CN111620698A - 低热导率纳米纤维构架的多级孔陶瓷海绵材料及制备方法 - Google Patents

低热导率纳米纤维构架的多级孔陶瓷海绵材料及制备方法 Download PDF

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CN111620698A
CN111620698A CN202010495519.7A CN202010495519A CN111620698A CN 111620698 A CN111620698 A CN 111620698A CN 202010495519 A CN202010495519 A CN 202010495519A CN 111620698 A CN111620698 A CN 111620698A
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sponge material
thermal conductivity
low
ceramic sponge
nanofiber
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CN111620698B (zh
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张笑妍
张深根
刘波
丁云集
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University of Science and Technology Beijing USTB
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Abstract

本发明涉及新型多级孔材料、纳米纤维材料技术领域，提供了一种低热导率纳米纤维构架的多级孔陶瓷海绵材料及制备方法，所述制备方法首次以硅溶胶、水溶性炭黑、单质硅为原料制备均匀分散的混合浆料；所述混合浆料经真空除气、冷冻注模、冷冻干燥制得直通孔结构的多孔坯体；所述多孔坯体通过反应烧结得到所述低热导率纳米纤维构架的多级孔陶瓷海绵材料。本发明具有低成本、无需高昂设备、工艺简单、高效合成、易于工业化生产的特点，所得新型泡沫陶瓷综合性能优越：低体积密度、良好渗透性、高比表面积、低热导率。

Description

低热导率纳米纤维构架的多级孔陶瓷海绵材料及制备方法
技术领域
本发明涉及新型多级孔材料、纳米纤维材料技术领域，特别涉及一种低热导率纳米纤维构架的多级孔陶瓷海绵材料及制备方法。
背景技术
陶瓷材料具有高强度、优异的高温力学/化学稳定性等特点，然而其脆性以及缺陷敏感性限制了其在超轻、高弹性材料领域的应用，尤其当多孔结构引入时材料的力学性能成为制约其进一步应用的关键。
目前，研究人员通过高效的溶液吹塑法制备得到了多体系的轻质耐高温三维陶瓷海绵(TiO2，ZrO2，BaTiO3等)，其结构由大量相互交错的陶瓷纤维组成，结果表明该材料具有高的能量吸收以及回弹特性，置于1300℃高温环境中压缩仍能保持良好的恢复力，有望应用于弹性电阻、光催化、隔热等领域。此外，化学气相沉积法也被成功用于SiC三维纳米纤维气凝胶的合成，该材料具有超低的密度(～5mg·cm-3)，优异的可回弹特性及抗疲劳性、耐高温性及低热导率(0.026W·m-1·K-1)等出色的综合性能。
然而，三维纳米结构材料的研究现多基于昂贵的实验设备、合成条件较为苛刻且多集中于金属氧化物体系，在高温领域具有广泛应用的金属氮化物/碳化物体系的研究尚属匮乏。并且因合成方法的限制，所得纳米纤维气凝胶常见于大量冗杂的纳米纤维无序交错堆叠而成，不利于其性能稳定性的实现。
