CN111499392A - 一种高硬度陶瓷及其制备方法 - Google Patents
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Abstract
本发明公开了一种高硬度陶瓷及其制备方法,属于陶瓷材料技术领域,该高硬度陶瓷以质量份计,包括以下组分:α‑氮化硅30‑50份、β‑氮化硅10‑30份、氧化铝5‑10份、氮化锆1‑5份、氮化钨3‑9份、五氧化二铌3‑7份、氟化镁1‑5份、碳化硅5‑15份、氮化硼1‑5份、碳化硼1‑3份;本发明的高硬度陶瓷材料在较高温度(>1200℃)时仍具有较高的高温力学性能和良好的化学稳定性,还具有高致密度、耐高温、高硬度、高密度、高强度的特点。
Description
技术领域
本发明涉及陶瓷材料技术领域,特别是涉及一种高硬度陶瓷及其制备方法。
背景技术
氮化硅是一种强共价键的化合物,作为原子晶体的氮化硅,具有很高的键能,在空气中能形成氧化物保护膜,具有良好的稳定性,及良好的高温性能,被认为是世界上最硬的物质之一,能耐受多种酸碱腐蚀,还具有热震性好、热膨胀系数小、绝缘、耐磨等优点。
氮化硅陶瓷是一种烧结时不收缩的无机材料。利用氮化硅的强度很高,尤其是热压氮化硅,制备的陶瓷材料具有较好的致密度和强度。氮化硅材料天生具有耐高温的性能,热压氮化硅一般常压下1900℃左右分解,抗高压蠕变能力强,不含粘结剂的反应烧结氮化硅负荷软化点也高达1800℃。
在一些需要高温高压的领域,比如超高温压痕仪器的高温压头,目前国外高温压痕仪器的最高使用温度950℃,不足以覆盖需要更高温度的如热障涂层等的服役温度。根据压痕测试的基本原理,高温压头在高温环境下应具备较高的硬度及强度、较好的化学稳定性及抗氧化能力。现有的高温压痕仪器在较低温度段(<500℃)大多采用金刚石立方氮化锆压头,在较高温度段(500-950℃)大多采用蓝宝石碳化钨压头。而上述压头由于氧化分解、强度衰减等问题,无法应用于更高的温度。
发明内容
本发明的目的是提供一种高硬度陶瓷及其制备方法,以解决上述现有技术存在的问题,其在高温高压环境下仍能保持良好的硬度及强度和化学稳定性。
为实现上述目的,本发明提供了如下方案:
本发明提供一种高硬度陶瓷,以质量份计,包括以下组分:
α-氮化硅30-50份、β-氮化硅10-30份、氧化铝5-10份、氮化锆1-5份、氮化钨3-9份、五氧化二铌3-7份、氟化镁1-5份、碳化硅5-15份、氮化硼1-5份、碳化硼1-3份。
进一步地,所述α-氮化硅的粒径为0.1-1.5μm,所述β-氮化硅的粒径为0.5-2μm,所述氧化铝、氮化钨、五氧化二铌、氟化镁的粒径均不超过2μm,所述氮化锆的粒径为1-2.5μm,所述碳化硅的粒径为0.1-0.4μm,所述氮化硼的粒径为1-2μm,所述碳化硼的粒径为0.5-1μm。
进一步地,所述α-氮化硅的粒径为0.5-1μm,所述β-氮化硅的粒径为1.2-1.8μm。
进一步地,所述α-氮化硅与所述β-氮化硅的质量比为2:1。
本发明还提供一种上述的高硬度陶瓷的制备方法,包括以下步骤:
(1)将α-氮化硅、氧化铝、氮化钨和氮化硼与溶剂混合后,在行星球磨机中进行球磨;
(2)将β-氮化硅、氮化锆、五氧化二铌、氟化镁和碳化硼混合后,在行星球磨机中进行球磨;
(3)将步骤(1)和步骤(2)球磨后的原料混合,在80-95℃、搅拌条件下,烘干1-3h,过筛,装入模具;
