CN116903380A - 一种柔性高导热氮化硼陶瓷基薄膜及其制备方法 - Google Patents
一种柔性高导热氮化硼陶瓷基薄膜及其制备方法 Download PDFInfo
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- 229910052582 BN Inorganic materials 0.000 title claims abstract description 103
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000000919 ceramic Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 55
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 43
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002243 precursor Substances 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 21
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004327 boric acid Substances 0.000 claims abstract description 20
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
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- 230000032683 aging Effects 0.000 claims description 14
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Abstract
本发明公开了一种柔性高导热氮化硼陶瓷基薄膜及其制备方法，属于柔性高导热材料制备技术领域，该制备方法包括以下步骤：首先以硼酸和三聚氰胺为原料制备氮化硼前驱体晶须；随后以氮化硼前驱体晶须、一维柔性高导热材料和粘结剂聚乙烯吡咯烷酮为原料，经静电纺丝、除炭处理和高温陶瓷化热处理，获得一种柔性高导热氮化硼陶瓷基薄膜的制备方法。本发明采用氮化硼制备高导热多孔陶瓷薄膜，其优势在于陶瓷化转化的硬质氮化硼晶须对原有一维柔性高导热材料“软‑硬”反应性结合，可得到一种高导热且柔韧性好的陶瓷薄膜。
Description
技术领域
本发明属于柔性高导热材料制备技术领域，涉及一种柔性高导热氮化硼陶瓷基薄膜及其制备方法。
背景技术
关于柔性多孔陶瓷报道最多的是超长1D纳米线(纤维)或2D纳米条带构筑的陶瓷气凝胶、泡沫、海绵或柔性纸等。然而，尽管上述陶瓷具有优异的柔性性能，但导热性能较低。原因在于，这类材料由纳米陶瓷构成。陶瓷化温度低(≤1400℃)，结晶度差，其柔韧性来源于纳米陶瓷材料内部结构缺陷(如非晶、高的位错密度、晶格畸变等)的协同作用，而这些缺陷使得材料本征热导率很低。为了提高陶瓷本征导热导率，必须通过提高纳米陶瓷的热处理温度而提高陶瓷结晶度，但会造成纳米陶瓷材料整体柔韧性显著降低。
关于纳米柔性氮化硼(BN)的制备方法，目前研究较多的是无机前驱体自组装结合原位转化制备BN晶须或纤维(首先以硼酸和三聚氰胺为原料制备前驱体纳米晶须，随后热处理转化为BN晶须)，该方法简单易行，且晶须在低于1400℃时具有良好的柔韧性。但是，该柔性氮化硼结晶度低，导致本征导热性能较低。当进一步提高BN晶须热处理温度(>1400℃)时，其本征导热性能提高，但显著变硬变脆。
发明内容
本发明的目的在于克服上述现有技术的缺点，提供一种柔性高导热氮化硼陶瓷基薄膜及其制备方法，以解决现有技术中纳米陶瓷薄膜柔韧性与导热性相矛盾的问题。本发明所制备得到的多孔陶瓷薄膜具有高热导率以及良好的柔韧性。