作为综合性能优异的高温结构陶瓷材料之一，Si3N4、SiC及Si2N2O材料具有优异的电学、热学和机械性能，耐高温、抗热冲击、抗氧化及抗雨蚀性能良好，在超高音速导弹飞行器、高温烟气过滤等领域有重要应用。碳热还原氮化法是常见的低成本制备硅基纳米纤维的有效途径，然而通过反应原料颗粒构架三维空间有序多孔结构，进一步采用碳热还原氮化法制备以纳米纤维为基元在三维空间有序编织而成的多级孔陶瓷则鲜有报道。此外，纳米纤维的生长通常基于气-液-固(VLS)和气-固(VS)两种反应机制，这就使得原料与反应环境中气体的全方位接触有利于纳米纤维的充分合成，因此在三维空间中构建开孔结构坯体可为气体在整个坯体内部均匀扩散提供最佳条件。
发明内容
本发明的目的在于克服现有技术的不足，提供了一种低热导率纳米纤维构架的多级孔陶瓷海绵材料及制备方法，该新型陶瓷海绵材料具有高气孔率、低热导率的特性。
本发明采用如下技术方案：
一种低热导率纳米纤维构架的多级孔陶瓷海绵材料的制备方法，以硅溶胶、水溶性炭黑、单质硅为原料制备均匀分散的混合浆料；所述混合浆料经真空除气、冷冻注模、冷冻干燥制得直通孔结构的多孔坯体；所述多孔坯体通过反应烧结得到所述低热导率纳米纤维构架的多级孔陶瓷海绵材料。
进一步的，所述制备方法具体包括：
S1、以硅溶胶、水溶性炭黑、单质硅颗粒中的一种或多种(其中不包括单一的水溶性炭黑)作为原料加入到含有一定浓度粘结剂的溶剂中，通过超声分散或者球磨配制均匀分散的混合浆料；
S2、所述混合浆料真空搅拌除气，倒入冷却模具中冷冻，获得冷冻素坯；
S3、将所述冷冻素坯冷冻干燥，得到具有直通孔型的多孔坯体；
S4、将步骤S3中得到的所述多孔坯体在惰性气氛下经反应烧结获得由纳米纤维编织而成的所述低热导率纳米纤维构架的多级孔陶瓷海绵材料。该新材料具有低体积密度、良好渗透性、高比表面积、热导率低的特性。
进一步的，步骤S1中，
所述硅溶胶为碱性硅溶胶，其含量占原料粉体总质量的0-100wt.％，粒径为10-100nm；
所述水溶性炭黑添加量占原料粉体总质量的0-20wt.％，粒径为10nm-1.0μm；
所述单质硅颗粒添加量占原料粉体总质量的0-100wt.％，粒径为10nm-1.0μm；
所述混合浆料固相含量为10-70wt.％。
进一步的，步骤S1中，
所述溶剂为去离子水、叔丁醇、莰烯中的一种；
所述粘结剂为羧甲基纤维素钠、聚乙烯醇、聚乙烯吡络烷酮、聚乙烯醇缩丁醛中的一种，所述粘结剂的加入量为所述混合浆料质量的0.1～5.0wt.％。
进一步的，步骤S2中，冷冻过程中温度为-10～-80℃，真空度≤10Pa。
进一步的，步骤S4中，
反应烧结过程以0.5～10℃/min升温速率加热至1200-1700℃，保温0.5～6h。
进一步的，反应烧结过程在氮气、氩气或真空环境中进行。
进一步的，以前期所得直通孔型泡沫坯体作为模板骨架，为随后的反应烧结合成纳米纤维提供充分的物质基础及空间基础，所制备的新型陶瓷海绵材料是由纳米纤维编织而成的多级孔结构，纳米纤维通过在多孔坯体气孔里的紧密编织最终得到一种新型多孔材料，体系涉及Si3N4、SiC、Si2N2O中的一种或多种复合材料。
单一的硅溶胶或单质硅颗粒可获得Si3N4纳米纤维(在氮气环境下)或者SiC(在氩气或真空环境下)、硅溶胶与炭黑或硅溶胶与单质硅颗粒两种物质反应可获得Si3N4/Si2N2O一种或两种复合纳米纤维(在氮气环境下)或者SiC(在氩气或真空环境下)、单质硅颗粒与炭黑反应可获得Si3N4纳米纤维(在氮气环境下)或者SiC(在氩气或真空环境下)、三种原料粉体一起可获得Si3N4/Si2N2O一种或两种复合纳米纤维(在氮气环境下)或者SiC(在氩气或真空环境下)。
