CN113582696A - 一种(ZrTiCoNb)C高熵碳化物陶瓷材料及其制备方法 - Google Patents

一种(ZrTiCoNb)C高熵碳化物陶瓷材料及其制备方法 Download PDF

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CN113582696A
CN113582696A CN202111007346.0A CN202111007346A CN113582696A CN 113582696 A CN113582696 A CN 113582696A CN 202111007346 A CN202111007346 A CN 202111007346A CN 113582696 A CN113582696 A CN 113582696A
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carbide ceramic
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张锐
王海龙
关莉
周雪梦
李明亮
娄元郑
张新月
高前程
樊磊
郭少杰
范冰冰
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Zhengzhou University of Aeronautics
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Abstract

本发明属于高熵陶瓷材料技术领域,公开了一种(ZrTiCoNb)C高熵碳化物陶瓷材料及其制备方法,所述制备方法包括:将锆源、钛源、钴源、铌源以及碳源通过机械研磨混合均匀,获得混合粉体;随后将获得的混合粉体预压制坯后,于1200~2000℃微波烧结1~2h,即得高熵碳化物陶瓷材料。本发明方法合成成本低且合成效率高,且通过本发明方法制得的高熵碳化物陶瓷材料,具有较低的氧含量以及较细的晶粒尺寸。

Description

一种(ZrTiCoNb)C高熵碳化物陶瓷材料及其制备方法
技术领域
本发明涉及高熵陶瓷材料技术领域,尤其涉及一种(ZrTiCoNb)C高熵碳化物陶瓷材料及其制备方法。
背景技术
高熵最初的概念是从高熵合金的发展得到的,已经形成了一种新的材料理论概念,已成为现在材料领域研究者们关注的热点。高熵材料突破了传统复合材料的限制,为开发新的材料体系打开了空间。高熵材料具有优良的性能,在热和环境保护,热电水分解催化和能源储存等方面有广泛的应用,由于体系内包含了多种组元,提高了整个陶瓷系统内部的混乱程度,同时也增加了系统的构型熵值。由于其特殊的微观结构,高熵陶瓷在基础科学研究或实际应用方面都具有巨大的潜力。
传统烧结高熵碳化物陶瓷材料方法有热压烧结、马弗炉烧结等,这些传统烧结方法都有同样的缺点,传统烧结方式加热样品是根据热传导、对流和辐射原理使热量从外部传至物料内部,热量总是由表及里传递进行加热物料,物料中不可避免地存在温度梯度,故物料加热不均匀,致使物料出现局部过热,也会导致样品烧结时间过长,能源利用不充分,成本高,污染大。
发明内容
为了解决上述现有技术中的不足,本发明提供一种(ZrTiCoNb)C高熵碳化物陶瓷材料及其制备方法,本发明采用微波烧结的方法,可以有效提高烧结速率,缩短整体烧结时间,提高能源利用效率。
本发明的一种(ZrTiCoNb)C高熵碳化物陶瓷材料及其制备方法是通过以下技术方案实现的:
本发明的第一个目的是提供一种(ZrTiCoNb)C高熵碳化物陶瓷材料的制备方法,包括以下步骤:
将锆源、钛源、钴源、铌源以及碳源通过机械研磨混合均匀,获得混合粉体;随后将获得的混合粉体预压制坯后,于1200~2000℃微波烧结1~2h,即得高熵碳化物陶瓷材料。
进一步地,所述微波烧结的加热加热频率为2.45GHz;,烧结温度为1200~2000℃,烧结时间为1~2h,升温速率为10~50℃/min。