为达到上述目的，本发明采用以下技术方案予以实现：
一种柔性高导热氮化硼陶瓷基薄膜的制备方法，包括以下步骤：
步骤1，将三聚氰胺和硼酸溶于水中，获得混合溶液，将混合溶液升温搅拌后，依次经过陈化和过滤，将过滤产物干燥后获得氮化硼前驱体晶须；
步骤2，将氮化硼晶须置于无水乙醇中超声分散，加入一维柔性高导热材料超声分散，然后加入粘结剂，搅拌后获得纺丝液；纺丝液经过静电纺丝处理，将纺丝物经过干燥、除炭处理和陶瓷化热处理后，获得氮化硼陶瓷基薄膜。
本发明的进一步改进在于：
优选的，步骤1中，混合溶液中，三聚氰胺的浓度为0.05-0.2M。
优选的，步骤1中，三聚氰胺和硼酸的摩尔比为1:1-1:4。
优选的，步骤1中，搅拌温度为80-100℃，陈化时间为20-30h。
优选的，步骤1中，干燥温度为70-100℃，干燥时间为30-40h。
优选的，步骤2中，氮化硼晶须在无水乙醇中的浓度为0.1-0.2g·mL-1；一维柔性高导热材料在无水乙醇中的浓度为0.005-0.1g·mL-1，聚乙烯吡咯烷酮在无水乙醇中的浓度为0.05-0.10g·mL-1。
优选的，步骤2中，一维柔性高导热材料为碳纳米管或氮化硼纳米管。
优选的，步骤2中，除炭处理的温度为400-600℃，时间为0.5-4h。
优选的，步骤2中，陶瓷化热处理升温速率为2-10℃/min，最终温度为1400-1800℃，时间为0.5-6h。
一种通过上述任意一项所述制备方法制得的柔性高导热氮化硼陶瓷基薄膜，由氮化硼晶须和纳米管搭接组成，所述纳米管为碳纳米管或氮化硼纳米管。
与现有技术相比，本发明具有以下有益效果：
本发明公开了一种柔性高导热氮化硼陶瓷基薄膜的制备方法，所述制备方法包括以下步骤：首先以硼酸和三聚氰胺为原料制备氮化硼前驱体晶须；进一步的，以氮化硼前驱体晶须、一维柔性高导热材料和粘结剂聚乙烯吡咯烷酮为原料，经静电纺丝、除炭处理(去除粘结剂)和高温陶瓷化热处理，获得一种柔性高导热氮化硼陶瓷基薄膜的制备方法。制备过程中，静电纺丝有助于增加氮化硼前驱体晶须与一维柔性高导热材料之间的接触。前驱体晶须陶瓷化转化过程中，通过物质扩散迁移，实现与一维柔性高导热材料反应性结合，最终形成纳米材料网络互连结构。2)高温陶瓷化处理(>1400℃)得到的氮化硼晶须为高导热硬质相，初始原料中引入的是一维柔性高导热材料。通过“软-硬”的化学结合以及软相的协同变形，实现整体材料的柔韧性与高导热性。
本发明还公开了一种柔性高导热氮化硼陶瓷基薄膜，该薄膜通过纳米管和氮化硼晶须相互搭接，形成了具有柔韧性和高导热性的薄膜。
附图说明
图1为实施例1制备所得柔性高导热氮化硼陶瓷基薄膜的XRD图谱。
图2为实施例1制备所得柔性高导热氮化硼陶瓷基薄膜的SEM图。
图3为实施例1制备所得柔性高导热氮化硼陶瓷基薄膜的宏观图片，说明其具备可弯曲的柔韧性。
具体实施方式
下面结合附图和具体的实施例对本发明做进一步详细描述：
本发明的实施例之一为公开了一种柔性高导热氮化硼陶瓷基薄膜的制备方法，主要包括以下步骤：
(1)将三聚氰胺和硼酸溶于去离子水中，升温并进行搅拌，经陈化、过滤和干燥后得到氮化硼前驱体晶须。
具体的，三聚氰胺浓度为0.05-0.2M，三聚氰胺和硼酸摩尔比为1:1-1:4。
具体的，搅拌过程中的温度为80-100℃，陈化时间为20-30h，干燥温度为70-100℃，干燥时间为30-40h。
(2)因氮化硼前驱体晶须较为难分散，因此首先将氮化硼前驱体晶须置于无水乙醇溶液中超声分散，获得氮化硼前驱体均匀分散液，随后加入一维柔性高导热材料再次进行超声分散，获得氮化硼前驱体以及一维柔性高导热材料均匀分散液。最后加入粘结剂聚乙烯吡咯烷酮，充分搅拌后得到纺丝液，经静电纺丝、干燥、除炭处理(去除粘结剂)、高温陶瓷化热处理，获得一维纳米材料软-硬结合构筑的高导热多孔陶瓷薄膜。
具体的，纺丝液中，氮化硼前驱体晶须的浓度为0.1-0.2g·mL-1，一维柔性高导热材料的浓度为0.005-0.5g·mL-1，粘结剂聚乙烯吡咯烷酮的浓度为0.05-0.10g·mL-1。
