CN114751737A - 一种锆酸稀土基高熵陶瓷纳米纤维及其制备方法和应用 - Google Patents
一种锆酸稀土基高熵陶瓷纳米纤维及其制备方法和应用 Download PDFInfo
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- CN114751737A CN114751737A CN202110957031.6A CN202110957031A CN114751737A CN 114751737 A CN114751737 A CN 114751737A CN 202110957031 A CN202110957031 A CN 202110957031A CN 114751737 A CN114751737 A CN 114751737A
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- rare earth
- zirconic acid
- salt
- zirconium
- acid rare
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 177
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 106
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- 239000000463 material Substances 0.000 claims abstract description 39
- 239000000835 fiber Substances 0.000 claims abstract description 25
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 4
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 3
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
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- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 3
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- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 3
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- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 3
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- 238000002411 thermogravimetry Methods 0.000 description 2
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- 241000272525 Anas platyrhynchos Species 0.000 description 1
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- PYOOBRULIYNHJR-UHFFFAOYSA-K trichloroholmium Chemical compound Cl[Ho](Cl)Cl PYOOBRULIYNHJR-UHFFFAOYSA-K 0.000 description 1
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Abstract
本发明提供了一种锆酸稀土基高熵陶瓷纳米纤维及其制备方法和应用。本发明的锆酸稀土基高熵陶瓷纳米纤维,包括助纺剂和稀土基材料,所述稀土基材料与助纺剂复合,所述稀土基材料具有下述化学通式:RE2Zr2O7,其中RE元素选自镧(La)、铈(Ce)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、镝(Dy)、钬(Ho)、铒(Er)、镱(Yb)、铥(Tm)、镥(Lu)、钪(Sc)和钇(Y)中的至少一种。本发明提供的锆酸稀土基高熵陶瓷纳米纤维不仅弥补了高熵锆酸盐陶瓷相关的研究空白,同时也丰富了材料体系。本发明的稀土基高熵陶瓷纳米纤维,单丝纤维的平均直径在80‑150nm之间并且均匀,制备工艺简单、成本低,利于工业化生产,并有良好的应用潜力。
Description
技术领域
高熵陶瓷技术领域,具体来说,本发明涉及一种锆酸稀土基高熵陶瓷纳米纤维及其制备方法和应用。
背景技术
目前传统材料的性能及发展已经到达了瓶颈、并无法满足各行业新技术日益增长的需要时,新材料的研究与开发显得尤为重要。“高熵”是近年来出现的新的材料设计理论,早在2004年叶均蔚教授最先提出了高熵合金的概念,同年牛津大学的Cantor等也提出了多主元合金的概念。“高熵”的概念从组成上一般定义为:由五种或五种主元以上呈等原子比或接近等原子比组成的多主元合金。而高熵的基本规律和特点也主要包括:热力学上的高熵效应、结构上的晶格畸变效应、动力学上的缓慢扩散效应和性能上的“鸡尾酒”效应,这些效应使得高熵合金展示出优异的耐磨性、高强度、高温下热稳定性好、良好的断裂抵抗性等特点。
在2015年,美国北卡罗莱纳州立大学的Rost、Maria和杜克大学的Curtarolo等首先合作报道了一种岩盐结构的熵稳定氧化物陶瓷,即高熵陶瓷。而高熵陶瓷将逐步成为无极非金属材料领域新的研究热点。
在过去的几十年,陶瓷纤维由于其陶瓷纤维由于其低热导率、质轻、高抗热震稳定性、高韧性以及良好的高温稳定性而受到广泛的应用与研究。但由于陶瓷在高温下容易发生材料相变和晶粒的异常生长,导致在纤维的机械强度变差。锆酸稀土基材料具有更高的服役温度和良好的热稳定性。稀土元素的掺杂可以降低热导率,提升热膨胀系数。而高熵陶瓷由于其迟滞扩散效应,可以抑制晶粒长大,从而增强材料的机械强度。
但是目前没有关于锆酸稀土基高熵陶瓷纳米纤维的任何报道,更没有锆酸稀土基高熵陶瓷纳米纤维的实际应用及领域。
发明内容
本发明提供了一种锆酸稀土基高熵陶瓷纳米纤维及其制备方法和应用。
本发明提供了一种锆酸稀土基高熵陶瓷纳米纤维,所述纳米纤维通过助纺剂和锆酸稀土基材料复合、纺丝、煅烧后制备得到;所述锆酸稀土基材料具有下述化学通式:RE2Zr2O7,其中RE元素选自镧(La)、铈(Ce)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、镝(Dy)、钬(Ho)、铒(Er)、镱(Yb)、铥(Tm)、镥(Lu)、钪(Sc)和钇(Y)等稀土元素中的至少五种。
优选地,所述锆酸稀土基高熵陶瓷纳米纤维呈单一晶相,且各元素呈均匀分布。
优选地,所述锆酸稀土基材料中,每种稀土元素的摩尔数相同。
根据本发明的实施方案,所述复合是指锆酸稀土基材料与助纺剂在纳米尺度的混合。
根据本发明的实施方案,所述纳米纤维具有萤石结构。