进一步地,机械研磨后,所述混合粉体的平均粒径为0.1~1μm。
进一步地,所述锆源、钛源、钴源、铌源以及碳源的直径均为1~3μm。
进一步地,所述混合粉体预压制坯是将混合粉体置于模具中,在7~12MPa的压力下预压1~2min而制得的;其中,坯体的厚度为3~5mm。
进一步地,所述机械研磨为湿式球磨,湿法球磨的球料比为3~6:1,控制剂为无水乙醇或丙酮,球磨转速为200~300r/min。
进一步地,所述锆源为锆氧化物;所述钛源为钛氧化物;所述钴源为钴氧化物;所述铌源为铌氧化物;所述碳源为碳黑。
进一步地,所述锆氧化物为ZrO2;所述钛氧化物为TiO2;所述钴氧化物为CoO;所述铌氧化物为Nb2O5
进一步地,所述锆源、钛源、钴源、铌源以及碳源的摩尔比为1:0.5~2:0.5~2:0.5~2:1~3。
进一步地,所述锆源、钛源、钴源、铌源以及碳源的摩尔比为1:1:1:1:2。
本发明的第二个目的是提供一种根据上述的制备方法制得高熵碳化物陶瓷材料。
本发明与现有技术相比,具有以下有益效果:
1)本发明以各组分的金属氧化物和碳黑为原料制备(ZrTiCoNb)C高熵碳化物陶瓷,通过碳热还原多种过渡金属氧化物,加强混合粉体的微波表现力,提高样品的微波效应,并通过湿式球磨混合得到(ZrTiCoNb)C高熵碳化物陶瓷混料粉体进行微波烧结,从而使物料的粒度变小,达到原料混合最大均匀性,可以有效降低烧结温度,而且可破坏物料原来的晶体结构,产生一定的晶相结合,提高表面能,帮助后续微波烧结制备高熵碳化物陶瓷材料。
2)本发明提供的制备方法制得(ZrTiCoNb)C高熵碳化物陶瓷复合材料,相比传统烧结工艺,微波烧结利用物质自身介质损耗来吸收微波,进行体积加热,样品升温速度快,保温时间短,可以有效降低(ZrTiCoNb)C高熵碳化物陶瓷复合材料的合成成本,提高陶瓷材料的合成效率。
3)本发明解决了(ZrTiCoNb)C高熵碳化物陶瓷材料的制备问题,通过严格控制微波烧结炉的各项参数,并通过XRD进行表征,最终获得了高熵碳化物陶瓷材料,丰富了陶瓷材料体系。
附图说明
图1为实施例1制备的(ZrTiCoNb)C高熵碳化物陶瓷材料的微波烧结升温曲线,其中,圆圈线表示烧结温度曲线;方块线表示微波输入功率曲线;三角线表示样品对微波的反射功率曲线;
图2为实施例1的XRD示意图,图中,图2下为实施例1中步骤1所得到的的混合粉体的XRD示意图,图2上为实施例1最终制得的(ZrTiCoNb)C高熵碳化物陶瓷材料的XRD示意图;
图3为实施例1制备的(ZrTiCoNb)C高熵碳化物陶瓷材料的SEM显微照片;
图4为实施例2的XRD示意图,图中,图4下为实施例2中步骤1所得到的的混合粉体的XRD示意图,图4上为实施例2最终制得的(ZrTiCoNb)C高熵碳化物陶瓷材料的XRD示意图;
图5为实施例2制备的(ZrTiCoNb)C高熵碳化物陶瓷材料的SEM显微照片;
图6为对比例1制备的(ZrTiCoNb)C高熵碳化物陶瓷材料的XRD示意图;
图7为对比例1制备的(ZrTiCoNb)C高熵碳化物陶瓷材料的SEM显微照片;
图8为对比例2制备的(ZrTiCoNb)C高熵碳化物陶瓷材料的SEM显微照片。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述。需要说明的是,下述各实施例中所述实验方法如无特殊说明,均为常规方法;采用的试剂和材料,如无特殊说明,均可在市场上购买得到。
实施例1
本实施例提供一种(ZrTiCoNb)C高熵碳化物陶瓷材料的制备方法,包括以下步骤:
步骤1,原料混合粉体制备:按照摩尔比为1:1:1:1:2分别称取ZrO2、TiO2、CoO、Nb2O5和碳黑粉体原料,利用湿式球磨方式使其均匀混合,球磨的球料比为5:1,控制剂为无水乙醇,转速为300r/min,球磨至混合粉体的平均粒径为0.5μm,获得混合粉体;
