CN116535215B - 一种非化学计量比多元碳化物陶瓷的制备方法 - Google Patents
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Abstract
本发明公开了一种非化学计量比多元碳化物陶瓷的制备方法,涉及碳化物陶瓷技术领域。该方法通过将两种及以上的过渡金属粉与碳粉高能球磨混匀,利用热压烧结技术,使元素粉末在高温下发生剧烈的化合反应,同时在压力的作用下烧结致密化,一步得到目标陶瓷块体。该方法制备的碳化物为具有面心立方结构的单相固溶体陶瓷,空间群为纯度高,孔隙率低,并且可以一步制备非化学计量比的陶瓷块,工艺简单,效率高。
Description
技术领域
本发明涉及碳化物陶瓷技术领域,具体涉及一种非化学计量比多元碳化物陶瓷的制备方法。
背景技术
随着人类文明进步,人类对太空的探索不断深入,世界范围内对高性能高超声速飞行器的需求日益迫切,这就要求使用的热防护材料具有足够的机械抗氧化性,能够承受极高温度的恶劣环境。超高温陶瓷(UHTCs)通常被定义为熔点在3000℃以上的化合物,主要由过渡金属的硼、碳或氮化物组成,尤其是碳化物由于具有极高的熔点、优异的高温力学性能和良好的抗烧蚀性能,目前成为满足高温性能要求的最有前景的候选材料。
然而传统的超高温碳化物,如ZrC和HfC,氧化后通常会在表面形成疏松的氧化层,抗氧化性较差,因此其应用受到很大的限制。大量研究表明,加入IV-VB族金属元素以获得多组分碳化物固溶体是提高超高温碳化物陶瓷抗氧化性的有效途径,如国防科技大学的ZhangJian等人的研究(ZhangJ,Wa ngS,LiW,etal.UnderstandingtheoxidationbehaviorofTa–Hf–Cternaryceramicsathi ghtemperature[J].CorrosionScience,2020,164:108348.)表明(Hf,Ta)C的抗氧化性与单个HfC或TaC二元碳化物相比显著增强,这归因于(Hf0.75Ta0.25)C中形成了致密的Hf6Ta2O17内层以及Hf-Ta-O-C过渡层作为氧屏障阻碍氧的扩散。另外,近年来也有部分研究报导在多元固溶体碳化物中加入碳空位可进一步提升其抗氧化性能,如中南大学的LunHuilin等人发表文献(LunH,YuanJ,ZengY,etal.Mechanismsresponsibleforenhancinglow-temperatureoxidationresistanceofno nstoichiometric(Zr,Ti)C[J].JournaloftheAmericanCeramicSociety,2022,105(8):5309-5324.)表明,当碳浓度为0.8时,Zr0.8Ti0.2C0.8相较于化学计量比的Zr0.8Ti0.2C具有更优异的抗氧化性能,其原因是形成了致密的t-(Zr,Ti)O2氧化物固溶体,可以更有效地保护内部基体。
目前,制备多元碳化物陶瓷的方法主要包括机械合金化法、碳热还原法、溶胶-凝胶法、自蔓延高温合成法、二元碳化物高温固溶法等等。上述制备方法具备各自的优势,但是其共同点是只能获得对应的多元碳化物固溶体粉末,需要结合后续的热压烧结、热等静压烧结或放电等离子体烧结等方式才能获得对应陶瓷块体,整个流程所需设备多,工艺复杂且制备周期长。此外,上述制备方法只能实现化学计量比的多元碳化物陶瓷制备,难以完成含有碳空位的非化学计量比的多元碳化物陶瓷制备。
发明内容
本发明的目的是提供一种非化学计量比多元碳化物陶瓷的制备方法,该方法制备的碳化物为具有面心立方结构的单相固溶体陶瓷,空间群为纯度高,孔隙率低,并且可以一步制备非化学计量比的陶瓷块,工艺简单,效率高。
为实现上述目的,本发明提供了一种非化学计量比多元碳化物陶瓷的制备方法,具体包括以下步骤:
S1、根据一定比例称取过渡金属粉和碳粉备用;
S2、将称取好的元素粉放入行星球磨罐中,利用高能球磨将其混合均匀;
S3、将混合元素粉放入烘箱中充分干燥并过筛;
S4、在石墨模具内腔粘附石墨纸;
S5、将干燥后的元素粉倒入石墨模具,并预压排出空气;
S6、将装载了元素粉的石墨模具放入热压烧结炉,高温高压烧结;
S7、随炉冷却后脱模得到目标成分陶瓷块。