有机泡沫体在热处理时会热解成碳，烧结的作用是使三种原料反应生长纳米纤维。
本发明一种低热导率纳米纤维构架的多级孔陶瓷海绵材料，使用上述的制备方法得到。
进一步的，所述多级孔陶瓷海绵材料由直径为1-300nm、长度为0.1-100μm的纳米纤维逐层编织而成，每层厚度为1.0μm-3.0mm，纳米纤维之间相互搭接形成的微孔结构，孔径为10nm-5.0μm；所述多级孔陶瓷海绵材料具有低体积密度、高比表面积、低热导率。
本发明的有益效果为：本发明方法首次以硅溶胶、水溶性炭黑及单质硅颗粒作为初始原料粉体配制均匀稳定分散的悬浮体，经过冷冻使溶剂结晶得到坯体，将其进一步经过真空冷冻干燥形成直通孔型多孔坯体，通过在不同气氛下进行反应烧结，最终得到具有低热导率的多层纳米纤维编织而成的陶瓷海绵新材料；本发明具有低成本、无需高昂设备、工艺简单、高效合成、易于工业化生产的特点，所得新型泡沫陶瓷综合性能优越：低体积密度、良好渗透性、高比表面积、低热导率。
附图说明
图1a所示为实施例1所制备的直通孔坯体的SEM照片(纵切面)。
图1b所示为实施例1所制备的直通孔坯体的SEM照片(横切面)。
图2a所示为实施例1所制备的Si3N4纳米纤维逐层编织陶瓷海绵的SEM照片(纳米纤维逐层编织陶瓷海绵)。
图2b所示为实施例1所制备的Si3N4纳米纤维逐层编织陶瓷海绵的SEM照片(纳米纤维编织形成孔结构)。
图2c所示为实施例1所制备的Si3N4纳米纤维逐层编织陶瓷海绵的SEM照片(纳米纤维形貌)。
具体实施方式
下文将结合具体附图详细描述本发明具体实施例。应当注意的是，下述实施例中描述的技术特征或者技术特征的组合不应当被认为是孤立的，它们可以被相互组合从而达到更好的技术效果。
实施例1
(1)以硅溶胶、水溶性炭黑、单质硅颗粒作为初始原料加入到含有一定浓度粘结剂的溶剂中，通过超声分散或者球磨配制均匀分散的混合浆料。其中，硅溶胶含量占原料粉体总质量的12.5wt.％，粒径为20nm，水溶性炭黑添加量占原料粉体总质量的5wt.％，粒径为0.5μm，单质硅颗粒添加量占原料粉体总质量的82.5wt.％，粒径为1.0μm；所得混合浆料固相含量为10wt.％。所述溶剂为去离子水，粘结剂为聚乙烯醇，加入量为浆料质量的5.0wt.％。
(2)将上述混合浆料进行真空搅拌除气，随后倒入冷却模具中冷冻，获得冷冻素坯。
(3)将步骤(2)中冷冻素坯置于真空冷冻干燥机中进行冷冻干燥，温度为-10℃，真空度为1Pa，得到具有直通孔型的多孔坯体。图1a、图1b示出了直通孔坯体的SEM照片的纵切面和横切面。
(4)将步骤(3)中多孔坯体在惰性气氛下经反应烧结可以获得一种全新的由Si3N4/Si2N2O纳米纤维编织而成的泡沫陶瓷材料。其中，反应烧结过程以5℃/min升温速率加热至1450℃，保温3h。上述热处理过程在氮气环境中进行。
所得新型多孔材料是由直径为5nm、长度为1μm的纳米纤维逐层编织而成，每层厚度为15μm，纳米纤维之间相互搭接形成的微孔结构，孔径为100nm；这种新型多孔材料具有低密度0.40g/cm3、比表面积为23.9m2/g、热导率较低为0.10W/(m·K)。图2a-图2c示出了所制备的Si3N4纳米纤维逐层编织陶瓷海绵的SEM照片(其中，2a-纳米纤维逐层编织陶瓷海绵；2b-纳米纤维编织形成孔结构；2c-纳米纤维形貌)。
实施例2