步骤2,高熵陶瓷粉体制备:取混合粉体30g,并将其在室温下预压制坯,预压压力为10mpa,预压保压时间为1min,生坯厚度为3mm,将生坯置于氧化铝坩埚中,附加由莫来石板和陶瓷纤维保温棉组成的四方体保温结构,于1500℃微波烧结,保温时间为20min,频率为2.45GHz,升温速率为20℃/min,即得(ZrTiCoNb)C高熵碳化物陶瓷材料。
实施例2
本实施例提供一种(ZrTiCoNb)C高熵碳化物陶瓷材料的制备方法,包括以下步骤:
步骤1,原料混合粉体制备:按照摩尔比为1:1:1:1:2分别称取ZrO2、TiO2、CoO、Nb2O5和碳黑粉体原料,利用湿式球磨方式使其均匀混合,球磨的球料比为5:1,控制剂为无水乙醇,转速为300r/min,球磨至混合粉体的平均粒径为0.5μm,获得混合粉体;
步骤2,高熵陶瓷粉体制备:取混合粉体50g,并将其在室温下预压制坯,预压压力为12mpa,预压保压时间为1.5min,生坯厚度为5mm,将生坯置于氧化铝坩埚中,附加由莫来石板和陶瓷纤维保温棉组成的四方体保温结构,于1360℃微波烧结,保温时间为30min,频率为2.45GHz,升温速率为30℃/min,即得(ZrTiCoNb)C高熵碳化物陶瓷材料。
实施例3
本实施例提供一种(ZrTiCoNb)C高熵碳化物陶瓷材料的制备方法,包括以下步骤:
步骤1,原料混合粉体制备:按照摩尔比为1:0.5:0.5:0.5:1分别称取ZrO2、TiO2、CoO、Nb2O5和碳黑粉体原料,利用湿式球磨方式使其均匀混合,球磨的球料比为3:1,控制剂为丙酮,转速为200r/min,球磨至混合粉体的平均粒径为1μm,获得混合粉体;
步骤2,高熵陶瓷粉体制备:取混合粉体30g,并将其在室温下预压制坯,预压压力为7mpa,预压保压时间为1min,生坯厚度为3mm,将生坯置于氧化铝坩埚中,附加保温结构,于1200℃微波烧结,保温时间为40min,频率为2.45MHz,升温速率为10℃/min,即得(ZrTiCoNb)C高熵碳化物陶瓷材料。
实施例4
本实施例提供一种(ZrTiCoNb)C高熵碳化物陶瓷材料的制备方法,包括以下步骤:
步骤1,原料混合粉体制备:按照摩尔比为1:2:2:2:3分别称取ZrO2、TiO2、CoO、Nb2O5和碳黑粉体原料,利用湿式球磨方式使其均匀混合,球磨的球料比为6:1,控制剂为丙酮,转速为250r/min,球磨至混合粉体的平均粒径为0.1μm,获得混合粉体;
步骤2,高熵陶瓷粉体制备:取混合粉体30g,并将其在室温下预压制坯,预压压力为9mpa,预压保压时间为2min,生坯厚度为4mm,将生坯置于氧化铝坩埚中,附加保温结构,于1200℃微波烧结,保温时间为40min,频率为2.45MHz,升温速率为10℃/min,即得(ZrTiCoNb)C高熵碳化物陶瓷材料。
对比例1
与实施例1相同,不同之处在于,采用马弗炉方式烧结,烧结温度为1400℃,烧结时间需8h。。
对比例2
与实施例2相同,不同之处在于,采用干式球磨方式,球料比为5:1,转速为300r/min。
实验部分
下面对以上实施例1~2与对比例1~2分别制得的高熵碳化物陶瓷复合材料进行物相分析和相关微观形貌测试:
为了观察不同变量下制备的高熵碳化物陶瓷复合材料的物相差别,利用X射线衍射分析仪(XRD)(日本理学电机株式会社SmartLab型)对实施例1~2得到(ZrTiCoNb)C高熵碳化物陶瓷材料及对比例1~2的材料进行物相表征;为了观察制备样品的微观形貌结构,利用扫描电子显微镜(SEM)(日本电子株式会社的JSM-7001F型)对实施例1~2的(ZrTiCoNb)C高熵碳化物陶瓷材料及对比例1~2的材料进行微观形貌表征。
图1为本发明实施例1制备的(ZrTiCoNb)C高熵碳化物陶瓷材料的微波烧结升温曲线,其中,圆圈线表示烧结温度曲线;方块线表示微波输入功率曲线;三角线表示样品对微波的反射功率曲线。从图1的微波烧结曲线可以看出,利用微波烧结样品在13min左右开始升温,在35min左右即可升温至1500℃,整体烧结时间在1h内。