优选的,所述步骤S1中过渡金属为Hf、Zr、Ti、Ta、Nb中的至少两种,过渡金属粉和碳粉的纯度均≥99%,其粒度均为微米或纳米级。
优选的,所述步骤S2中球磨转速为150-300rpm,球磨时长6-12h,球磨介质为无水乙醇,球磨罐和球体材料为碳化钨,球料比为4~6:1。
优选的,所述步骤S3中烘箱温度为30-40℃,烘干时间≥20h,过筛目数≥200目。
优选的,真空烧结气氛,热压烧结炉中真空度小于5Pa,热压烧结炉以10℃/min的升温速率从室温升至800℃,以7℃/min从800℃升温至1500℃,以5℃/min从1500℃升温至1800-2100℃,并于设定温度保温0.5-2h。
因此,本发明提供了一种非化学计量比多元碳化物陶瓷的制备方法,针对现有制备方法有益效果如下:
(1)该方法制备的碳化物为具有面心立方结构的单相固溶体陶瓷,空间群为纯度高,孔隙率低,并且可以一步制备非化学计量比的陶瓷块,工艺简单,效率高;
(2)本方法工艺简单,周期短,组分设计灵活,可制备包含化学计量比/非化学计量比在内的宽范围元素比例的陶瓷;
(3)本方法包括但不限于多元碳化物陶瓷的制备,还可扩展至多元氮化物和硼化物等领域,极大扩宽了多元超高温陶瓷的成分设计范围,有利于优化多元超高温陶瓷中各组份含量,实现高性能超高温陶瓷的制备。
下面通过附图和实施例,对本发明的技术方案做进一步的详细描述。
附图说明
图1是本发明实施例1、实施例2和实施例3制得的碳化物陶瓷块的XR D图谱;
图2是本发明实施例1制得的碳化物陶瓷块的宏观形貌图;
图3是本发明实施例1制得的碳化物陶瓷块的扫描电镜图;
图4是本发明实施例2制得的碳化物陶瓷块的宏观形貌图;
图5是本发明实施例2制得的碳化物陶瓷块的扫描电镜图;
图6是本发明实施例3制得的碳化物陶瓷块的宏观形貌图;
图7是本发明实施例3制得的碳化物陶瓷块的扫描电镜图。
具体实施方式
以下对在附图中提供的本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围,而是仅仅表示本发明的选定实施例。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
本发明提供了一种非化学计量比多元碳化物陶瓷的制备方法,包括以下步骤:
S1、将Hf粉、Ti粉、C粉分别称量17.6g、1.0g、1.4g备用,其中Hf粉和Ti粉的粒度为325目,纯度≥99.9%,碳粉的粒度为30nm,纯度≥99.5%;
S2、将称量好的元素粉放入碳化钨的行星球磨罐中,高能球磨10h将其混合均匀,其中球磨介质为乙醇,球料比为5:1,转速150rpm;
S3、将混合元素粉放入30℃烘箱中,充分干燥24h,并过200目筛;
S4、在石墨模具内腔粘附石墨纸;
S5、将干燥后的元素粉倒入石墨模具,并采用1T的压力预压排出尽可能多的空气;
S6、将装载了元素粉的石墨模具放入热压烧结炉,真空烧结气氛,热压烧结炉中真空度小于5Pa,以10℃/min的升温速率从室温升至800℃,以7℃/mi n从800℃升温至1500℃,以5℃/min从1500℃升温至1900℃,并于设定温度保温1h;
S7、随炉冷却后利用液压机脱模得到Hf0.83Ti0.17C陶瓷块。
实施例2
本发明提供了一种非化学计量比多元碳化物陶瓷的制备方法,包括以下步骤:
S1、将Hf粉、Ti粉、C粉分别称量17.8g、1.0g、1.2g备用,其中Hf粉和Ti粉的粒度为325目,纯度≥99.9%,碳粉的粒度为30nm,纯度≥99.5%;
S2、将称量好的元素粉放入碳化钨的行星球磨罐中,高能球磨10h将其混合均匀,其中球磨介质为乙醇,球料比为5:1,转速150rpm;
S3、将混合元素粉放入30℃烘箱中,充分干燥24h,并过200目筛;
S4、在石墨模具内腔粘附石墨纸;
S5、将干燥后的元素粉倒入石墨模具,并采用1T的压力预压排出尽可能多的空气;
S6、将装载了元素粉的石墨模具放入热压烧结炉,真空烧结气氛,热压烧结炉中真空度小于5Pa,以10℃/min的升温速率从室温升至800℃,以7℃/min从800℃升温至1500℃,以5℃/min从1500℃升温至1900℃,并于设定温度保温1h;
S7、随炉冷却后利用液压机脱模得到Hf0.83Ti0.17C0.83陶瓷块。
实施例3
本发明提供了一种非化学计量比多元碳化物陶瓷的制备方法,包括以下步骤:
S1、将Hf粉、Zr粉、Ti粉、Nb粉、C粉分别称量12.6g、4.3g、0.7g、0.7g、1.7g备用,其中Hf粉、Zr粉、Ti粉的粒度为325目,纯度≥99.9%,Nb粉的粒度为100nm,纯度≥99.9%,碳粉的粒度为30nm,纯度≥99.5%;
S2、将称量好的元素粉放入碳化钨的行星球磨罐中,高能球磨8h将其混合均匀,其中球磨介质为乙醇,球料比为5:1,转速250rpm;
S3、将混合元素粉放入30℃烘箱中,充分干燥24h,并过200目筛;
S4、在石墨模具内腔粘附石墨纸;
S5、将干燥后的元素粉倒入石墨模具,并采用1T的压力预压排出尽可能多的空气;
S6、将装载了元素粉的石墨模具放入热压烧结炉,真空烧结气氛,热压烧结炉中真空度小于5Pa,以10℃/min的升温速率从室温升至800℃,以7℃/min从800℃升温至1500℃,以5℃/min从1500℃升温至1900℃,并于设定温度保温1h;
S7、随炉冷却后利用液压机脱模得到Hf0.5Zr0.33Ti0.11Nb0.06C陶瓷块。
如图1所示,XRD图谱表明实施例1,实施例2和实施例3所制备的碳化物陶瓷块有且只有一组近似HfC的衍射峰,说明实施例1,实施例2和实施例3所获得的陶瓷块已经实现完全固溶,具有典型的单一相面心立方结构。
如图2、4、6所示,碳化物陶瓷块的宏观形貌图表明实施例1、2、3所制得的碳化物陶瓷块十分致密,未观察到大尺寸孔隙和裂纹。
如图3、5、7所示,碳化物陶瓷块的扫描电镜图表明实施例1、2、3制得的碳化物陶瓷块成分均匀,未观察到明显的元素偏聚,表明形成均一固溶体。
表1为实施例1、2、3所制得的碳化物陶瓷块的相对密度及开孔率统计,通过阿基米德排水法测量并计算所得。
表1
实施例1 | 实施例2 | 实施例3 | |
相对密度% | 96.02 | 97.68 | 95.07 |
开孔率% | 0.76 | 0.94 | 0.86 |
如表1所示,实施例1、2、3所制得的碳化物陶瓷块的相对密度均大于95%,开孔率均保持在1%以下。
因此,本发明提供了一种非化学计量比多元碳化物陶瓷的制备方法,使用过渡金属元素粉末和碳粉末为原料,采用热压烧结技术使元素粉末在高温下发生剧烈的化合反应,同时在压力的作用下烧结致密化,一步得到多元碳化物陶瓷块体;本方法工艺简单、周期短、组分设计灵活,可以实现高致密度、低开孔率、高纯度的多元碳化物单一相固溶体陶瓷,为新一代超高温多元陶瓷在航天航空、核能等领域的应用提供创新高效的制备途径。
最后应说明的是:以上实施例仅用以说明本发明的技术方案而非对其进行限制,尽管参照较佳实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对本发明的技术方案进行修改或者等同替换,而这些修改或者等同替换亦不能使修改后的技术方案脱离本发明技术方案的精神和范围。
Claims (2)
1.一种非化学计量比多元碳化物陶瓷的制备方法,其特征在于,具体包括以下步骤:
S1、根据一定比例称取过渡金属粉和碳粉备用;
S2、将称取好的元素粉放入行星球磨罐中,利用高能球磨将其混合均匀;
S3、将混合元素粉放入烘箱中充分干燥并过筛;
S4、在石墨模具内腔粘附石墨纸;
S5、将干燥后的元素粉倒入石墨模具,并预压排出空气;
S6、将装载了元素粉的石墨模具放入热压烧结炉,高温高压烧结;
S7、随炉冷却后脱模得到目标成分陶瓷块;
所述步骤S1中过渡金属为Hf、Zr、Ti、Ta、Nb中的至少两种,过渡金属粉和碳粉的纯度均≥99%,其粒度均为微米或纳米级;
所述步骤S6中热压烧结条件为:真空烧结气氛,烧结炉中真空度小于5Pa,热压烧结炉以10℃/min的升温速率从室温升至800℃,以7℃/min从800℃升温至1500℃,以5℃/min从1500℃升温至1800-2100℃,并于设定温度保温0.5-2h;
所述步骤S2中球磨转速为150-300rpm,球磨时长6-12h,球磨介质为无水乙醇,球磨罐和球体材料为碳化钨,球料比为4~6:1。
2.根据权利要求1所述的一种非化学计量比多元碳化物陶瓷的制备方法,其特征在于:所述步骤S3中烘箱温度为30-40℃,烘干时间≥20h,过筛目数≥200目。
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