CN116041075A - 一种空心陶瓷微球及其制备方法和应用 - Google Patents
一种空心陶瓷微球及其制备方法和应用 Download PDFInfo
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- CN116041075A CN116041075A CN202310343310.2A CN202310343310A CN116041075A CN 116041075 A CN116041075 A CN 116041075A CN 202310343310 A CN202310343310 A CN 202310343310A CN 116041075 A CN116041075 A CN 116041075A
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- hollow ceramic
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Abstract
本发明公开了一种空心陶瓷微球及其制备方法和应用。本发明的空心陶瓷微球的制备方法包括以下步骤：1）将聚合物陶瓷前驱体溶液和有机聚合物溶液混合，得到外相注射液；2）将外相注射液和内相注射液通过同轴针头进行方波脉冲式注射制成核壳结构的液滴，并使核壳结构的液滴在收集液中固化定型，得到核壳结构的微球；3）将核壳结构的微球加热固化，再进行排胶和热解，再进行烧结，即得空心陶瓷微球。本发明的空心陶瓷微球大小均一、表面形态好、尺寸和组成可调控，且其制备方法简单、快速，适合用作防护涂层中的填料以及电磁屏蔽材料，具有广阔的应用前景。
Description
技术领域
本发明涉及陶瓷材料技术领域，具体涉及一种空心陶瓷微球及其制备方法和应用。
背景技术
空心陶瓷微球是一种具有中空内腔的球形陶瓷颗粒材料，具有轻质、分散性优良、绝热隔音、化学稳定性强、电磁屏蔽性能好等众多优势。近年来，空心陶瓷微球被广泛应用在涂层填充剂材料、电磁屏蔽材料、航空航天及海洋船舶的轻质结构材料、隔热保温材料等不同技术领域，是工业领域大力发展的材料之一，在军用及民用市场均具有广阔的应用前景。
目前，空心陶瓷微球的制备方法主要包括模板法和无模板法。模板法存在模板难以去除、去除模板时球壳易被破坏等问题，而无模板法则存在微球尺寸难以调控、微球产率较低等问题，均难以完全满足实际应用要求。
因此，开发一种可以制备出大小均一、尺寸和组成可调控的空心陶瓷微球的方法具有十分重要的意义。
发明内容
本发明的目的在于提供一种空心陶瓷微球及其制备方法和应用。
本发明所采取的技术方案是：
一种空心陶瓷微球的制备方法包括以下步骤：
1)将聚合物陶瓷前驱体溶液和有机聚合物溶液混合，得到外相注射液；
2)将外相注射液和内相注射液通过同轴针头进行方波脉冲式注射制成核壳结构的液滴，并使核壳结构的液滴在收集液中固化定型，得到核壳结构的微球；
3)将核壳结构的微球加热固化，再进行排胶和热解，再进行烧结，即得空心陶瓷微球。
优选的，步骤1）所述聚合物陶瓷前驱体溶液中的聚合物陶瓷前驱体为含锆的聚合物陶瓷前驱体。
进一步优选的，步骤1）所述聚合物陶瓷前驱体溶液中的聚合物陶瓷前驱体为碳化锆前驱体、氧化锆前驱体、碳化锆-碳化硅前驱体、氧化锆-氧化硅前驱体中的至少一种。
优选的，步骤1）所述聚合物陶瓷前驱体溶液通过以下方法制成：将含锆化合物和有机配体分散在有机溶剂中，再加水进行水解，即得含锆的聚合物陶瓷前驱体溶液，或者，将含锆化合物和有机配体分散在有机溶剂中，再加入硅烷偶联剂，再加水进行水解，即得含锆的聚合物陶瓷前驱体溶液。
优选的，所述含锆化合物、有机配体的摩尔比为1:0.2～10。
优选的，所述含锆化合物为正丙醇锆、叔丁醇锆、氯氧化锆中的至少一种。