图2为本发明实施例1的XRD示意图,图中,图2下为实施例1中步骤1所得到的的混合粉体的XRD示意图,图2上为实施例1最终制得的(ZrTiCoNb)C高熵碳化物陶瓷材料的XRD示意图。图3为实施例1制备的(ZrTiCoNb)C高熵碳化物陶瓷材料的SEM显微照片。
图4为本发明实施例2的XRD示意图,图中,图4下为实施例2中步骤1所得到的的混合粉体的XRD示意图,图4上为实施例2最终制得的(ZrTiCoNb)C高熵碳化物陶瓷材料的XRD示意图。图5为实施例2制备的(ZrTiCoNb)C高熵碳化物陶瓷材料的SEM显微照片。
图6为对比例1制备的(ZrTiCoNb)C高熵碳化物陶瓷材料的XRD示意图;图7为对比例1制备的(ZrTiCoNb)C高熵碳化物陶瓷材料的SEM显微照片。
图8为对比例2制备的(ZrTiCoNb)C高熵碳化物陶瓷材料的SEM显微照片。
参阅图5和图8,对比实施例2和对比例2,湿式球磨比普通干式球磨可以使物料混合更为均匀细小,原料粉体间的氧含量会降低,并且论证了微波烧结高熵陶瓷碳化物复合材料的优势,对比传统烧结方法,微波烧结制备高熵陶瓷可以大幅度缩短烧结时间,节省了实验成本与能耗。
本发明的方法相较于其他传统烧结方法,采用微波加热方式,通过被加热体内部偶极分子高频往复运动,产生“内摩擦热”而使被加热物料温度升高,使物料内外部均匀加热,且加热速度快,仅需传统加热方式能耗的几分之一或几十分之一就可达到加热目的。利用微波加热技术可以有效降低(ZrTiCoNb)C高熵碳化物陶瓷的合成成本,提高合成效率。
显然,上述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做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。

Claims (10)

1.一种(ZrTiCoNb)C高熵碳化物陶瓷材料的制备方法,其特征在于,包括以下步骤:
将锆源、钛源、钴源、铌源以及碳源通过机械研磨混合均匀,获得混合粉体;随后将获得的混合粉体预压制坯后,于1200~2000℃微波烧结1~2h,即得高熵碳化物陶瓷材料。
2.根据权利要求1所述的制备方法,其特征在于,所述微波烧结的加热频率为2.45GHz,烧结温度为1200~2000℃,烧结时间为1~2h,升温速率为10~50℃/min。
3.根据权利要求1所述的制备方法,其特征在于,机械研磨后,所述混合粉体的粒径为0.1~1μm。
4.根据权利要求1所述的制备方法,其特征在于,所述混合粉体预压制坯是将混合粉体置于模具中,在7~12MPa的压力下预压1~2min而制得的;其中,坯体的厚度为3~5mm。
5.根据权利要求1所述的制备方法,其特征在于,所述机械研磨为湿式球磨,湿法球磨的球料比为3~6:1,控制剂为无水乙醇或丙酮,球磨转速为200~300r/min。
6.根据权利要求1所述的制备方法,其特征在于,所述锆源为锆氧化物;所述钛源为钛氧化物;所述钴源为钴氧化物;所述铌源为铌氧化物;所述碳源为碳黑。
7.根据权利要求6所述的制备方法,其特征在于,所述锆氧化物为ZrO2;所述钛氧化物为TiO2;所述钴氧化物为CoO;所述铌氧化物为Nb2O5
8.根据权利要求1所述的制备方法,其特征在于,所述锆源、钛源、钴源、铌源以及碳源的摩尔比为1:0.5~2:0.5~2:0.5~2:1~3。
9.根据权利要求8所述的制备方法,其特征在于,所述锆源、钛源、钴源、铌源以及碳源的摩尔比为1:1:1:1:2。
10.一种权利要求1~9任意一项所述的制备方法制得的高熵碳化物陶瓷材料。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115582547A (zh) * 2022-10-18 2023-01-10 郑州航空工业管理学院 一种Cu/C/SiC复合材料及其制备方法