根据本发明的实施方案,所述锆酸稀土基高熵陶瓷纳米纤维的直径均匀。优选地,所述纳米纤维的平均直径为80-150nm。
根据本发明的实施方案,所述助纺剂和锆酸稀土基材料的用量比为(0.25-0.6)g:0.0005mol,优选为0.51g:0.0005mol。
根据本发明的实施方案,所述助纺剂选自聚乙烯吡咯烷酮(PVP)、聚氧化乙烯(PEO)、聚乙烯醇(PVA)、聚丙烯腈(PAN)或聚醋酸乙烯脂(PVAc)中的至少一种。
根据本发明的实施方案,所述锆酸稀土基材料由由锆的化合物和稀土盐混合得到。
优选地,所述稀土盐选自硝酸稀土盐、氯化稀土盐、醋酸稀土盐、溴化稀土盐、碘化稀土盐中的至少一种,优选为氯化稀土盐。
优选地,所述锆的化合物选自四氯化锆、硝酸氧锆、氧氯化锆中的至少一种,优选为氧氯化锆。
根据本发明示例性的实施方案,所述锆酸稀土基高熵陶瓷纳米纤维材料的结构式例如为(La0.2Sm0.2Eu0.2Gd0.2Tm0.2)2Zr2O7、(Sm0.2Eu0.2Gd0.2Ho0.2Er0.2)2Zr2O7或(La0.2Ce0.2Nd0.2Sm0.2Yb0.2)2Zr2O7。
本发明还提供上述锆酸稀土基高熵陶瓷纳米纤维的制备方法,包括以下步骤:
(1)将稀土基材料的前驱体和锆的化合物溶解于溶剂中得到锆酸稀土基前驱体溶液;
(2)在步骤(1)中的锆酸稀土基前驱体溶液中加入助纺剂,得到锆酸稀土基前驱体纺丝液;
(3)将步骤(2)所制得的锆酸稀土基前驱体纺丝液进行静电纺丝,得到锆酸稀土基前驱体纤维;
(4)将步骤(3)所制得的锆酸稀土基前驱体纤维煅烧后,即得锆酸稀土基高熵陶瓷纳米纤维。
根据本发明的实施方案,步骤(1)中,所述稀土基材料的前驱体含有至少五种所需化学计量的稀土元素,所述稀土元素具有如上所述含义。优选地,所述稀土基材料的前驱体由稀土盐提供,优选为可溶性稀土盐。优选地,所述可溶性稀土盐选自硝酸稀土盐、氯化稀土盐、醋酸稀土盐、溴化稀土盐、碘化稀土盐中的至少一种,优选为氯化稀土盐。优选地,所述锆的化合物优选为锆的可溶性化合物。优选地,所述锆的可溶性化合物选自四氯化锆、硝酸氧锆、氧氯化锆中的至少一种,优选为氧氯化锆。
其中,术语“可溶性”是指具有可溶于所用的溶剂中的特性。
优选地,在步骤(1)中,可溶性稀土盐中的稀土总元素和锆的可溶性化合物中的锆元素的摩尔比选自1:(1-1.01),优选为1:1。
优选地,所述稀土基材料的前驱体中各稀土元素的摩尔量可以相同或不同,优选为相同。示例性地,所述稀土基材料的前驱体中的稀土元素包括La、Ce、Sm、Eu和Gd,La:Ce:Sm:Eu:Gd的摩尔比为1:1:1:1:1。
根据本发明的实施方案,步骤(1)中,所述溶剂选自水、甲醇、乙醇、正丙醇、异丙醇、N,N-二甲基甲酰胺中的至少一种。优选地,所述溶剂为水、乙醇和DMF的混合溶剂。
根据本发明的实施方案,步骤(1)中,所述锆酸稀土基前驱体溶液的具体制备方法包括:将含有所需化学计量的稀土元素的可溶性稀土盐在室温条件下溶解于溶剂中,再加入锆的可溶性化合物充分溶解,制得锆酸稀土基前驱体溶液;或将锆的可溶性化合物在室温条件下溶解于溶剂中,再加入含有所需化学计量的稀土元素的可溶性稀土盐充分溶解,制得锆酸稀土基前驱体溶液;或将锆的可溶性化合物和含有所需化学计量的稀土元素的可溶性稀土盐在室温条件下充分溶解于溶剂中,制得锆酸稀土基前驱体溶液。
根据本发明的实施方案,步骤(1)中,本领域技术人员可根据纺丝工艺的要求调整溶剂的加入量,只要能得到所需纺丝液即可。示例性地,所述锆酸稀土基前驱体溶液中锆元素的摩尔浓度为0.01-0.1mol/L,例如为0.087mol/L。
根据本发明的实施方案,步骤(2)中,所述助纺剂在室温下溶解。其中,所述室温是指10-40℃。
根据本发明的实施方案,所述助纺剂与锆酸稀土基前驱体纺丝液的质量比为(0.01~0.05):10。
