CN111410538A - 一种增韧碳化硅陶瓷及其制备方法 - Google Patents

一种增韧碳化硅陶瓷及其制备方法 Download PDF

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CN111410538A
CN111410538A CN202010382038.5A CN202010382038A CN111410538A CN 111410538 A CN111410538 A CN 111410538A CN 202010382038 A CN202010382038 A CN 202010382038A CN 111410538 A CN111410538 A CN 111410538A
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silicon carbide
parts
powder
ball
toughened
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戴培赟
王东娟
李晓丽
张吉亮
刘茹
路金喜
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WEIFANG SCHOOL OF ECONOMICS
WEIFANG BUSINESS VOCATIONAL COLLEGE
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Abstract

本发明公开了一种增韧碳化硅陶瓷及其制备方法，属于陶瓷材料技术领域，本发明以碳化硅微粉、碳化硼微粉、炭黑、片状氧化铝、氟化镁、氧化镧、碳纳米管、增强纤维、Ti‑Si‑Fe合金粉为原料，在经过两段球磨后使其充分混合，在细化原料的同时获得一些球形粉体，增强粉体流动性，使其易于后续压制成型；本发明制备的增韧碳化硅陶瓷材料具有极好的硬度、密度、强度和韧性，在高温条件下仍能保持大部分性能，克服了现有技术中长径比很高的晶须和纤维难以混合均匀导致陶瓷品质不均的问题，使得碳化硅陶瓷材料具有优异的性能。

Description

一种增韧碳化硅陶瓷及其制备方法
技术领域
本发明涉及陶瓷材料技术领域，特别是涉及一种增韧碳化硅陶瓷及其制备方法。
背景技术
碳化硅陶瓷材料具有高温强度大、高温抗氧化性强、耐磨损性能好、热稳定性佳、热膨胀系数小、热导率大、硬度高、抗热震和耐化学腐蚀等优良特性，在汽车、机械化工、环境保护、空间技术、信息电子、能源等领域有着日益广泛的应用，已经成为一种在很多工业领域性能优异的其他材料不可替代的结构陶瓷。
但是与其它各类陶瓷类似，碳化硅陶瓷同样面临脆性问题，如何提供高韧性的碳化硅陶瓷，是该生产领域关注的重要课题。目前，陶瓷的韧化方式主要有相变增韧、纤维(晶须)增韧、颗粒增韧以及复合增韧。含有碳化硅晶须或碳纤维的增韧碳化硅陶瓷确实是一类具有较高韧性的碳化硅陶瓷，但是，由于其中含有的碳化硅晶须原料成本较高，使得整个增韧陶瓷成品的成本随之上升，引入碳化硅晶须或碳纤维进行增韧，确能使碳化硅陶瓷韧性大幅度提高，但是，长径比很高的碳化硅晶须以及碳纤维总的来说较难与其它碳化硅陶瓷生产原料混合均匀，这在一定程度上影响了增韧碳化硅陶瓷成品的品质均匀性。
发明内容
本发明的目的是提供一种增韧碳化硅陶瓷及其制备方法，以解决上述现有技术存在的问题，提高生产原料混合程度，提高陶瓷产品的韧性。
为实现上述目的，本发明提供了如下方案：
本发明提供一种增韧碳化硅陶瓷，以重量份计，包括以下组分：
碳化硅微粉80-100份、碳化硼微粉1-3份、炭黑15-30份、片状氧化铝2-4份、氟化镁1-3份、氧化镧0.5-1份、碳纳米管15-30份、增强纤维3-5份、Ti-Si-Fe合金粉3-5份。
进一步地，所述碳化硅微粉的粒径为1-3μm，所述碳化硼微粉的粒径为0.5-1μm，所述Ti-Si-Fe合金粉的粒径为0.2-0.8μm。
进一步地，所述增强纤维为碳化硅晶须、氧化锆晶须、氧化铝晶须、二氧化硅晶须、二氧化钛晶须中的一种或多种。