优选的，所述有机配体为草酸、乙酸、甲酸、硝酸、水杨酸、柠檬酸、羟基乙酸、乙酰丙酮、乙二胺、三乙胺、二乙醇胺中的至少一种。
优选的，所述硅烷偶联剂为甲基三乙氧基硅烷、二甲基二乙氧基硅烷、乙烯基三乙氧基硅烷、二甲氧基甲基乙烯基硅烷中的至少一种。
优选的，所述含锆化合物、硅烷偶联剂的摩尔比为1:0.2～1。
优选的，步骤1）所述有机聚合物溶液中的有机聚合物为聚丙烯腈、酚醛树脂、聚苯乙烯、聚甲基丙烯酸甲酯、聚乙烯吡咯烷酮中的至少一种。
进一步优选的，步骤1）所述有机聚合物溶液中的有机聚合物为聚丙烯腈、酚醛树脂中的至少一种。聚丙烯腈和酚醛树脂的残碳率较高，不仅可以辅助微球成型，而且还可以补充碳源。
优选的，步骤1）所述外相注射液中聚合物陶瓷前驱体的质量分数为1%～50%、有机聚合物的质量分数为1%～30%。
进一步优选的，步骤1）所述外相注射液中聚合物陶瓷前驱体的质量分数为5%～20%、有机聚合物的质量分数为5%～10%。
优选的，步骤2）所述内相注射液为液体石蜡、醋酸纤维素溶液、聚丙烯溶液、二甲基硅油、聚乙二醇溶液、丙三醇、乙二醇中的至少一种。
优选的，步骤2）所述方波脉冲式注射的相关参数为：同轴针头的内置针头规格为20G～30G，外置针头规格为15G～25G；外相注射液的供给速度为0.1mL/min～1mL/min，内相注射液的供给速度为0.01mL/min～0.5mL/min；脉冲宽度为1s～3s，脉冲周期为2s～5s。
进一步优选的，步骤2）所述方波脉冲式注射的相关参数为：同轴针头的内置针头规格为22G～30G，外置针头规格为17G～21G；外相注射液的供给速度为0.2mL/min～0.8mL/min，内相注射液的供给速度为0.03mL/min～0.2mL/min；脉冲宽度为1s～2s，脉冲周期为2s～4s。
优选的，步骤2）所述收集液为水、乙醇、甲醇、丙醇、异丙醇、正丁醇、叔丁醇、正己醇中的至少一种。
优选的，步骤3）所述加热固化在100℃～300℃下进行。
进一步优选的，步骤3）所述加热固化在200℃～250℃下进行。
优选的，步骤3）所述排胶和热解在300℃～600℃下进行，排胶和热解的时间为1h～24h。
优选的，步骤3）所述烧结在800℃～1700℃下进行，烧结的时间为1h～12h。
进一步优选的，步骤3）所述烧结在1100℃～1600℃下进行，烧结的时间为1h～4h。
一种空心陶瓷微球，其由上述制备方法制成。
一种如上所述的空心陶瓷微球在制备防护涂层材料或电磁屏蔽材料中的应用。
本发明的空心陶瓷微球的制备原理：本发明利用不同溶液在同轴针头内外层流速及粘度不同，通过脉冲式注射将内层液滴间断注入外层液滴中，外层液滴对内层液滴形成包裹，进而获得核壳结构微球，再在固化定型后通过溶剂的交换与固化时的溶剂挥发去除内层溶液，最终得到空心微球；空心陶瓷微球的内外层尺寸以及壁厚等参数可以通过调整注射泵供给速度、针头规格等参数进行灵活精确地调控，同时，通过调节聚合物陶瓷前驱体（具有流变学性能的可控性、陶瓷组分的可选和可调性以及性能的可控性，使用聚合物前驱体制备得到的陶瓷组分均匀，可以避免粉体烧结反应不充分的问题，而通过调节官能团和共聚的小分子单体的种类则可以实现多种元素的掺杂，实现分子级微观组成的精确调控）溶液组分、前驱体溶液比例及聚合物分子量可以实现对高分子链间的相互作用力及反应活性的调节，进而可以改变微球内部的形态，获得致密或多孔的不同球壁结构。
本发明的有益效果是：本发明的空心陶瓷微球大小均一、表面形态好、尺寸和组成可调控，且其制备方法简单、快速，适合用作防护涂层中的填料以及电磁屏蔽材料，具有广阔的应用前景。
具体来说：
1）本发明的空心陶瓷微球大小均一、表面形态好、组成与尺寸可调控，且球形外壳赋予其流动性和分散性，因而可以均匀分布在涂层材料中作为填料使用，同时，其中空内腔可以使一定频率范围内的电磁波在球内经过多次反射进行损耗，进而可以提高对电磁波能量的吸收，增强其电磁屏蔽效能，因而也可以用于电磁屏蔽材料；