根据本发明的实施方案,步骤(1)或(2)中的溶解还可以在搅拌下进行,本发明对搅拌方式和搅拌时间不做具体的限定,以实现可溶性稀土盐或锆的可溶性化合物的充分溶解即可。例如,所述搅拌可以是在磁力搅拌条件下,或是机械搅拌条件下进行。例如,步骤(1)和(2)中,搅拌时间可以分别为1~6h或1~12h。
根据本发明的实施方案,本发明对步骤(3)的静电纺丝工艺不做具体限定,可采用本领域技术人员常用的静电纺丝条件进行纺丝操作,通过调节喷头与收集板的距离、纺丝电压、喷射速率可制得不同形貌的锆酸稀土盐前驱体纤维。
根据本发明示例性的实施方案,步骤(3)的静电纺丝工艺包括:纺丝电压15-22kV,喷丝速度0.1-0.5ml/h,接收距离10-60cm、纺丝湿度25~35%、纺丝温度20~27℃。其中,术语“接收距离”是指喷头与收集板的距离。根据本发明的实施方案,步骤(4)的煅烧工艺包括:在一定气氛下,在1000~1100℃高温煅烧2h,随炉降温。
根据本发明的实施方案,所述气氛选自氮气、氩气、氦气、空气中的至少一种。
根据本发明的实施方案,煅烧前的升温方式包括:分段升温至1000~1100℃。例如,先升温至600~800℃,然后再升温至1000~1100℃。
根据本发明示例性的实施方案,煅烧前的升温方式具体包括:先以1~2℃/min的升温速率升温至600~800℃,然后再以1~5℃/min的升温速率升温至1000~1100℃。
本发明还提供上述锆酸稀土基高熵陶瓷纳米纤维材料的应用,例如用于保温隔热、陶瓷增韧等领域。
本发明的有益效果在于:
(1)本发明采用溶胶凝胶法结合静电纺丝制备稀土基高熵陶瓷纳米纤维,克服了传统方法只能制备粉体、块体和涂层形态高熵陶瓷的局限,将锆酸高熵陶瓷的存在形式拓展到了纤维领域,该方法可通过材料的高熵作用获得低导热系数的纳米纤维材料。
(2)本发明提供一种锆酸稀土基高熵陶瓷纳米纤维,所述纳米纤维具有萤石结构,由于纳米纤维的结构中至少有五种稀土元素,而稀土元素具有较为独特的电子层结构,引入高熵概念以其迟滞扩散效应使纳米纤维的晶粒缓慢长大,增强纤维的机械性能。且由于较大的晶格畸变,该纳米纤维热导率低至0.23W·m-1·K-1,使其在广大领域展现出较好的应用前景。
(3)本发明提供的锆酸稀土基高熵陶瓷纳米纤维不仅弥补了高熵锆酸盐陶瓷相关的研究空白,同时也丰富了材料体系。
(4)本发明的稀土基高熵陶瓷纳米纤维,单丝纤维的平均直径在80-150nm之间并且均匀,制备工艺简单、成本低,利于工业化生产,并有良好的应用潜力。
附图说明
图1为实施例1中合成的(La0.2Sm0.2Eu0.2Gd0.2Tm0.2)2Zr2O7高熵陶瓷纳米纤维的XRD图。
图2为实施例1中合成的(La0.2Sm0.2Eu0.2Gd0.2Tm0.2)2Zr2O7高熵陶瓷纳米纤维的SEM照片。
图3为实施例2中合成的(Sm0.2Eu0.2Gd0.2Ho0.2Er0.2)2Zr2O7高熵陶瓷纳米纤维的EDS图。
图4为实施例4中合成的(La0.2Sm0.2Eu0.2Gd0.2Tm0.2)2Zr2O7高熵陶瓷纳米纤维的热重分析图。
具体实施方式
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解,下列实施例仅为示例性地说明和解释本发明,而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
除非另有说明,以下实施例中使用的原料和试剂均为市售商品,或者可以通过已知方法制备。
实施例1
一种锆酸稀土基高熵陶瓷纳米纤维及制备方法,包括步骤如下;