进一步地，所述碳纳米管为OD 1-2nm，length 1-30nm，CNTs purity＞90wt％，Ash＜1.5wt％的碳纳米管。
本发明还提供一种上述的增韧碳化硅陶瓷的制备方法，包括以下步骤：
(1)将碳化硅微粉、炭黑、碳化硼微粉与碳纳米管加入乙醇中超声，乙醇加入体积为碳化硅微粉体积的200-500倍，形成乙醇悬浮液；
(2)将片状氧化铝、氟化镁、氧化镧和Ti-Si-Fe合金粉混合，进行球磨，球磨1-2h后，加入增强纤维，进行球磨2-5h；
(3)在步骤(2)的混合料中加入步骤(1)所述的乙醇悬浮液，球磨5-10h，形成浆料；
(4)将步骤(3)所得的浆料在80-95℃、搅拌条件下，烘干1-2h，装入模具；
(5)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0.5-2h；
(6)以30-40℃/min的降温速率降温至700-900℃，煅烧1-3h，再以100-150℃/min的升温速率升温至1300-1400℃，煅烧1-2h，保温1-2h，最后以20-30℃/min的降温速率降温至室温，即得所述增韧碳化硅陶瓷。
进一步地，步骤(2)中，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。
进一步地，步骤(3)中，所述球磨的参数为：球料比2:1，磨球为氧化锆球，球磨转速为100-150r/min。
进一步地，所述惰性气体为氩气。
本发明公开了以下技术效果：
本发明以碳化硅微粉、碳化硼微粉、炭黑、片状氧化铝、氟化镁、氧化镧、碳纳米管、增强纤维、Ti-Si-Fe合金粉为原料，在经过两段球磨后使其充分混合，在细化原料的同时获得一些球形粉体，增强粉体流动性，使其易于后续压制成型；然后，本发明采用合理组分配方，各种原料的重量比是经过多次反复试验得出的，试验证明过多或过少的碳化硼微粉均不利于材料的烧结致密；而炭黑的比例和原料的氧份含量有关，原料氧份含量高，则需要较多的炭黑，反之可降低炭黑的添加量；另一方面，炭黑还可作为碳纳米管的润滑剂，炭黑可通过碳碳单键或双键与碳纳米管紧密连接，将碳纳米管包覆，从而提高碳纳米管的分散均匀性，也可避免在球磨和烧结过程中碳纳米管被硅相消耗，保留碳纳米管的纤维结构，充分发挥碳纤维的增韧作用；氟化镁和氧化镧的引入有助于抑制碳化硅晶粒的长大，从而细化晶粒，有助于增韧；因此，本发明的配方通过发挥各组分之间的协同作用，实现了材料的高强度和高韧性。
本发明利用碳纳米管进行增韧强化，结合增强纤维晶须和片状氧化铝，片状氧化铝颗粒易于与其他物料均匀混合，并弱化混料不均带来的负面影响；本发明的方案兼顾利用热膨胀失配诱发微裂纹、裂纹偏转、裂纹桥联、拔出效应等作用机制，碳纳米管在外界负载作用下从基质中拔出时，因界面摩擦而消耗掉一部分外界负载能量，从而达到增强目的，其增强效果受碳纳米管与界面滑动阻力的影响；另外，当基质断裂时，由于碳纳米管弹性模量、强度高可承受外界载荷并在断开的裂纹面之间起到桥梁连接作用，桥接的碳纳米管可对基质产生裂纹闭合的力，消耗外界载荷做功，从而提高材料韧性。
本发明制备的增韧碳化硅陶瓷材料具有极好的硬度、密度、强度和韧性，在高温条件下仍能保持大部分性能，克服了现有技术中长径比很高的晶须和纤维难以混合均匀导致陶瓷品质不均的问题，使得碳化硅陶瓷材料具有优异的性能。
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
一种增韧碳化硅陶瓷，以重量份计，包括以下组分：
碳化硅微粉90份、碳化硼微粉2份、炭黑23份、片状氧化铝3份、氟化镁2份、氧化镧0.8份、碳纳米管23份、增强纤维4份、Ti-Si-Fe合金粉4份。
碳化硅微粉的粒径为1-3μm，碳化硼微粉的粒径为0.5-1μm，Ti-Si-Fe合金粉的粒径为0.2-0.8μm，增强纤维为碳化硅晶须、氧化锆晶须、氧化铝晶须等质量比混合物，碳纳米管为OD 1-2nm，length 1-30nm，CNTs purity＞90wt％，Ash＜1.5wt％的碳纳米管。