2）本发明将聚合物陶瓷前驱体与脉冲式同轴注射技术相结合，提供了一种简单、方便且快速制备空心陶瓷微球的方法，适合进行大规模工业化生产。
附图说明
图1为实施例1和实施例2中的空心陶瓷微球的实物图。
图2为实施例2中的空心陶瓷微球的表面的SEM图。
图3为实施例2中的空心陶瓷微球的断面的SEM图。
图4为实施例2中的空心陶瓷微球的XRD图。
图5为实施例3中的空心陶瓷微球的断面的SEM图。
图6为实施例4中的空心陶瓷微球的断面的SEM图。
图7为实施例4中的空心陶瓷微球的XRD图。
图8为实施例5中的空心陶瓷微球的断面的SEM图。
图9为实施例6中的空心陶瓷微球的XRD图。
具体实施方式
下面结合具体实施例对本发明作进一步的解释和说明。
实施例1：
一种空心陶瓷微球，其制备方法包括以下步骤：
1）将15g的正丙醇锆、2.5g的甲基三乙氧基硅烷和2.5g的乙烯基三甲氧基硅烷分散在80g的正丙醇中，再加入3g的乙酸，再滴加1.5g的去离子水进行缩聚反应，反应5h后将溶液浓缩至50g，得到聚合物陶瓷前驱体溶液；
2）将10g的聚丙烯腈（数均分子量为50000）分散在90g的N,N-二甲基甲酰胺中，得到聚丙烯腈溶液；
3）将聚合物陶瓷前驱体溶液和聚丙烯腈溶液混合，得到外相注射液；
4）将50g的液体石蜡作为内相注射液，将乙醇作为收集液；
5）将外相注射液和内相注射液通过22G/17G同轴针头进行方波脉冲式注射制成核壳结构的液滴，同轴针头与收集液液面的距离5cm，外相注射液的供给速度为0.4mL/min，内相注射液的供给速度为0.1mL/min，内相注射泵由信号发生器产生的方波脉冲控制，脉冲宽度为1s，脉冲周期为3s，并使核壳结构的液滴在收集液中固化定型，过滤，得到核壳结构的微球；
6）将核壳结构的微球置于烘箱中250℃固化1h，再置于氩气保护的管式炉中500℃进行2h的排胶和热解，再升温至1100℃进行2h烧结，即得空心陶瓷微球（直径1mm左右，实物图如图1所示，上排）。
实施例2：
一种空心陶瓷微球，其制备方法包括以下步骤：
1）将15g的正丙醇锆、2.5g的甲基三乙氧基硅烷和2.5g的乙烯基三甲氧基硅烷分散在80g的正丙醇中，再加入3g的乙酸，再滴加1.5g的去离子水进行缩聚反应，反应5h后将溶液浓缩至50g，得到聚合物陶瓷前驱体溶液；
2）将10g的聚丙烯腈（数均分子量为50000）分散在90g的N,N-二甲基甲酰胺中，得到聚丙烯腈溶液；
3）将聚合物陶瓷前驱体溶液和聚丙烯腈溶液混合，得到外相注射液；
4）将50g的液体石蜡作为内相注射液，将乙醇作为收集液；
5）将外相注射液和内相注射液通过30G/21G同轴针头进行方波脉冲式注射制成核壳结构的液滴，同轴针头与收集液液面的距离5cm，外相注射液的供给速度为0.4mL/min，内相注射液的供给速度为0.1mL/min，内相注射泵由信号发生器产生的方波脉冲控制，脉冲宽度为1s，脉冲周期为4s，并使核壳结构的液滴在收集液中固化定型，过滤，得到核壳结构的微球；
6）将核壳结构的微球置于烘箱中250℃固化1h，再置于氩气保护的管式炉中500℃进行2h的排胶和热解，再升温至1100℃进行2h烧结，即得空心陶瓷微球（直径500μm左右，实物图如图1所示，下排）。
性能测试：
1）本实施例中的空心陶瓷微球的表面的扫描电子显微镜（SEM）图如图2所示，断面的SEM图如图3所示。
由图2和图3可知：本实施例中的空心陶瓷微球的直径在500μm左右，具有明显的空心结构，球壁较薄，且空心陶瓷微球的球壁具有多孔结构。
2）本实施例中的空心陶瓷微球的X射线衍射（XRD）图如图4所示。
由图4可知：本实施例中的空心陶瓷微球的主要晶型为氧化锆和氧化硅。
实施例3：
一种空心陶瓷微球，其制备方法包括以下步骤：