(4)将装有原料的模具在真空度10-3-10-2MPa的条件下,以50-60℃/min的升温速率加热至1400-1600℃,充入惰性气体加压至10-20MPa,进行恒温烧结0.2-1.5h;
(5)以30-40℃/min的降温速率将温度降至800-900℃,煅烧1-3h,再以100-130℃/min的升温速率升温至1200-1300℃,煅烧1-2h,保温1.2h,最后以20-30℃/min的降温速率将温度降至室温,即得高强度陶瓷。
进一步地,步骤(1)中,所述溶剂为乙醇,所述乙醇的加入量以更好没过原料和磨球为准。
进一步地,所述球磨的参数为:球料比3-5:1,磨球为等量的玛瑙球和氧化锆球,球磨转速为150-200r/min,球磨时间2-4h。
进一步地,步骤(2)中,所述球磨的参数为:球料比2:1,磨球为等量的玛瑙球和碳化硅陶瓷球,球磨转速为100-150r/min,球磨时间1-3h。
本发明公开了以下技术效果:
本发明的高硬度陶瓷材料在较高温度(>1200℃)时仍具有较高的高温力学性能和良好的化学稳定性,还具有高致密度、耐高温、高硬度、高密度、高强度的特点,并且该陶瓷材料的制备工艺简单,一般来说,陶瓷的热压工艺对温度和压力的要求极高,一般只有在1800℃和10-40MPa以上的温度和压力情况下,才能得到致密度和硬度良好的陶瓷材料,而本发明通过对氮化硅晶型进行配比,搭配碳化硅和氮化硼等原料,并对其粒径进行严格要求,在加以球磨工艺,使得本发明热压加工工艺采用的温度和压力低,非常有利于降低生产成本,也可以降低生产工艺对设备的要求。
具体实施方式
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本申请说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。
本发明中所述的“份”如无特别说明,均按质量份计。
实施例1
一种高硬度陶瓷,以质量份计,包括以下组分:
α-氮化硅40份、β-氮化硅20份、氧化铝8份、氮化锆3份、氮化钨6份、五氧化二铌5份、氟化镁3份、碳化硅10份、氮化硼3份、碳化硼2份。
所述α-氮化硅的粒径为0.8μm,所述β-氮化硅的粒径为1.5μm,所述氧化铝、氮化钨、五氧化二铌、氟化镁的粒径均为1μm,所述氮化锆的粒径为1.8μm,所述碳化硅的粒径为0.2μm,所述氮化硼的粒径为1.5μm,所述碳化硼的粒径为0.7μm。
上述的高硬度陶瓷的制备方法,包括以下步骤:
(1)将α-氮化硅、氧化铝、氮化钨和氮化硼与乙醇混合,让乙醇没过原料和磨球,在行星球磨机中进行球磨,球磨的参数为:球料比4:1,磨球为等量的玛瑙球和氧化锆球,球磨转速为180r/min,球磨时间3h;
(2)将β-氮化硅、氮化锆、五氧化二铌、氟化镁和碳化硼混合后,在行星球磨机中进行球磨,球磨的参数为:球料比2:1,磨球为等量的玛瑙球和碳化硅陶瓷球,球磨转速为130r/min,球磨时间2h;
(3)将步骤(1)和步骤(2)球磨后的原料混合,在88℃、搅拌条件下,烘干2h,过筛,装入模具;
(4)将装有原料的模具在真空度10-3MPa的条件下,以55℃/min的升温速率加热至1500℃,充入氦气加压至15MPa,进行恒温烧结0.9h;
(5)以35℃/min的降温速率将温度降至850℃,煅烧2h,再以115℃/min的升温速率升温至1250℃,煅烧1.5h,保温1.2h,最后以25℃/min的降温速率将温度降至室温,即得高强度陶瓷。