具体的，一维柔性高导热材料为碳纳米管、氮化硼纳米管等。
具体的，静电纺丝薄膜除炭温度为400-600℃，时间为0.5-4h。
具体的，静电纺丝薄膜高温陶瓷化热处理升温速率为2-10℃/min，最终温度为1400-1800℃，保温时间为0.5-6h。最后获得由纳米管和氮化硼晶须相互搭接的高导热多孔陶瓷薄膜。
下面结合具体的实施例进一步的说明：
实施例1
一种柔性高导热氮化硼陶瓷基薄膜的制备方法，包括以下步骤：
(1)将三聚氰胺和硼酸以摩尔比为1:3的比例溶于1L水中，其中三聚氰胺的摩尔浓度为0.16M，放置于油浴锅中95℃并进行搅拌，搅拌至澄清后持续搅拌30min后，室温冷却并经陈化24h，过滤，在鼓风干燥箱中80℃干燥后36h得到氮化硼前驱体晶须；
(2)将步骤(1)所得的氮化硼前驱体晶须称取1.4g置于10mL无水乙醇溶液中超声分散15min，随后加入0.09g碳纳米管再次进行超声分散15min，最后加入粘结剂聚乙烯吡咯烷酮0.79g，充分搅拌后得到纺丝液，以纺丝电压18kV，推进速度2.5mL/h进行静电纺丝。后置于80℃干燥2h得到前驱体薄膜；
(3)将(2)中得到的薄膜在马弗炉中以2.5℃/min的升温速度升温至500℃，保温2h，随炉冷却进行稳定化除炭；
(4)将(3)中得到的薄膜样品置于管式炉中以5℃/min的升温速度升温至1400℃，保温0.5h以进行高温陶瓷化热处理，获得高导热多孔陶瓷薄膜。
本实施例得到一种柔性高导热氮化硼陶瓷基薄膜，如图1，这种薄膜的XRD结构表征说明其是由碳纳米管和氮化硼纳米晶须构成的三维多孔结构(如图2)，且具备一定的柔性(如图3)。当浸渍聚合物后，复合材料面内热导率为2.47W·m-1K-1，面外热导率为0.67W·m-1K-1。
实施例2
一种柔性高导热氮化硼陶瓷基薄膜的制备方法，包括以下步骤：
(1)将三聚氰胺和硼酸以摩尔比为1:3的比例溶于1L水中，其中三聚氰胺的摩尔浓度为0.16M，放置于油浴锅中95℃并进行搅拌，搅拌至澄清后持续搅拌30min后，室温冷却并经陈化24h，过滤，在鼓风干燥箱中80℃干燥后36h得到氮化硼前驱体晶须；
(2)将步骤(1)所得的氮化硼前驱体晶须称取1.8g置于10mL无水乙醇溶液中超声分散15min，随后加入0.09g碳纳米管再次进行超声分散15min，最后加入粘结剂聚乙烯吡咯烷酮0.79g，充分搅拌2h后得到纺丝液，以纺丝电压18kV，推进速度2.5mL/h进行静电纺丝。后置于80℃干燥2h得到前驱体薄膜；
(3)将(2)中得到的薄膜在马弗炉中以2.5℃/min的升温速度升500℃，保温2h，随炉冷却进行稳定化除炭。
(4)将(3)中得到的薄膜样品置于管式炉中以5℃/min的升温速度升温至1600℃，保温1h以进行高温陶瓷化热处理，获得氮化硼纳米管-氮化硼复合薄膜。
本实施例得到的一种一维纳米材料软-硬结合构筑的高导热多孔陶瓷薄膜，其浸渍聚合物后复合材料面内热导率为3.18W·m-1K-1，面外热导率为0.79W·m-1K-1。
实施例3
一种柔性高导热氮化硼陶瓷基薄膜的制备方法，包括以下步骤：
(1)将三聚氰胺和硼酸以摩尔比为1:3的比例溶于1L水中，其中三聚氰胺的摩尔浓度为0.16M，放置于油浴锅中95℃并进行搅拌，搅拌至澄清后持续搅拌30min后，室温冷却并经陈化24h，过滤，在鼓风干燥箱中80℃干燥后36h得到氮化硼前驱体晶须；
(2)将步骤(1)所得的氮化硼前驱体晶须称取1.4g置于10mL无水乙醇溶液中超声分散15min，随后加入0.12g碳纳米管再次进行超声分散15min，最后加入粘结剂聚乙烯吡咯烷酮0.79g，充分搅拌后得到纺丝液，以纺丝电压18kV，推进速度2.5mL/h进行静电纺丝。后置于80℃干燥2h得到前驱体薄膜；
(3)将(2)中得到的薄膜在马弗炉中以2.5℃/min的升温速度升温至500℃，保温2h，随炉冷却进行稳定化除炭。