1）将15g的正丙醇锆和5g的甲基三乙氧基硅烷分散在80g的正丙醇中，再加入3g的乙酰丙酮，再滴加2g的去离子水进行缩聚反应，反应5h后将溶液浓缩至50g，得到聚合物陶瓷前驱体溶液；
2）将10g的聚丙烯腈（数均分子量为50000）分散在90g的N,N-二甲基甲酰胺中，得到聚丙烯腈溶液；
3）将聚合物陶瓷前驱体溶液和聚丙烯腈溶液混合，得到外相注射液；
4）将50g的液体石蜡作为内相注射液，将乙醇作为收集液；
5）将外相注射液和内相注射液通过30G/21G同轴针头进行方波脉冲式注射制成核壳结构的液滴，同轴针头与收集液液面的距离5cm，外相注射液的供给速度为0.4mL/min，内相注射液的供给速度为0.07mL/min，内相注射泵由信号发生器产生的方波脉冲控制，脉冲宽度为1s，脉冲周期为4s，并使核壳结构的液滴在收集液中固化定型，过滤，得到核壳结构的微球；
6）将核壳结构的微球置于烘箱中250℃固化1h，再置于氩气保护的管式炉中500℃进行2h的排胶和热解，再升温至1100℃进行2h烧结，即得空心陶瓷微球（直径500μm左右）。
性能测试：
本实施例中的空心陶瓷微球的断面的SEM图如图5所示。
由图5可知：本实施例中的空心陶瓷微球的直径在500μm左右，具有明显的空心结构，球壁较厚，且空心陶瓷微球的球壁具有多孔结构。
实施例4：
一种空心陶瓷微球，其制备方法包括以下步骤：
1）将20g的正丙醇锆分散在80g的正丙醇中，再加入3g的乙酰丙酮，再滴加2g的去离子水进行缩聚反应，反应5h后将溶液浓缩至50g，得到聚合物陶瓷前驱体溶液；
2）将10g的聚丙烯腈（数均分子量为150000）分散在90g的N,N-二甲基甲酰胺中，得到聚丙烯腈溶液；
3）将聚合物陶瓷前驱体溶液和聚丙烯腈溶液混合，得到外相注射液；
4）将50g的液体石蜡作为内相注射液，将乙醇作为收集液；
5）将外相注射液和内相注射液通过30G/21G同轴针头进行方波脉冲式注射制成核壳结构的液滴，同轴针头与收集液液面的距离5cm，外相注射液的供给速度为0.4mL/min，内相注射液的供给速度为0.15mL/min，内相注射泵由信号发生器产生的方波脉冲控制，脉冲宽度为1s，脉冲周期为4s，并使核壳结构的液滴在收集液中固化定型，过滤，得到核壳结构的微球；
6）将核壳结构的微球置于烘箱中250℃固化1h，再置于马弗炉中500℃进行2h的排胶和热解，再升温至1400℃进行2h烧结，即得空心陶瓷微球（直径500μm左右）。
性能测试：
1）本实施例中的空心陶瓷微球的断面的SEM图如图6所示。
由图6可知：本实施例中的空心陶瓷微球的直径在500μm左右，具有明显的空心结构，球壁较薄。
2）本实施例中的空心陶瓷微球的XRD图如图7所示。
由图7可知：本实施例中的空心陶瓷微球的主要晶型为氧化锆。
实施例5：
一种空心陶瓷微球，其制备方法包括以下步骤：
1）将20g的正丙醇锆分散在80g的正丙醇中，再加入5g的乙酸，再滴加2g的去离子水进行缩聚反应，反应5h后将溶液浓缩至50g，得到聚合物陶瓷前驱体溶液；
2）将10g的聚丙烯腈（数均分子量为150000）分散在90g的N,N-二甲基甲酰胺中，得到聚丙烯腈溶液；
3）将聚合物陶瓷前驱体溶液和聚丙烯腈溶液混合，得到外相注射液；
4）将50g的液体石蜡作为内相注射液，将乙醇作为收集液；
5）将外相注射液和内相注射液通过30G/21G同轴针头进行方波脉冲式注射制成核壳结构的液滴，同轴针头与收集液液面的距离5cm，外相注射液的供给速度为0.4mL/min，内相注射液的供给速度为0.1mL/min，内相注射泵由信号发生器产生的方波脉冲控制，脉冲宽度为1s，脉冲周期为3s，并使核壳结构的液滴在收集液中固化定型，过滤，得到核壳结构的微球；
6）将核壳结构的微球置于烘箱中250℃固化1h，再置于马弗炉中500℃进行2h的排胶和热解，再升温至1400℃进行2h烧结，即得空心陶瓷微球（直径500μm左右）。
性能测试：
本实施例中的空心陶瓷微球的断面的SEM图如图8所示。