实施例2
一种高硬度陶瓷,以质量份计,包括以下组分:
α-氮化硅30份、β-氮化硅30份、氧化铝5份、氮化锆5份、氮化钨3份、五氧化二铌7份、氟化镁1份、碳化硅15份、氮化硼1份、碳化硼3份。
所述α-氮化硅的粒径为0.1μm,所述β-氮化硅的粒径为2μm,所述氧化铝、氮化钨、五氧化二铌、氟化镁的粒径均为1μm,所述氮化锆的粒径为1μm,所述碳化硅的粒径为0.4μm,所述氮化硼的粒径为1μm,所述碳化硼的粒径为1μm。
上述的高硬度陶瓷的制备方法,包括以下步骤:
(1)将α-氮化硅、氧化铝、氮化钨和氮化硼与乙醇混合,让乙醇没过原料和磨球,在行星球磨机中进行球磨,球磨的参数为:球料比3:1,磨球为等量的玛瑙球和氧化锆球,球磨转速为200r/min,球磨时间2h;
(2)将β-氮化硅、氮化锆、五氧化二铌、氟化镁和碳化硼混合后,在行星球磨机中进行球磨,球磨的参数为:球料比2:1,磨球为等量的玛瑙球和碳化硅陶瓷球,球磨转速为150r/min,球磨时间1h;
(3)将步骤(1)和步骤(2)球磨后的原料混合,在95℃、搅拌条件下,烘干1h,过筛,装入模具;
(4)将装有原料的模具在真空度10-2MPa的条件下,以50℃/min的升温速率加热至1600℃,充入氦气加压至10MPa,进行恒温烧结1.5h;
(5)以30℃/min的降温速率将温度降至900℃,煅烧1h,再以130℃/min的升温速率升温至1200℃,煅烧2h,保温1.2h,最后以20℃/min的降温速率将温度降至室温,即得高强度陶瓷。
实施例3
一种高硬度陶瓷,以质量份计,包括以下组分:
α-氮化硅50份、β-氮化硅10份、氧化铝10份、氮化锆1份、氮化钨9份、五氧化二铌3份、氟化镁5份、碳化硅5份、氮化硼5份、碳化硼1份。
所述α-氮化硅的粒径为1.5μm,所述β-氮化硅的粒径为0.5μm,所述氧化铝、氮化钨、五氧化二铌、氟化镁的粒径均为2μm,所述氮化锆的粒径为2.5μm,所述碳化硅的粒径为0.1μm,所述氮化硼的粒径为2μm,所述碳化硼的粒径为0.5μm。
上述的高硬度陶瓷的制备方法,包括以下步骤:
(1)将α-氮化硅、氧化铝、氮化钨和氮化硼与乙醇混合,让乙醇没过原料和磨球,在行星球磨机中进行球磨,球磨的参数为:球料比5:1,磨球为等量的玛瑙球和氧化锆球,球磨转速为150r/min,球磨时间4h;
(2)将β-氮化硅、氮化锆、五氧化二铌、氟化镁和碳化硼混合后,在行星球磨机中进行球磨,球磨的参数为:球料比2:1,磨球为等量的玛瑙球和碳化硅陶瓷球,球磨转速为100r/min,球磨时间3h;
(3)将步骤(1)和步骤(2)球磨后的原料混合,在80℃、搅拌条件下,烘干3h,过筛,装入模具;
(4)将装有原料的模具在真空度10-3MPa的条件下,以60℃/min的升温速率加热至1400℃,充入氩气加压至20MPa,进行恒温烧结0.2h;
(5)以40℃/min的降温速率将温度降至800℃,煅烧3h,再以100℃/min的升温速率升温至1300℃,煅烧1h,保温1.2h,最后以30℃/min的降温速率将温度降至室温,即得高强度陶瓷。
实施例4
一种高硬度陶瓷,以质量份计,包括以下组分:
α-氮化硅40份、β-氮化硅30份、氧化铝8份、氮化锆3份、氮化钨6份、五氧化二铌5份、氟化镁3份、碳化硅10份、氮化硼3份、碳化硼2份。