上述的增韧碳化硅陶瓷的制备方法，包括以下步骤：
(1)将碳化硅微粉、炭黑、碳化硼微粉与碳纳米管加入乙醇中超声，乙醇加入体积为碳化硅微粉体积的400倍，形成乙醇悬浮液；
(2)将片状氧化铝、氟化镁、氧化镧和Ti-Si-Fe合金粉混合，进行球磨，球磨参数为：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1.5h后，加入增强纤维，进行球磨3.5h；
(3)在步骤(2)的混合料中加入步骤(1)所述的乙醇悬浮液，球磨8h，球磨参数为：球料比2:1，磨球为氧化锆球，球磨转速为130r/min，形成浆料；
(4)将步骤(3)所得的浆料在88℃、搅拌条件下，烘干1.5h，装入模具；
(5)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℃，充入为氩气加压至15MPa，进行恒温烧结1.5h；
(6)以35℃/min的降温速率降温至800℃，煅烧2h，再以130℃/min的升温速率升温至1350℃，煅烧1.5h，保温1.5h，最后以25℃/min的降温速率降温至室温，即得所述增韧碳化硅陶瓷。
实施例2
一种增韧碳化硅陶瓷，以重量份计，包括以下组分：
碳化硅微粉80份、碳化硼微粉3份、炭黑15份、片状氧化铝4份、氟化镁1份、氧化镧1份、碳纳米管15份、增强纤维5份、Ti-Si-Fe合金粉3份。
碳化硅微粉的粒径为1-3μm，碳化硼微粉的粒径为0.5-1μm，Ti-Si-Fe合金粉的粒径为0.2-0.8μm，增强纤维为碳化硅晶须，碳纳米管为OD 1-2nm，length 1-30nm，CNTspurity＞90wt％，Ash＜1.5wt％的碳纳米管。
上述的增韧碳化硅陶瓷的制备方法，包括以下步骤：
(1)将碳化硅微粉、炭黑、碳化硼微粉与碳纳米管加入乙醇中超声，乙醇加入体积为碳化硅微粉体积的500倍，形成乙醇悬浮液；
(2)将片状氧化铝、氟化镁、氧化镧和Ti-Si-Fe合金粉混合，进行球磨，球磨参数为：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1h后，加入增强纤维，进行球磨5h；
(3)在步骤(2)的混合料中加入步骤(1)所述的乙醇悬浮液，球磨5h，球磨参数为：球料比2:1，磨球为氧化锆球，球磨转速为150r/min，形成浆料；
(4)将步骤(3)所得的浆料在80℃、搅拌条件下，烘干2h，装入模具；
(5)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℃，充入为氩气加压至20MPa，进行恒温烧结0.5h；
(6)以40℃/min的降温速率降温至700℃，煅烧3h，再以100℃/min的升温速率升温至1400℃，煅烧1h，保温2h，最后以20℃/min的降温速率降温至室温，即得所述增韧碳化硅陶瓷。
实施例3
一种增韧碳化硅陶瓷，以重量份计，包括以下组分：
碳化硅微粉100份、碳化硼微粉1份、炭黑30份、片状氧化铝2份、氟化镁3份、氧化镧0.5份、碳纳米管30份、增强纤维3份、Ti-Si-Fe合金粉5份。
碳化硅微粉的粒径为1-3μm，碳化硼微粉的粒径为0.5-1μm，Ti-Si-Fe合金粉的粒径为0.2-0.8μm，增强纤维为二氧化钛晶须，碳纳米管为OD 1-2nm，length 1-30nm，CNTspurity＞90wt％，Ash＜1.5wt％的碳纳米管。
上述的增韧碳化硅陶瓷的制备方法，包括以下步骤：
(1)将碳化硅微粉、炭黑、碳化硼微粉与碳纳米管加入乙醇中超声，乙醇加入体积为碳化硅微粉体积的200倍，形成乙醇悬浮液；
(2)将片状氧化铝、氟化镁、氧化镧和Ti-Si-Fe合金粉混合，进行球磨，球磨参数为：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2h后，加入增强纤维，进行球磨2h；
(3)在步骤(2)的混合料中加入步骤(1)所述的乙醇悬浮液，球磨10h，球磨参数为：球料比2:1，磨球为氧化锆球，球磨转速为100r/min，形成浆料；