(1)以硅溶胶、水溶性炭黑作为初始原料加入到含有一定浓度粘结剂的溶剂中，通过超声分散或者球磨配制均匀分散的混合浆料。其中，硅溶胶含量占原料粉体总质量的88wt.％，粒径为10nm，水溶性炭黑添加量占原料粉体总质量的12wt.％，粒径为1.0μm；所得混合浆料固相含量为42wt.％。所述溶剂为去离子水，粘结剂为羧甲基纤维素钠，加入量为浆料质量的0.1wt.％。
(2)将上述混合浆料进行真空搅拌除气，随后倒入冷却模具中冷冻，获得冷冻素坯。
(3)将步骤(2)中冷冻素坯置于真空冷冻干燥机中进行冷冻干燥，温度为-60℃，真空度为5Pa，得到具有直通孔型的多孔坯体。
(4)将步骤(3)中多孔坯体在惰性气氛下经反应烧结可以获得一种全新的由SiC纳米纤维编织而成的泡沫陶瓷材料。其中，反应烧结过程以0.5℃/min升温速率加热至1500℃，保温0.5h。上述热处理过程在氩气环境中进行。
所得新型多孔材料是由直径为300nm、长度为100μm的纳米纤维逐层编织而成，每层厚度为1μm，纳米纤维之间相互搭接形成的微孔结构，孔径为5.0μm；这种新型多孔材料具有低密度0.70g/cm3、比表面积为18.2m2/g、热导率较低为0.35W/(m·K)。
实施例3
(1)以硅溶胶、水溶性炭黑、单质硅颗粒作为初始原料加入到含有一定浓度粘结剂的溶剂中，通过超声分散或者球磨配制均匀分散的混合浆料。其中，硅溶胶含量占原料粉体总质量的10wt.％，粒径为80nm，水溶性炭黑添加量占原料粉体总质量的0wt.％，粒径为30nm，单质硅颗粒添加量占原料粉体总质量的90wt.％，粒径为50nm；所得混合浆料固相含量为30wt.％。所述溶剂为叔丁醇，粘结剂为聚乙烯吡络烷酮，加入量为浆料质量的2.0wt.％。
(2)将上述混合浆料进行真空搅拌除气，随后倒入冷却模具中冷冻，获得冷冻素坯。
(3)将步骤(2)中冷冻素坯置于真空冷冻干燥机中进行冷冻干燥，温度为-80℃，真空度为1Pa，得到具有直通孔型的多孔坯体。
(4)将步骤(3)中多孔坯体在惰性气氛下经反应烧结可以获得一种全新的由Si3N4纳米纤维编织而成的泡沫陶瓷材料。其中，反应烧结过程以10℃/min升温速率加热至1650℃，保温6h。上述热处理过程在氮气环境中进行。
所得新型多孔材料是由直径为50nm、长度为10μm的纳米纤维逐层编织而成，每层厚度为1mm，纳米纤维之间相互搭接形成的微孔结构，孔径为10nm；这种新型多孔材料具有低密度0.03g/cm3、比表面积为88.2m2/g、热导率较低为0.08W/(m·K)。
实施例4
(1)以硅溶胶、水溶性炭黑、单质硅颗粒作为初始原料加入到含有一定浓度粘结剂的溶剂中，通过超声分散或者球磨配制均匀分散的混合浆料。其中，硅溶胶含量占原料粉体总质量的60wt.％，粒径为50nm，水溶性炭黑添加量占原料粉体总质量的20wt.％，粒径为0.5μm，单质硅颗粒添加量占原料粉体总质量的20wt.％，粒径为0.6μm；所得混合浆料固相含量为20wt.％。所述溶剂为莰烯，粘结剂为聚乙烯醇缩丁醛，加入量为浆料质量的3.0wt.％。
(2)将上述混合浆料进行真空搅拌除气，随后倒入冷却模具中冷冻，获得冷冻素坯。
(3)将步骤(2)中冷冻素坯置于真空冷冻干燥机中进行冷冻干燥，温度为-50℃，真空度为2Pa，得到具有直通孔型的多孔坯体。
(4)将步骤(3)中多孔坯体在惰性气氛下先后经排胶、反应烧结可以获得一种全新的由Si2N2O/SiC纳米纤维编织而成的泡沫陶瓷材料。其中，反应烧结过程以10℃/min升温速率加热至1350℃，保温4h。上述热处理过程在真空环境中进行。
