷材料 Download PDF

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CN109824363A
CN109824363A CN201810195522.XA CN201810195522A CN109824363A CN 109824363 A CN109824363 A CN 109824363A CN 201810195522 A CN201810195522 A CN 201810195522A CN 109824363 A CN109824363 A CN 109824363A
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pottery material
toughness
boride
toughness pottery
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陈瑞凯
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Abstract

一种韧性陶瓷材料，该韧性陶瓷材料的组成为至少一种硼化物及一种耐火金属或是至少两种硼化物、至少一种碳化物及一种耐火金属，其中使用上述材料进行加热熔炼能够形成该韧性陶瓷材料，而于加热熔炼为韧性陶瓷材料的过程中，该耐火金属皆会与硼化物或/及碳化物反应，因此金属胶结相会流失而形成为一具有高韧性的纯陶瓷结构。

Description

韧性陶瓷材料
技术领域
本发明关于一种韧性陶瓷材料，特别是一种能够将至少一种硼化物及一种耐火金属或是至少两种硼化物、至少一种碳化物及一种耐火金属进行加热熔炼形成为一具有高韧性的纯陶瓷结构。
背景技术
Cemented carbides为胶结碳化物，是一种由WC与Co组成的复合材料。十九世纪初，Henri Moissan人造合成碳化钨(WC)。碳化钨硬度高，原欲作为钻石的替代材料，却因存在易脆及孔洞等缺点，而不便用于工程上。1923年和Baumhauer发现碳化钨与钴或镍，经烧结制程后，可同时保有陶瓷材料的硬度，以及金属的韧性，这对模具工业，造成巨大影响，材料并广泛应用在切削工具、矿产采掘、与军事武器的部分零件上。原料钨约有60％用在胶结碳化物的生产上。1930年使用需求量为十公吨，2008年使用需求量则达五万公吨，78年内成长了5000倍。
胶结碳化物由两部份组成，一为强化相、另一为胶结相。如上述所提的碳化钨WC扮演着强化相的角色，拥有高熔点、高韧性、以及良好抗磨耗等特性，而钴则为胶结相，拥有金属良好的导电、导热性之外，还有提供最重要的特性--韧度，使复材不易脆裂。近年的研究，大多以WC与Co统硬质金属为基础，将强化相衍生出TiC与TaC等，胶结相衍生出Mo,Ni与Fe等，并通称这些材料为「瓷金复材」(Cermet composites)；传统Hard metals硬质金属以及瓷金复材，主要生产制程为烧结法，并且将胶结相进行「少量」的多元添加；然而，上述以传统烧结法制成的超硬合金需担心复材致密度问题，且制程相对较复杂，成本较高，复材的工作温度也有其极限。
因此，若能够以熔炼方式进行制备材料，将能够克服上述问题，然而若是能够于加热熔炼为韧性陶瓷材料的过程中，透过不同配方，使耐火金属能够仅与硼化物或/及碳化物反应，而金属胶结相会流失并形成为一具有高韧性的纯陶瓷结构，如此应为一最佳解决方案。
发明内容
本发明的目的在于提供一种韧性陶瓷材料，其能够克服现有技术的缺陷，能以熔炼方式进行制备材料，形成为一具有高韧性的纯陶瓷结构。
为实现上述目的，本发明公开了一种韧性陶瓷材料，其特征在于：该韧性陶瓷材料的组成为至少一种硼化物及一种耐火金属，其中该硼化物选自于TiB2、ZrB2、NbB2、HfB2、TaB2或W2B5，而该耐火金属为钨或钽，其中使用硼化物与耐火金属进行加热熔炼形成该韧性陶瓷材料。