所述α-氮化硅的粒径为0.8μm,所述β-氮化硅的粒径为1.5μm,所述氧化铝、氮化钨、五氧化二铌、氟化镁的粒径均为1μm,所述氮化锆的粒径为1.8μm,所述碳化硅的粒径为0.2μm,所述氮化硼的粒径为1.5μm,所述碳化硼的粒径为0.7μm。
上述的高硬度陶瓷的制备方法,包括以下步骤:
(1)将α-氮化硅、氧化铝、氮化钨和氮化硼与乙醇混合,让乙醇没过原料和磨球,在行星球磨机中进行球磨,球磨的参数为:球料比4:1,磨球为等量的玛瑙球和氧化锆球,球磨转速为180r/min,球磨时间3h;
(2)将β-氮化硅、氮化锆、五氧化二铌、氟化镁和碳化硼混合后,在行星球磨机中进行球磨,球磨的参数为:球料比2:1,磨球为等量的玛瑙球和碳化硅陶瓷球,球磨转速为130r/min,球磨时间2h;
(3)将步骤(1)和步骤(2)球磨后的原料混合,在88℃、搅拌条件下,烘干2h,过筛,装入模具;
(4)将装有原料的模具在真空度10-3MPa的条件下,以55℃/min的升温速率加热至1500℃,充入氩气加压至15MPa,进行恒温烧结0.9h;
(5)以35℃/min的降温速率将温度降至850℃,煅烧2h,再以115℃/min的升温速率升温至1250℃,煅烧1.5h,保温1.2h,最后以25℃/min的降温速率将温度降至室温,即得高强度陶瓷。
实施例5
一种高硬度陶瓷,以质量份计,包括以下组分:
α-氮化硅30份、β-氮化硅20份、氧化铝8份、氮化锆3份、氮化钨6份、五氧化二铌5份、氟化镁3份、碳化硅10份、氮化硼3份、碳化硼2份。
所述α-氮化硅的粒径为0.8μm,所述β-氮化硅的粒径为1.5μm,所述氧化铝、氮化钨、五氧化二铌、氟化镁的粒径均为1μm,所述氮化锆的粒径为1.8μm,所述碳化硅的粒径为0.2μm,所述氮化硼的粒径为1.5μm,所述碳化硼的粒径为0.7μm。
上述的高硬度陶瓷的制备方法,包括以下步骤:
(1)将α-氮化硅、氧化铝、氮化钨和氮化硼与乙醇混合,让乙醇没过原料和磨球,在行星球磨机中进行球磨,球磨的参数为:球料比4:1,磨球为等量的玛瑙球和氧化锆球,球磨转速为180r/min,球磨时间3h;
(2)将β-氮化硅、氮化锆、五氧化二铌、氟化镁和碳化硼混合后,在行星球磨机中进行球磨,球磨的参数为:球料比2:1,磨球为等量的玛瑙球和碳化硅陶瓷球,球磨转速为130r/min,球磨时间2h;
(3)将步骤(1)和步骤(2)球磨后的原料混合,在88℃、搅拌条件下,烘干2h,过筛,装入模具;
(4)将装有原料的模具在真空度10-3MPa的条件下,以55℃/min的升温速率加热至1500℃,充入氦气加压至15MPa,进行恒温烧结0.9h;
(5)以35℃/min的降温速率将温度降至850℃,煅烧2h,再以115℃/min的升温速率升温至1250℃,煅烧1.5h,保温1.2h,最后以25℃/min的降温速率将温度降至室温,即得高强度陶瓷。
对比例1
与实施例1的不同之处在于,将β-氮化硅替换为等量的α-氮化硅。
对比例2
与实施例1的不同之处在于,将α-氮化硅替换为等量的β-氮化硅。
对比例3
与实施例1的不同之处在于,所述α-氮化硅和β-氮化硅的粒径均为3微米。
对比例4
与实施例1的不同之处在于,将碳化硼等量替换为氮化硼。
对比例5
与实施例1的不同之处在于,将氮化硼等量替换为碳化硼。
对比例6
与实施例1的不同之处在于,不进行步骤(1)的球磨步骤,将所有原料直接进行步骤(2)的球磨步骤。