(1)分别称取0.0002mol的氯化镧、氯化钐、氯化铕、氯化钆、氯化铥与0.001mol的氧氯化锆与烧杯中,然后加入10ml的无水乙醇和0.5ml的超纯水以及1ml的N,N-二甲基甲酰胺(DMF),于30℃条件下充分搅拌直至完全溶解,形成澄清的锆酸稀土盐前驱体溶液。
(2)将步骤(1)所得的锆酸稀土盐前驱体溶液中加入0.42g聚乙烯吡咯烷酮(PVP),在30℃条件下充分搅拌直至溶解成澄清黏稠可纺溶液即为锆酸稀土前驱体纺丝溶液。
(3)将步骤(2)所得的锆酸稀土前驱体纺丝溶液在温度为23℃,湿度为35%的环境下进行静电纺丝制备锆酸稀土盐前驱体纤维。静电纺丝试验的纺丝电压为22kV,喷丝速率为0.4ml/h,喷头与收集板距离为15cm。
(4)将步骤(3)所得的锆酸稀土盐前驱体纤维放置管式炉进行排胶煅烧,以1℃/min的升温速率到650℃,然后以2℃/min的升温速率至1000℃,保温2h,随炉降温,即得(La0.2Sm0.2Eu0.2Gd0.2Tm0.2)2Zr2O7高熵陶瓷纳米纤维。
所述(La0.2Sm0.2Eu0.2Gd0.2Tm0.2)2Zr2O7高熵陶瓷纳米纤维XRD如图1所示,表明得到的锆酸稀土基高熵陶瓷纳米纤维为萤石结构材料,同时其特征峰无杂峰结晶度较好,说明获得的产物晶型完整。
所述(La0.2Sm0.2Eu0.2Gd0.2Tm0.2)2Zr2O7高熵陶瓷纳米纤维SEM如图2所示,纤维直径较细并且均匀,表面光滑,无气孔、裂纹等破损缺陷。
实施例2
(1)分别称取0.0002mol的氯化钐、氯化铕、氯化钆、氯化钬、氯化铒与0.001mol的氧氯化锆与烧杯中,然后加入10ml的无水乙醇和0.5ml的超纯水以及1ml的N,N-二甲基甲酰胺(DMF),于30℃条件下充分搅拌直至完全溶解,形成澄清的锆酸稀土盐前驱体溶液。
(2)将步骤(1)所得的锆酸稀土盐前驱体溶液中加入0.51g聚乙烯吡咯烷酮(PVP),在30℃条件下充分搅拌直至溶解成澄清黏稠可纺溶液即为锆酸稀土前驱体纺丝溶液。
(3)将步骤(2)所得的锆酸稀土前驱体纺丝溶液在温度为23℃,湿度为35%的环境下进行静电纺丝制备锆酸稀土盐前驱体纤维。静电纺丝试验的纺丝电压为22kV,喷丝速率为0.5ml/h,喷头与收集板距离为15cm。
(4)将步骤(3)所得的锆酸稀土盐前驱体纤维放置管式炉进行排胶煅烧,以1℃/min的升温速率到650℃,然后以2℃/min的升温速率至1000℃,保温2h,随炉降温,即得锆酸稀土基高熵陶瓷纳米纤维。
所述锆酸稀土基高熵陶瓷纳米纤维EDS如图3所示,看出五种稀土离子(Sm、Eu、Gd、Ho、Er)和锆(Zr)离子均匀分布在陶瓷纤维体上,实现了元素的均匀掺杂。
纤维直径较粗,纤维易粘接。由于前驱体纺丝溶液粘度较大,降低了其可纺性。
实施例3
(1)分别称取0.0002mol的氯化镧、氯化铈、氯化钕、氯化钐、氯化镱与0.001mol的氧氯化锆与烧杯中,然后加入10ml的无水乙醇和0.5ml的超纯水以及1ml的N,N-二甲基甲酰胺(DMF),于30℃条件下充分搅拌直至完全溶解,形成澄清的锆酸稀土盐前驱体溶液。
(2)将步骤(1)所得的锆酸稀土盐前驱体溶液中加入0.25g聚乙烯吡咯烷酮(PVP),在30℃条件下充分搅拌直至溶解成澄清黏稠可纺溶液即为锆酸稀土前驱体纺丝溶液。
(3)将步骤(2)所得的锆酸稀土前驱体纺丝溶液在温度为23℃,湿度为35%的环境下进行静电纺丝制备锆酸稀土盐前驱体纤维。静电纺丝试验的纺丝电压为22kV,喷丝速率为0.5ml/h,喷头与收集板距离为15cm。
(4)将步骤(3)所得的锆酸稀土盐前驱体纤维放置管式炉进行排胶煅烧,以1℃/min的升温速率到650℃,然后以2℃/min的升温速率至1000℃,保温2h,随炉降温,即得(La0.2Ce0.2Nd0.2Sm0.2Yb0.2)2Zr2O7。纳米纤维。