其中，使用硼化物与耐火金属进行加热熔炼为韧性陶瓷材料的过程中，该耐火金属皆会与硼化物反应，因此金属胶结相会流失而形成为一纯陶瓷结构。
其中，该韧性陶瓷材料的微结构由MB2相、MB相或/及W2B相所组成。
还公开了一种韧性陶瓷材料，其特征在于：该韧性陶瓷材料的组成为至少两种硼化物、至少一种碳化物及一种耐火金属，其中该硼化物选自于TiB2、ZrB2、NbB2、HfB2、TaB2或W2B5，而该碳化物选自于SiC、B4C、TiC、NbC、TaC、WC，且该耐火金属为钨，其中使用硼化物、碳化物与耐火金属进行加热熔炼形成该韧性陶瓷材料。
其中，使用硼化物、碳化物与耐火金属进行加热熔炼为韧性陶瓷材料的过程中，该耐火金属会与硼化物或/及碳化物反应，因此金属胶结相会流失而形成为一纯陶瓷结构。
其中，该韧性陶瓷材料的微结构由MB2相、MC相、MB相或/及W2B相所组成。
通过上述内容，本发明能实现如下技术效果：
1.本发明能够以熔炼方式进行制备材料，将能够克服上述问题，然而若是能够于加热熔炼为韧性陶瓷材料的过程中，透过不同配方，使耐火金属能够仅与硼化物或/及碳化物反应，而金属胶结相会流失并形成为一具有高韧性的纯陶瓷结构。
2.由于本发明是的韧性陶瓷是由熔融反应而来，更由于因熔融制成而可有100％密度，而有高韧性，且熔炼出的制品更具有一定的硬度及韧性，且高温下的硬度稳定性好，因此非常是适用于一般产业的使用。
附图说明
图1：本发明韧性陶瓷材料的制备流程示意图。
图2：本发明韧性陶瓷材料的第一实施的XRD分析示意图。
图3：本发明韧性陶瓷材料的第二实施的XRD分析示意图。
图4：本发明韧性陶瓷材料的第三实施的XRD分析示意图。
图5：本发明韧性陶瓷材料的第四实施的XRD分析示意图。
图6：本发明韧性陶瓷材料的第五实施的XRD分析示意图。
图7：本发明韧性陶瓷材料的第六实施的XRD分析示意图。
图8：本发明韧性陶瓷材料的第七实施的XRD分析示意图。
图9：本发明韧性陶瓷材料的第八实施的XRD分析示意图。
图10：本发明韧性陶瓷材料的第九实施的XRD分析示意图。
图11：本发明韧性陶瓷材料的第十实施的XRD分析示意图。
图12：本发明韧性陶瓷材料的第十一实施的XRD分析示意图。
图13：本发明韧性陶瓷材料的第十二实施的XRD分析示意图。
图14：本发明韧性陶瓷材料的第十三实施的XRD分析示意图。
图15：本发明韧性陶瓷材料的第十四实施的XRD分析示意图。
具体实施方式
有关于本发明其他技术内容、特点与功效，在以下配合参考图式的较佳实施例的详细说明中，将可清楚的呈现。
请参阅图1，其制备方法如下：
(1)本发明的韧性陶瓷材料是将至少一种硼化物及一种耐火金属(或是至少两种硼化物、至少一种碳化物及一种耐火金属)充分混合后，置于真空电弧熔炼炉的水冷铜模的凹槽中101；
(2)之后将真空电弧熔炼炉抽真空(将腔体压力抽至2.4×10-2torr)后，通纯氩气(Ar气体)使压力提升至8.0torr左右，并再度抽真空(抽至2.4×10-2torr，此通Ar气体再抽气的动作称为purge)，而上述动作反复数次后，最后通Ar气体使腔体压力回到8.0torr并进行熔炼102；
(3)而熔炼完成后待试片冷却，将其翻面后再度熔炼，并反复此动作数次，以确保试片的均匀度，最后等待试片冷却后，使腔体压力回到1大气压，并取出所形成的韧性陶瓷材料试片103。
其中，该硼化物选自于TiB2、ZrB2、NbB2、HfB2、TaB2或W2B5，而该耐火金属为钨或钽(或该硼化物选自于TiB2、ZrB2、NbB2、HfB2、TaB2或W2B5，而该碳化物选自于SiC、B4C、TiC、NbC、TaC、WC，且该耐火金属为钨或钽)。