(4)将(3)中得到的薄膜样品置于管式炉中以5℃/min的升温速度升温至1600℃，保温2h以进行高温陶瓷化热处理，获得氮化硼纳米管-氮化硼复合薄膜；
本实施例得到的一种柔性高导热氮化硼陶瓷基薄膜的制备方法，其浸渍聚合物后复合材料面内热导率为4.82W·m-1K-1，面外热导率为0.79W·m-1K-1。
实施例4
一种柔性高导热氮化硼陶瓷基薄膜的制备方法，包括以下步骤：
(1)将三聚氰胺和硼酸以摩尔比为1:4的比例溶于1L水中，其中三聚氰胺的摩尔浓度为0.05M，放置于油浴锅中90℃并进行搅拌，搅拌至澄清后持续搅拌30min后，室温冷却并经陈化25h，过滤，在鼓风干燥箱中85℃干燥后30h得到氮化硼前驱体晶须；
(2)将步骤(1)所得的氮化硼前驱体晶须称取1g置于10mL无水乙醇溶液中超声分散15min，随后加入0.05g碳纳米管再次进行超声分散15min，最后加入粘结剂聚乙烯吡咯烷酮0.6g，充分搅拌2h后得到纺丝液，以纺丝电压18kV，推进速度2.5mL/h进行静电纺丝。后置于80℃干燥2h得到前驱体薄膜；
(3)将(2)中得到的薄膜在马弗炉中以2.5℃/min的升温速度升600℃，保温3h，随炉冷却进行稳定化除炭。
(4)将(3)中得到的薄膜样品置于管式炉中以10℃/min的升温速度升温至1500℃，保温3h以进行高温陶瓷化热处理，获得氮化硼纳米管-氮化硼复合薄膜。
实施例5
一种柔性高导热氮化硼陶瓷基薄膜的制备方法，包括以下步骤：
(1)将三聚氰胺和硼酸以摩尔比为1:1的比例溶于1L水中，其中三聚氰胺的摩尔浓度为0.1M，放置于油浴锅中100℃并进行搅拌，搅拌至澄清后持续搅拌30min后，室温冷却并经陈化20h，过滤，在鼓风干燥箱中90℃干燥后40h得到氮化硼前驱体晶须；
(2)将步骤(1)所得的氮化硼前驱体晶须称取0.07g置于10mL无水乙醇溶液中超声分散15min，随后加入0.1g氮化硼纳米管再次进行超声分散15min，最后加入粘结剂聚乙烯吡咯烷酮0.7g，充分搅拌2h后得到纺丝液，以纺丝电压18kV，推进速度2.5mL/h进行静电纺丝。后置于80℃干燥2h得到前驱体薄膜；
(3)将(2)中得到的薄膜在马弗炉中以2.5℃/min的升温速度升400℃，保温2h，随炉冷却进行稳定化除炭。
(4)将(3)中得到的薄膜样品置于管式炉中以2℃/min的升温速度升温至1700℃，保温4h以进行高温陶瓷化热处理，获得氮化硼纳米管-氮化硼复合薄膜。
实施例6
一种柔性高导热氮化硼陶瓷基薄膜的制备方法，包括以下步骤：
(1)将三聚氰胺和硼酸以摩尔比为1:2的比例溶于1L水中，其中三聚氰胺的摩尔浓度为0.12M，放置于油浴锅中80℃并进行搅拌，搅拌至澄清后持续搅拌30min后，室温冷却并经陈化30h，过滤，在鼓风干燥箱中95℃干燥后38h得到氮化硼前驱体晶须；
(2)将步骤(1)所得的氮化硼前驱体晶须称取1.2g置于10mL无水乙醇溶液中超声分散15min，随后加入0.5g碳纳米管再次进行超声分散15min，最后加入粘结剂聚乙烯吡咯烷酮0.5g，充分搅拌2h后得到纺丝液，以纺丝电压18kV，推进速度2.5mL/h进行静电纺丝。后置于80℃干燥2h得到前驱体薄膜；
(3)将(2)中得到的薄膜在马弗炉中以2.5℃/min的升温速度升500℃，保温1h，随炉冷却进行稳定化除炭。
(4)将(3)中得到的薄膜样品置于管式炉中以4℃/min的升温速度升温至1800℃，保温5h以进行高温陶瓷化热处理，获得氮化硼纳米管-氮化硼复合薄膜。
实施例7
一种柔性高导热氮化硼陶瓷基薄膜的制备方法，包括以下步骤：
(1)将三聚氰胺和硼酸以摩尔比为1:1的比例溶于1L水中，其中三聚氰胺的摩尔浓度为0.2M，放置于油浴锅中85℃并进行搅拌，搅拌至澄清后持续搅拌30min后，室温冷却并经陈化22h，过滤，在鼓风干燥箱中100℃干燥后38h得到氮化硼前驱体晶须；