由图8可知：本实施例中的空心陶瓷微球的直径在500μm左右，具有明显的空心结构，球壁较薄，且球壁较为致密。
实施例6：
一种空心陶瓷微球，其制备方法包括以下步骤：
1）将15g的正丙醇锆、2.5g的甲基三乙氧基硅烷和2.5g的二甲基二乙氧基硅烷分散在80g的正丙醇中，再加入3g的乙二胺，再滴加1.5g的去离子水进行缩聚反应，反应5h后将溶液浓缩至50g，得到聚合物陶瓷前驱体溶液；
2）将5g的聚丙烯腈（数均分子量为150000）和和5g的线性酚醛树脂（数均分子量为800）分散在90g的N,N-二甲基甲酰胺中，得到聚丙烯腈-线性酚醛树脂溶液；
3）将聚合物陶瓷前驱体溶液和聚丙烯腈-线性酚醛树脂溶液混合，得到外相注射液；
4）将50g的液体石蜡作为内相注射液，将乙醇作为收集液；
5）将外相注射液和内相注射液通过30G/21G同轴针头进行方波脉冲式注射制成核壳结构的液滴，同轴针头与收集液液面的距离5cm，外相注射液的供给速度为0.4mL/min，内相注射液的供给速度为0.1mL/min，内相注射泵由信号发生器产生的方波脉冲控制，脉冲宽度为1s，脉冲周期为3s，并使核壳结构的液滴在收集液中固化定型，过滤，得到核壳结构的微球；
6）将核壳结构的微球置于烘箱中250℃固化1h，再置于氩气保护的管式炉中500℃进行2h的排胶和热解，再升温至1550℃进行2h烧结，即得空心陶瓷微球（直径500μm左右）。
性能测试：
本实施例中的空心陶瓷微球的XRD图如图9所示。
由图9可知：本实施例中的空心陶瓷微球的主要晶型为碳化锆。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (7)
1.一种空心陶瓷微球的制备方法，其特征在于，包括以下步骤：
1)将聚合物陶瓷前驱体溶液和有机聚合物溶液混合，得到外相注射液；
2)将外相注射液和内相注射液通过同轴针头进行方波脉冲式注射制成核壳结构的液滴，并使核壳结构的液滴在收集液中固化定型，得到核壳结构的微球；
3)将核壳结构的微球加热固化，再进行排胶和热解，再进行烧结，即得空心陶瓷微球；
步骤1）所述聚合物陶瓷前驱体溶液中的聚合物陶瓷前驱体为含锆的聚合物陶瓷前驱体；
步骤1）所述有机聚合物溶液中的有机聚合物为聚丙烯腈、酚醛树脂、聚苯乙烯、聚甲基丙烯酸甲酯、聚乙烯吡咯烷酮中的至少一种；
步骤2）所述内相注射液为液体石蜡、醋酸纤维素溶液、聚丙烯溶液、二甲基硅油、聚乙二醇溶液、丙三醇、乙二醇中的至少一种。
2.根据权利要求1所述的空心陶瓷微球的制备方法，其特征在于：步骤1）所述外相注射液中聚合物陶瓷前驱体的质量分数为1%～50%、有机聚合物的质量分数为1%～30%。
3.根据权利要求1所述的空心陶瓷微球的制备方法，其特征在于：步骤2）所述方波脉冲式注射的相关参数为：同轴针头的内置针头规格为20G～30G，外置针头规格为15G～25G；外相注射液的供给速度为0.1mL/min～1mL/min，内相注射液的供给速度为0.01mL/min～0.5mL/min；脉冲宽度为1s～3s，脉冲周期为2s～5s。
4.根据权利要求1所述的空心陶瓷微球的制备方法，其特征在于：步骤2）所述收集液为水、乙醇、甲醇、丙醇、异丙醇、正丁醇、叔丁醇、正己醇中的至少一种。
5.根据权利要求1所述的空心陶瓷微球的制备方法，其特征在于：步骤3）所述加热固化在100℃～300℃下进行；步骤3）所述排胶和热解在300℃～600℃下进行，排胶和热解的时间为1h～24h；步骤3）所述烧结在800℃～1700℃下进行，烧结的时间为1h～12h。
6.一种空心陶瓷微球，其特征在于，由权利要求1～5中任意一项所述的制备方法制成。
7.一种如权利要求6所述的空心陶瓷微球在制备防护涂层材料或电磁屏蔽材料中的应用。
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