所得新型多孔材料是由直径为80nm、长度为50μm的纳米纤维逐层编织而成，每层厚度为0.5mm，纳米纤维之间相互搭接形成的微孔结构，孔径为100nm；这种新型多孔材料具有低密度0.12g/cm3、比表面积为20.6m2/g、热导率较低为0.19W/(m·K)。
本文虽然已经给出了本发明的几个实施例，但是本领域的技术人员应当理解，在不脱离本发明精神的情况下，可以对本文的实施例进行改变。上述实施例只是示例性的，不应以本文的实施例作为本发明权利范围的限定。

Claims (10)

1.一种低热导率纳米纤维构架的多级孔陶瓷海绵材料的制备方法，其特征在于，所述制备方法以硅溶胶、水溶性炭黑、单质硅为原料制备均匀分散的混合浆料；所述混合浆料经真空除气、冷冻注模、冷冻干燥制得直通孔结构的多孔坯体；所述多孔坯体经反应烧结得到所述低热导率纳米纤维构架的多级孔陶瓷海绵材料。
2.如权利要求1所述的低热导率纳米纤维构架的多级孔陶瓷海绵材料的制备方法，其特征在于，所述制备方法具体包括：
S1、以硅溶胶、水溶性炭黑、单质硅颗粒中的一种或多种作为原料加入到含有一定浓度粘结剂的溶剂中，通过超声分散或者球磨配制均匀分散的混合浆料；当原料为单一原料时不包括水溶性炭黑；
S2、所述混合浆料真空搅拌除气，倒入冷却模具中冷冻，获得冷冻素坯；
S3、将所述冷冻素坯冷冻干燥，得到具有直通孔型的多孔坯体；
S4、将步骤S3中得到的所述多孔坯体在惰性气氛下经反应烧结获得由纳米纤维编织而成的所述低热导率纳米纤维构架的多级孔陶瓷海绵材料。
3.如权利要求2所述的低热导率纳米纤维构架的多级孔陶瓷海绵材料的制备方法，其特征在于，步骤S1中，
所述硅溶胶含量占原料粉体总质量的0-100wt.％，粒径为10-100nm；
所述水溶性炭黑添加量占原料粉体总质量的0-20wt.％，粒径为10nm-1.0μm；
所述单质硅颗粒添加量占原料粉体总质量的0-100wt.％，粒径为10nm-1.0μm；
所述混合浆料固相含量为10-70wt.％。
4.如权利要求2所述的低热导率纳米纤维构架的多级孔陶瓷海绵材料的制备方法，其特征在于，步骤S1中，
所述溶剂为去离子水、叔丁醇、莰烯中的一种；
所述粘结剂为羧甲基纤维素钠、聚乙烯醇、聚乙烯吡络烷酮、聚乙烯醇缩丁醛中的一种，所述粘结剂的加入量为所述混合浆料质量的0.1～5.0wt.％。
5.如权利要求2所述的低热导率纳米纤维构架的多级孔陶瓷海绵材料的制备方法，其特征在于，步骤S2中，冷冻过程中温度为-10～-80℃，真空度≤10Pa。
6.如权利要求2所述的低热导率纳米纤维构架的多级孔陶瓷海绵材料的制备方法，其特征在于，步骤S4中，
反应烧结过程以0.5～10℃/min升温速率加热至1200-1700℃，保温0.5～6h。
7.如权利要求6所述的低热导率纳米纤维构架的多级孔陶瓷海绵材料的制备方法，其特征在于，反应烧结过程在氮气、氩气或真空环境中进行。
8.如权利要求1-7任一项所述的低热导率纳米纤维构架的多级孔陶瓷海绵材料的制备方法，其特征在于，纳米纤维为Si3N4、SiC、Si2N2O中的一种或多种，纳米纤维在多孔坯体的气孔里紧密编织形成新型多孔材料。
9.一种低热导率纳米纤维构架的多级孔陶瓷海绵材料，使用如权利要求1-8任一项所述的制备方法得到。
10.如权利要求9所述的低热导率纳米纤维构架的多级孔陶瓷海绵材料，其特征在于，所述多级孔陶瓷海绵材料由直径为1-300nm、长度为0.1-100μm的纳米纤维逐层编织而成，每层厚度为1.0μm-3.0mm，纳米纤维之间相互搭接形成的微孔结构，孔径为10nm-5.0μm；所述多级孔陶瓷海绵材料具有低体积密度、高比表面积、低热导率。
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