纤维直径较细但有大量粘结球,纺丝不连续有液滴。由于前驱体纺丝液浓度过低,也降低了其可纺性。
实施例4
(1)分别称取0.0002mol的氯化镧、氯化钐、氯化铕、氯化钆、氯化铥与0.001mol的氧氯化锆与烧杯中,然后加入10ml的无水乙醇和0.5ml的超纯水以及1ml的N,N-二甲基甲酰胺(DMF),于30℃条件下充分搅拌直至完全溶解,形成澄清的锆酸稀土盐前驱体溶液。
(2)将步骤(1)所得的锆酸稀土盐前驱体溶液中加入0.42g聚乙烯吡咯烷酮(PVP),在30℃条件下充分搅拌直至溶解成澄清黏稠可纺溶液即为锆酸稀土前驱体纺丝溶液。
(3)将步骤(2)所得的锆酸稀土前驱体纺丝溶液在温度为23℃,湿度为35%的环境下进行静电纺丝制备锆酸稀土盐前驱体纤维。静电纺丝试验的纺丝电压为22kV,喷丝速率为0.4ml/h,喷头与收集板距离为15cm。
(4)将步骤(3)所得的锆酸稀土盐前驱体纤维放置管式炉进行排胶煅烧,以1℃/min的升温速率到650℃,然后以5℃/min的升温速率至1000℃,保温2h,随炉降温,即得锆酸稀土基高熵陶瓷纳米纤维。
锆酸稀土基高熵陶瓷纳米纤维的热重分析如图4所示,0~100℃左右重量损失主要来源于水的蒸发,100℃到600℃的重量损失主要由于PVP等有机物的分解。600℃以上几乎无重量损失。
测试例
将实施例4制备得到的锆酸稀土基高熵陶瓷纳米纤维通过如下方法测得热导率,测试结果为0.23W·m-1·K-1。
热导率测试方法:热导率测试仪器为Hot Disk TPS 2200型热常数分析仪,采用瞬变平面热源法技术,在数秒内完成导热系数、热扩散系数、热容等物性的测试。测试范围宽(0.005~500W·m-1·K-1),精度高(±3%)。
以上,对本发明的实施方式进行了说明。但是,本发明不限定于上述实施方式。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种锆酸稀土基高熵陶瓷纳米纤维,其特征在于,所述纳米纤维通过助纺剂和锆酸稀土基材料复合、纺丝、煅烧后制备得到;所述锆酸稀土基材料具有下述化学通式:RE2Zr2O7,其中RE元素选自镧(La)、铈(Ce)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、镝(Dy)、钬(Ho)、铒(Er)、镱(Yb)、铥(Tm)、镥(Lu)、钪(Sc)和钇(Y)中的至少五种。
2.根据权利要求1所述的锆酸稀土基高熵陶瓷纳米纤维,其特征在于,所述锆酸稀土基高熵陶瓷纳米纤维呈单一晶相,且各元素呈均匀分布。
优选地,所述锆酸稀土基材料中,每种稀土元素的摩尔数相同。
优选地,所述复合是指锆酸稀土基材料与助纺剂在纳米尺度的混合。
优选地,所述纳米纤维具有萤石结构。
优选地,所述锆酸稀土基高熵陶瓷纳米纤维的直径均匀。优选地,所述纳米纤维的平均直径为80-150nm。
3.根据权利要求1或2所述的锆酸稀土基高熵陶瓷纳米纤维,其特征在于,所述助纺剂和锆酸稀土基材料的用量比为(0.25-0.6)g:0.0005mol。
优选地,所述助纺剂选自聚乙烯吡咯烷酮(PVP)、聚氧化乙烯(PEO)、聚乙烯醇(PVA)、聚丙烯腈(PAN)或聚醋酸乙烯脂(PVAc)中的至少一种。
优选地,所述锆酸稀土基材料由锆的化合物和稀土盐混合得到。
优选地,所述稀土盐选自硝酸稀土盐、氯化稀土盐、醋酸稀土盐、溴化稀土盐、碘化稀土盐中的至少一种,优选为氯化稀土盐。
优选地,所述锆的化合物选自四氯化锆、硝酸氧锆、氧氯化锆中的至少一种,优选为氧氯化锆。
4.根据权利要求1-3任一项所述的锆酸稀土基高熵陶瓷纳米纤维,其特征在于,所述锆酸稀土基高熵陶瓷纳米纤维材料的结构式为(La0.2Sm0.2Eu0.2Gd0.2Tm0.2)2Zr2O7、(Sm0.2Eu0.2Gd0.2Ho0.2Er0.2)2Zr2O7或(La0.2Ce0.2Nd0.2Sm0.2Yb0.2)2Zr2O7。