(2)将步骤(1)所得的氮化硼前驱体晶须称取1.5g置于10mL无水乙醇溶液中超声分散15min，随后加入0.05g碳纳米管再次进行超声分散15min，最后加入粘结剂聚乙烯吡咯烷酮0.8g，充分搅拌2h后得到纺丝液，以纺丝电压18kV，推进速度2.5mL/h进行静电纺丝。后置于80℃干燥2h得到前驱体薄膜；
(3)将(2)中得到的薄膜在马弗炉中以2.5℃/min的升温速度升450℃，保温0.5h，随炉冷却进行稳定化除炭。
(4)将(3)中得到的薄膜样品置于管式炉中以8℃/min的升温速度升温至1550℃，保温6h以进行高温陶瓷化热处理，获得氮化硼纳米管-氮化硼复合薄膜。
实施例8
一种柔性高导热氮化硼陶瓷基薄膜的制备方法，包括以下步骤：
(1)将三聚氰胺和硼酸以摩尔比为1:4的比例溶于1L水中，其中三聚氰胺的摩尔浓度为0.15M，放置于油浴锅中90℃并进行搅拌，搅拌至澄清后持续搅拌30min后，室温冷却并经陈化28h，过滤，在鼓风干燥箱中90℃干燥后32h得到氮化硼前驱体晶须；
(2)将步骤(1)所得的氮化硼前驱体晶须称取1.9g置于10mL无水乙醇溶液中超声分散15min，随后加入0.1g碳纳米管再次进行超声分散15min，最后加入粘结剂聚乙烯吡咯烷酮1g，充分搅拌2h后得到纺丝液，以纺丝电压18kV，推进速度2.5mL/h进行静电纺丝。后置于80℃干燥2h得到前驱体薄膜；
(3)将(2)中得到的薄膜在马弗炉中以2.5℃/min的升温速度升550℃，保温4h，随炉冷却进行稳定化除炭。
(4)将(3)中得到的薄膜样品置于管式炉中以6℃/min的升温速度升温至1650℃，保温2h以进行高温陶瓷化热处理，获得氮化硼纳米管-氮化硼复合薄膜。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.一种柔性高导热氮化硼陶瓷基薄膜的制备方法，其特征在于，包括以下步骤：
步骤1，将三聚氰胺和硼酸溶于水中，获得混合溶液，将混合溶液升温搅拌后，依次经过陈化和过滤，将过滤产物干燥后获得氮化硼前驱体晶须；
步骤2，将氮化硼晶须置于无水乙醇中超声分散，加入一维柔性高导热材料超声分散，然后加入粘结剂，搅拌后获得纺丝液；纺丝液经过静电纺丝处理，将纺丝物经过干燥、除炭处理和陶瓷化热处理后，获得氮化硼陶瓷基薄膜。
2.根据权利要求1所述的一种柔性高导热氮化硼陶瓷基薄膜的制备方法，其特征在于，步骤1中，混合溶液中，三聚氰胺的浓度为0.05-0.2M。
3.根据权利要求1所述的一种柔性高导热氮化硼陶瓷基薄膜的制备方法，其特征在于，步骤1中，三聚氰胺和硼酸的摩尔比为1:1-1:4。
4.根据权利要求1所述的一种柔性高导热氮化硼陶瓷基薄膜的制备方法，其特征在于，步骤1中，搅拌温度为80-100℃，陈化时间为20-30h。
5.根据权利要求1所述的一种柔性高导热氮化硼陶瓷基薄膜的制备方法，其特征在于，步骤1中，干燥温度为70-100℃，干燥时间为30-40h。
6.根据权利要求1所述的一种柔性高导热氮化硼陶瓷基薄膜的制备方法，其特征在于，步骤2中，氮化硼晶须在无水乙醇中的浓度为0.1-0.2g·mL-1；一维柔性高导热材料在无水乙醇中的浓度为0.005-0.1g·mL-1，聚乙烯吡咯烷酮在无水乙醇中的浓度为0.05-0.10g·mL-1。
7.根据权利要求1所述的一种柔性高导热氮化硼陶瓷基薄膜的制备方法，其特征在于，步骤2中，一维柔性高导热材料为碳纳米管或氮化硼纳米管。
8.根据权利要求1所述的一种柔性高导热氮化硼陶瓷基薄膜的制备方法，其特征在于，步骤2中，除炭处理的温度为400-600℃，时间为0.5-4h。
9.根据权利要求1所述的一种柔性高导热氮化硼陶瓷基薄膜的制备方法，其特征在于，步骤2中，陶瓷化热处理升温速率为2-10℃/min，最终温度为1400-1800℃，时间为0.5-6h。
10.一种通过权利要求1-9任意一项所述制备方法制得的柔性高导热氮化硼陶瓷基薄膜，其特征在于，由氮化硼晶须和纳米管搭接组成，所述纳米管为碳纳米管或氮化硼纳米管。
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