而本发明会举出几个以下不同实施例，以下几个实施例皆能够明显看出金属胶结相会流失并形成为一具有高韧性的纯陶瓷结构，其中第一实施(B1B2+Ta)的成份为(TiB2)0.3(ZrB2)0.3Ta0.4，其中XRD分析如图2所示，峰值分析显示相组成为MB,MB2,M2B，且明显没有胶结相Ta固溶体讯号，其中第一实施所制备出的韧性陶瓷材料具有近似纯陶瓷的特性，且M2B相分率高造成机械性质硬脆，整体硬度值为1842±74HV，破裂韧性为6.44±0.99MPa m1/2。
其中第二实施(SB4)的成份为(NbB2)0.6W0.4，其中XRD峰值图3所示，峰值显示此成份有三种相，分别为M2B,MB,MB2，由于第二实施中的W几乎全和B反应形成MB或M2B，因此耐火金属胶结相流失形成纯陶瓷结构，而第二实施的硬度和韧性表现算是相当优秀，复材整体硬度值为1944±56HV，破裂韧性为7.72±0.72MPa m1/2。
其中第三实施(B3B5)的成份为[(HfB2)(TaB2)]0.6W0.4，其中XRD峰值如图4所示，峰值显示此成份有三种相，分别为M2B,MB,MB2，而第三实施的成份整体硬度值为1911±93HV，破裂韧性为5.12±0.34MPa m1/2。
其中第四实施(B3B6)的成份为[(HfB2)(W2B5)0.5]0.6W0.4，其中XRD峰值如图5所示，峰值显示此成份有两种相，分别为MB及MB2，而第四实施的整体硬度值为1841±87HV，破裂韧性为5.66±0.34MPa m1/2。
其中第五实施(B4B5)的成份为[(NbB2)(TaB2)]0.6W0.4，其中XRD峰值如图6所示，峰值显示此成份有两种相，分别为MB及MB2，第五实施中同样没有保留住胶结相，因此同为纯陶瓷的结构，而复材整体硬度值为1996±81HV，破裂韧性为6.06±0.24MPa m1/2。
其中第六实施(B4B6)的成份为[(NbB2)(W2B5)0.5]0.6W0.4，其中XRD峰值如图7所示，峰值显示此成份有三种相，分别为M2B,MB,MB2，而第六实施的硬度韧性表现相当良好，此成份整体硬度值为2165±28HV，破裂韧性为7.88±0.17MPam1/2。
其中第七实施((6B)6W4)的成份为[(TiB2)(ZrB2)(HfB2)(NbB2)(TaB2)(W2B5)0.5]0.6W0.4，其中XRD峰值如图8所示，峰值显示此成份有两种相，分别为MB及MB2，而第七实施的整体硬度为1841±87HV，破裂韧性为5.06±0.41MPa m1/2。
其中第八实施(B3B4+W)的成份为[(HfB2)(NbB2)]0.4W0.6，其中XRD峰值如图9所示，峰值显示此成份有三种相，分别为M2B,MB,MB2，而第八实施也如同前几个实施例一般，也是失去金属胶结相(大部份钨金属皆反应形成此硬脆相以及部份形成MB)，而复材整体硬度值为1742±48HV，破裂韧性为6.88±0.44MPam1/2。
其中第九实施(B3B5+W)的成份为[(HfB2)(TaB2)]0.4W0.6，其中XRD峰值如图10所示，峰值显示此成份有两种相，分别为W2B和MB，而第九实施也同样没有明显胶结相残留，其整体硬度值为1863±66HV，破裂韧性为6.56±0.44MPa m1/2。
其中第十实施((5B)5W5)的成份为[(TiB2)(ZrB2)(HfB2)(NbB2)(TaB2)]0.5W0.5，其中XRD峰值如图11所示，峰值显示此成份有三种相，分别为W2B,MB,MB2，而第十实施的成份整体硬度值为2076±56HV，破裂韧性为5.99±0.50MPa m1/2。
其中第十一实施((4B)4W6)的成份为[(TiB2)(ZrB2)(NbB2)(TaB2)]0.4W0.6，其XRD峰值如图12所示，峰值显示此成份有三种相，同样为W2B,MB,MB2，其机械性质和(5B)5W5相近，硬度值为2045±47HV，破裂韧性为5.77±0.37MPa m1/2。