CN115925392A (zh) * 2022-12-13 2023-04-07 郑州航空工业管理学院 一种过渡金属高熵陶瓷氧化物复合材料粉体及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109180188A (zh) * 2018-10-08 2019-01-11 中南大学 一种高熵含硼碳化物超高温陶瓷粉体及其制备方法
CN110078512A (zh) * 2019-05-17 2019-08-02 淄博星澳新材料研究院有限公司 超高温高熵碳化物粉体及其制备方法
CN110484796A (zh) * 2019-09-20 2019-11-22 吉林大学 一种过渡金属碳化物高熵陶瓷颗粒及其制备方法
CN110606749A (zh) * 2019-09-29 2019-12-24 石家庄铁道大学 一种高熵硼化物陶瓷材料及其制备方法
CN112457017A (zh) * 2020-12-09 2021-03-09 安徽工业大学 一种高性能(TiTaHfZrNb)C高熵碳化物陶瓷及其制备方法
CN112723862A (zh) * 2020-12-29 2021-04-30 太原理工大学 简单低耗制备高熵氧化物陶瓷材料的方法
US20210147242A1 (en) * 2019-11-15 2021-05-20 The Regents Of The University Of California Metallic multicomponent carbides
CN112830785A (zh) * 2021-01-19 2021-05-25 山东大学 一种层状高熵双硼碳化物陶瓷粉体及其制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109180188A (zh) * 2018-10-08 2019-01-11 中南大学 一种高熵含硼碳化物超高温陶瓷粉体及其制备方法
CN110078512A (zh) * 2019-05-17 2019-08-02 淄博星澳新材料研究院有限公司 超高温高熵碳化物粉体及其制备方法
CN110484796A (zh) * 2019-09-20 2019-11-22 吉林大学 一种过渡金属碳化物高熵陶瓷颗粒及其制备方法
CN110606749A (zh) * 2019-09-29 2019-12-24 石家庄铁道大学 一种高熵硼化物陶瓷材料及其制备方法
US20210147242A1 (en) * 2019-11-15 2021-05-20 The Regents Of The University Of California Metallic multicomponent carbides
CN112457017A (zh) * 2020-12-09 2021-03-09 安徽工业大学 一种高性能(TiTaHfZrNb)C高熵碳化物陶瓷及其制备方法
CN112723862A (zh) * 2020-12-29 2021-04-30 太原理工大学 简单低耗制备高熵氧化物陶瓷材料的方法
CN112830785A (zh) * 2021-01-19 2021-05-25 山东大学 一种层状高熵双硼碳化物陶瓷粉体及其制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115582547A (zh) * 2022-10-18 2023-01-10 郑州航空工业管理学院 一种Cu/C/SiC复合材料及其制备方法
CN115582547B (zh) * 2022-10-18 2024-02-23 郑州航空工业管理学院 一种Cu/C/SiC复合材料及其制备方法
CN115925392A (zh) * 2022-12-13 2023-04-07 郑州航空工业管理学院 一种过渡金属高熵陶瓷氧化物复合材料粉体及其制备方法

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