(4)将步骤(3)所得的浆料在95℃、搅拌条件下，烘干1h，装入模具；
(5)将装有原料的模具在真空度10-3MPa的条件下，以50℃/min的升温速率加热至1600℃，充入为氩气加压至10MPa，进行恒温烧结2h；
(6)以30℃/min的降温速率降温至900℃，煅烧1h，再以150℃/min的升温速率升温至1300℃，煅烧2h，保温1h，最后以30℃/min的降温速率降温至室温，即得所述增韧碳化硅陶瓷。
对比例1
与实施例1的不同之处在于，将Ti-Si-Fe合金粉等量替换为增强纤维。
对比例2
与实施例1的不同之处在于，将炭黑等量替换为多孔碳。
对比例3
与实施例1的不同之处在于，不进行步骤(2)的球磨，直接将剩余原料与步骤(1)的乙醇悬浮液混合后球磨。
对比例4
与实施例1的不同之处在于，所述步骤(6)为：以35℃/min的降温速率将温度1350℃，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1-3及对比例1-4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，断裂韧性按照GB/T 4742-1984测试。
表1
Figure BDA0002482371550000091
Figure BDA0002482371550000101
由上表可知，本发明提供的陶瓷材料具有更好的硬度、密度、强度及断裂韧性，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)

1.一种增韧碳化硅陶瓷，其特征在于，以重量份计，包括以下组分：
碳化硅微粉80-100份、碳化硼微粉1-3份、炭黑15-30份、片状氧化铝2-4份、氟化镁1-3份、氧化镧0.5-1份、碳纳米管15-30份、增强纤维3-5份、Ti-Si-Fe合金粉3-5份。
2.根据权利要求1所述的增韧碳化硅陶瓷，其特征在于，所述碳化硅微粉的粒径为1-3μm，所述碳化硼微粉的粒径为0.5-1μm，所述Ti-Si-Fe合金粉的粒径为0.2-0.8μm。
3.根据权利要求1所述的增韧碳化硅陶瓷，其特征在于，所述增强纤维为碳化硅晶须、氧化锆晶须、氧化铝晶须、二氧化硅晶须、二氧化钛晶须中的一种或多种。
4.根据权利要求1所述的增韧碳化硅陶瓷，其特征在于，所述碳纳米管为OD 1-2nm，length 1-30nm，CNTs purity＞90wt％，Ash＜1.5wt％的碳纳米管。
5.一种权利要求1-4任一项所述的增韧碳化硅陶瓷的制备方法，其特征在于，包括以下步骤：
(1)将碳化硅微粉、炭黑、碳化硼微粉与碳纳米管加入乙醇中超声，乙醇加入体积为碳化硅微粉体积的200-500倍，形成乙醇悬浮液；
(2)将片状氧化铝、氟化镁、氧化镧和Ti-Si-Fe合金粉混合，进行球磨，球磨1-2h后，加入增强纤维，进行球磨2-5h；
(3)在步骤(2)的混合料中加入步骤(1)所述的乙醇悬浮液，球磨5-10h，形成浆料；
(4)将步骤(3)所得的浆料在80-95℃、搅拌条件下，烘干1-2h，装入模具；
(5)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0.5-2h；
(6)以30-40℃/min的降温速率降温至700-900℃，煅烧1-3h，再以100-150℃/min的升温速率升温至1300-1400℃，煅烧1-2h，保温1-2h，最后以20-30℃/min的降温速率降温至室温，即得所述增韧碳化硅陶瓷。
6.根据权利要求5所述的增韧碳化硅陶瓷的制备方法，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。
7.根据权利要求5所述的增韧碳化硅陶瓷的制备方法，其特征在于，步骤(3)中，所述球磨的参数为：球料比2:1，磨球为氧化锆球，球磨转速为100-150r/min。
8.根据权利要求5所述的增韧碳化硅陶瓷的制备方法，其特征在于，所述惰性气体为氩气。
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