其中第十二实施(+SiC)的成份为[(TiB2)(ZrB2)(SiC)]0.6W0.4，其中XRD峰值如图13所示，峰值显示此成份有四种相，分别为SiC,MSi2,MB,MB2，此试片的整体硬度值为1898±65HV，破裂韧性为5.89±0.53MPa m1/2。
其中第十三实施(+B4C)的成份为[(TiB2)(ZrB2)(B4C)]0.6W0.4，其中XRD峰值如图14所示，峰值显示此成份有三种相，分别为MC,MB,MB2，本实施例成份因含有过多硼原子而产生大量粗大的MB2相以及少量MB相，胶结相钨均反应成此类陶瓷硼化物因而没有观察到有金属固溶体生成。
其中第十四实施(+TZ)的成份为[(TiC)(NbC)(TaC)(WC)(TiB2)(ZrB2)]0.6W0.4，其中XRD峰值如图15所示，峰值显示此成份有三种相，分别为MC,MB及M2B，本实施例中微结构中未观察到胶结相钨固溶体，也没有原先NT列的层状结构，仅有大量M2B伴随MC点状分布其中，其整体硬度值为2203±83HV，破裂韧性为6.03±0.25MPa m1/2。
而上述实施中的微结构都没有观察到金属胶结相残留，因成份中含有大量的硼原子，加上金属胶结相易和硼反应，因此难以保留胶结相钨固溶体，故复材会形成近似纯陶瓷的结构。
本发明所提供的韧性陶瓷材料，与其他习用技术相互比较时，其优点如下：
1.本发明能够以熔炼方式进行制备材料，将能够克服上述问题，然而若是能够于加热熔炼为韧性陶瓷材料的过程中，透过不同配方，使耐火金属能够仅与硼化物或/及碳化物反应，而金属胶结相会流失并形成为一具有高韧性的纯陶瓷结构。
2.由于本发明是的韧性陶瓷是由熔融反应而来，更由于因熔融制成而可有100％密度，而有高韧性，且熔炼出的制品更具有一定的硬度及韧性，且高温下的硬度稳定性好，因此非常是适用于一般产业的使用。
本发明已透过上述的实施例揭露如上，然其并非用以限定本发明，任何熟悉此一技术领域具有通常知识者，在了解本发明前述的技术特征及实施例，并在不脱离本发明的精神和范围内，当可作些许的更动与润饰，因此本发明的专利保护范围须视本说明书所附的权利要求所界定者为准。

Claims (6)

1.一种韧性陶瓷材料，其特征在于：该韧性陶瓷材料的组成为至少一种硼化物及一种耐火金属，其中该硼化物选自于TiB2、ZrB2、NbB2、HfB2、TaB2或W2B5，而该耐火金属为钨或钽，其中使用硼化物与耐火金属进行加热熔炼形成该韧性陶瓷材料。
2.如权利要求1所述的韧性陶瓷材料，其特征在于，使用硼化物与耐火金属进行加热熔炼为韧性陶瓷材料的过程中，该耐火金属皆会与硼化物反应，因此金属胶结相会流失而形成为一纯陶瓷结构。
3.如权利要求1所述的韧性陶瓷材料，其特征在于，该韧性陶瓷材料的微结构由MB2相、MB相或/及W2B相所组成。
4.一种韧性陶瓷材料，其特征在于：该韧性陶瓷材料的组成为至少两种硼化物、至少一种碳化物及一种耐火金属，其中该硼化物选自于TiB2、ZrB2、NbB2、HfB2、TaB2或W2B5，而该碳化物选自于SiC、B4C、TiC、NbC、TaC、WC，且该耐火金属为钨，其中使用硼化物、碳化物与耐火金属进行加热熔炼形成该韧性陶瓷材料。
5.如权利要求4所述的韧性陶瓷材料，其特征在于：使用硼化物、碳化物与耐火金属进行加热熔炼为韧性陶瓷材料的过程中，该耐火金属会与硼化物或/及碳化物反应，因此金属胶结相会流失而形成为一纯陶瓷结构。
6.如权利要求4所述的韧性陶瓷材料，其特征在于，该韧性陶瓷材料的微结构由MB2相、MC相、MB相或/及W2B相所组成。
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Application publication date: 20190531