对比例7
与实施例1的不同之处在于,所述步骤(5)为:以35℃/min的降温速率将温度1200-1300℃,煅烧3.5h,保温1.2h,最后以25℃/min的降温速率将温度降至室温。
将实施例1-5及对比例1-7得到的陶瓷材料制成样品,并对其进行测试,结果如表1所示,密度按照GB/T 2413-1981测试,室温弯曲强度按照GB/T 6569-2006测试,高温弯曲强度按照GB/T 14390-1993测试,硬度按照维氏硬度压痕法测试。
表1
由上表可知,本发明提供的高硬度陶瓷具有更好的硬度、密度及强度,且各个参数及配比密切相关,本发明所取得的技术效果是所有配比及其制备方法的配合得到的。
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (8)
1.一种高硬度陶瓷,其特征在于,以质量份计,包括以下组分:
α-氮化硅30-50份、β-氮化硅10-30份、氧化铝5-10份、氮化锆1-5份、氮化钨3-9份、五氧化二铌3-7份、氟化镁1-5份、碳化硅5-15份、氮化硼1-5份、碳化硼1-3份。
2.根据权利要求1所述的高硬度陶瓷,其特征在于,所述α-氮化硅的粒径为0.1-1.5μm,所述β-氮化硅的粒径为0.5-2μm,所述氧化铝、氮化钨、五氧化二铌、氟化镁的粒径均不超过2μm,所述氮化锆的粒径为1-2.5μm,所述碳化硅的粒径为0.1-0.4μm,所述氮化硼的粒径为1-2μm,所述碳化硼的粒径为0.5-1μm。
3.根据权利要求2所述的高硬度陶瓷,其特征在于,所述α-氮化硅的粒径为0.5-1μm,所述β-氮化硅的粒径为1.2-1.8μm。
4.根据权利要求3所述的高硬度陶瓷,其特征在于,所述α-氮化硅与所述β-氮化硅的质量比为2:1。
5.一种权利要求1-4任一项所述的高硬度陶瓷的制备方法,其特征在于,包括以下步骤:
(1)将α-氮化硅、氧化铝、氮化钨和氮化硼与溶剂混合后,进行球磨;
(2)将β-氮化硅、氮化锆、五氧化二铌、氟化镁和碳化硼混合后,进行球磨;
(3)将步骤(1)和步骤(2)球磨后的原料混合,在80-95℃、搅拌条件下,烘干1-3h,过筛,装入模具;
(4)将装有原料的模具在真空度10-3-10-2MPa的条件下,以50-60℃/min的升温速率加热至1400-1600℃,充入惰性气体加压至10-20MPa,进行恒温烧结0.2-1.5h;
(5)以30-40℃/min的降温速率将温度降至800-900℃,煅烧1-3h,再以100-130℃/min的升温速率升温至1200-1300℃,煅烧1-2h,保温1.2h,最后以20-30℃/min的降温速率将温度降至室温,即得高强度陶瓷。
6.根据权利要求5所述的高硬度陶瓷的制备方法,其特征在于,步骤(1)中,所述溶剂为乙醇,所述乙醇的加入量以刚好没过原料和磨球为准。
7.根据权利要求6所述的高硬度陶瓷的制备方法,其特征在于,所述球磨的参数为:球料比3-5:1,磨球为等量的玛瑙球和氧化锆球,球磨转速为150-200r/min,球磨时间2-4h。
8.根据权利要求5所述的高硬度陶瓷的制备方法,其特征在于,步骤(2)中,所述球磨的参数为:球料比2:1,磨球为等量的玛瑙球和碳化硅陶瓷球,球磨转速为100-150r/min,球磨时间1-3h。
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