5.权利要求1-4任一项所述的锆酸稀土基高熵陶瓷纳米纤维的制备方法,其特征在于,包括以下步骤:
(1)将稀土基材料的前驱体和锆的可溶性化合物溶解于溶剂中得到锆酸稀土基前驱体溶液;
(2)在步骤(1)中的锆酸稀土基前驱体溶液中加入助纺剂,得到锆酸稀土基前驱体纺丝液;
(3)将步骤(2)所制得的锆酸稀土基前驱体纺丝液进行静电纺丝,得到锆酸稀土基前驱体纤维;
(4)将步骤(3)所制得的锆酸稀土基前驱体纤维煅烧后,即得锆酸稀土基高熵陶瓷纳米纤维。
优选地,步骤(1)中,所述稀土基材料的前驱体包括至少五种所需化学计量的稀土元素,所述稀土元素具有如上所述含义。优选地,所述稀土基材料的前驱体由稀土盐提供,优选为可溶性稀土盐。优选地,所述可溶性稀土盐选自硝酸稀土盐、氯化稀土盐、醋酸稀土盐、溴化稀土盐、碘化稀土盐中的至少一种,优选为氯化稀土盐。优选地,所述锆的化合物优选为锆的可溶性化合物。优选地,所述锆的可溶性化合物选自四氯化锆、硝酸氧锆、氧氯化锆中的至少一种,优选为氧氯化锆。
优选地,在步骤(1)中,可溶性稀土盐中的稀土元素和锆的可溶性化合物中的锆元素的摩尔比选自1:(1-1.01)。
优选地,所述稀土基材料的前驱体中各稀土元素的摩尔量可以相同或不同,优选为相同。
优选地,步骤(1)中,所述溶剂选自水、甲醇、乙醇、正丙醇、异丙醇、N,N-二甲基甲酰胺中的至少一种。优选地,所述溶剂为水、乙醇和DMF的混合溶剂。
优选地,步骤(1)中,所述锆酸稀土基前驱体溶液的具体制备方法包括:将含有所需化学计量的稀土元素的可溶性稀土盐在室温条件下溶解于溶剂中,再加入锆的可溶性化合物充分溶解,制得锆酸稀土基前驱体溶液;或将锆的可溶性化合物在室温条件下溶解于溶剂中,再加入含有所需化学计量的稀土元素的可溶性稀土盐充分溶解,制得锆酸稀土基前驱体溶液;或将锆的可溶性化合物和含有所需化学计量的稀土元素的可溶性稀土盐在室温条件下充分溶解于溶剂中,制得锆酸稀土基前驱体溶液。
示例性地,所述锆酸稀土基前驱体溶液中锆元素的摩尔浓度为0.01-0.1mol/L,例如为0.087mol/L。
6.根据权利要求5所述的制备方法,其特征在于,步骤(2)中,所述助纺剂在室温下溶解。其中,所述室温是指10-40℃。
优选地,所述助纺剂与锆酸稀土基前驱体纺丝液的质量比为(0.01~0.05):10。
7.根据权利要求5或6所述的制备方法,其特征在于,步骤(1)或(2)中的溶解还可以在搅拌下进行。例如,所述搅拌可以是在磁力搅拌条件下,或是机械搅拌条件下进行。例如,步骤(1)和(2)中,搅拌时间可以分别为1~6h或1~12h。
8.根据权利要求5-7任一项所述的制备方法,其特征在于,步骤(3)的静电纺丝工艺包括:纺丝电压15-22kV,喷丝速度0.1-0.5ml/h,接收距离10-60c、纺丝湿度25~35%、纺丝温度20~27℃。
9.根据权利要求5-8任一项所述的制备方法,其特征在于,步骤(4)的煅烧工艺包括:在一定气氛下,在1000~1100℃高温煅烧2h,随炉降温。
优选地,所述气氛选自氮气、氩气、氦气、空气中的至少一种。
优选地,煅烧前的升温方式包括:分段升温至1000~1100℃。例如,先升温至600~800℃,然后再升温至1000~1100℃。
优选地,煅烧前的升温方式具体包括:先以1~2℃/min的升温速率升温至600~800℃,然后再以1~5℃/min的升温速率升温至1000~1100℃。
10.权利要求1-4任一项所述的锆酸稀土基高熵陶瓷纳米纤维材料的应用,例如用于保温隔热、陶瓷增韧等领域。
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