CN109265152A - 陶瓷空心球的制备方法 - Google Patents

陶瓷空心球的制备方法 Download PDF

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CN109265152A
CN109265152A CN201810974337.0A CN201810974337A CN109265152A CN 109265152 A CN109265152 A CN 109265152A CN 201810974337 A CN201810974337 A CN 201810974337A CN 109265152 A CN109265152 A CN 109265152A
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ceramic
hollow ball
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slurry
ceramic hollow
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CN109265152B (zh
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吕志刚
胡可辉
冯骞
李欣怡
魏亚蒙
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Tsinghua University
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Abstract

本发明公开了一种陶瓷空心球的制备方法。该方法包括以下步骤：将原料进行混合搅拌均匀得到陶瓷浆料，原料按重量份计，包含：陶瓷微粉、造孔剂、烧结助剂、分散剂及光敏树脂；然后用泡沫塑料载体沾取陶瓷浆料，得到包裹浆料的泡沫塑料载体；再将其悬浮于与陶瓷浆料不互溶的透明液态介质中，通过光源照射固化包裹泡沫塑料载体的陶瓷浆料；然后过滤，干燥，脱脂，烧结，得陶瓷空心球。本发明基于光固化陶瓷浆料成型技术，结合陶瓷结构性能对陶瓷浆料配方进行优化，对制备过程进行改进，获得致密度高、性能好的陶瓷空心球，采用该方法制备陶瓷空心球，大小可控，孔隙率及孔隙大小可调；且具有工艺简单、快速，绿色环保，成本低，适应性广等优点。

Description

陶瓷空心球的制备方法
技术领域
本发明涉及特种陶瓷成型技术领域，特别是涉及一种陶瓷空心球的制备方法。
背景技术
目前，陶瓷球在日用陶瓷、工业陶瓷领域应用十分广泛，主要成型方式包括挤出圆滚法、干法压制、颗粒直接圆滚法等，但这些方法成型过程中需要专用设备，其成本太高，且成型的陶瓷球坯体密度低导致烧结松散，使得陶瓷球应用发展受到限制。
光固化成型技术是一种节能、环保、快速的成型技术，光固化材料以其绿色环保、反应快速等优势，在材料应用领域迅速拓展。本发明正是从这一点出发，对陶瓷球的制备工艺进行的改进。
发明内容
基于上述问题，本发明的目的在于提供一种陶瓷空心球的制备方法，该方法基于光固化陶瓷浆料成型技术，结合陶瓷结构性能对陶瓷浆料的配方进行优化，对陶瓷空心球的制备过程进行改进，可获得致密度高、性能好的陶瓷空心球，且该方法所制备的陶瓷空心球大小可控，孔隙率及孔隙大小可调。
上述目的是通过以下技术方案实现的：
一种陶瓷空心球的制备方法，包括以下步骤：将原料进行混合并搅拌均匀，得到性能稳定的陶瓷浆料，其中，所述原料按重量份计，包含：
然后用泡沫塑料载体沾取所述陶瓷浆料，得到包裹浆料的泡沫塑料载体；将包裹浆料的泡沫塑料载体悬浮于透明液态介质中，其中，所述透明液态介质与陶瓷浆料不互溶，通过光源照射固化包裹泡沫塑料载体的陶瓷浆料；接着，进行过滤，干燥，脱脂，于800℃～1700℃下烧结0.2h～5h，制得所需陶瓷空心球。
有益效果：
本发明陶瓷空心球的制备方法结合陶瓷结构性能对陶瓷浆料的原料配方进行优化，得到分散均匀，稳定性、流动性、以及光固化特性均较好的陶瓷浆料，然后基于光固化成型技术，对陶瓷空心球的制备过程进行改进，并对工艺参数进行改进，获得的陶瓷空心球固化效果好、致密度高、成孔均匀。采用本发明制备陶瓷空心球，其大小可控，孔隙率以及孔隙大小可调，通过控制泡沫塑料载体的尺寸来控制陶瓷空心球的大小，通过控制原料陶瓷粉体的固含量来调整孔隙率，通过控制烧结条件中终烧温度和保温时间来控制孔隙率。
本发明制备陶瓷空心球的方法具有工艺简单易操作、制备速度快，技术要求低，绿色环保，成本低等优点；该方法适用性广：适合于多种陶瓷及复合陶瓷材料的陶瓷球的制备，既可完成单相陶瓷空心球的制备，也可完成复合陶瓷空心球的制备。
附图说明
图1是本发明陶瓷空心球的制备方法的流程示意图。
具体实施方式
下面将结合本发明附图以及具体实施例，对本发明的技术方案进行清楚、完整地描述：
图1示意性地示出了本发明陶瓷空心球的制备方法。如图1所示，本发明提供的陶瓷空心球的制备方法，包括以下步骤：将原料进行混合并搅拌均匀，得到性能稳定的陶瓷浆料，其中，所述原料按重量份计，包含：陶瓷微粉50份～90份，造孔剂0份～20份，烧结助剂2份～15份，分散剂2份～12份，以及光敏树脂10份～50份；然后用泡沫塑料载体沾取陶瓷浆料，得到包裹浆料的泡沫塑料载体；将包裹浆料的泡沫塑料载体悬浮于透明液态介质中，通过光源照射使得包裹泡沫塑料载体的陶瓷浆料均匀固化，其中，所述透明液态介质与陶瓷浆料不互溶的水；然后，进行过滤，干燥，置于马弗炉中400℃～800℃脱脂，于800℃～1700℃下烧结0.2h～5h，得到致密度高、性能好的陶瓷空心球，采用该方法制备陶瓷空心球，大小可控，孔隙率以及孔隙大小可调。本发明原料配比混合后得到的陶瓷浆料均匀、性能稳定，促使陶瓷浆料整体对光的折射和透射性增强，从而光可在陶瓷浆料中均匀传播，更有利于陶瓷浆料的均匀固化。本发明采用泡沫塑料载体沾取陶瓷浆料在特定条件下制成的陶瓷空心球成孔均匀、大小可控，孔隙率以及孔隙大小可调。
所述陶瓷微粉可以为氧化铝、氧化硅、氧化锆、碳化硅、氮化硅、羟基磷灰石、玻璃粉中的一种或几种。优选粒径小于50μm的陶瓷微粉，更优选地为平均粒径为5μm的陶瓷微粉。本发明通过从原料上调整陶瓷粉体的粒径和固含量，达到孔隙率以及孔隙大小可调，从而得到致密性更高的陶瓷空心球。
所述造孔剂包括无机造孔剂，和/或有机造孔剂中的一种或多种。例如造孔剂可以为碳酸铵、碳酸氢铵、氯化铵、氮化硅、煤粉、碳粉、锯末、萘、淀粉、聚乙烯醇、尿素、甲基丙烯酸甲酯、聚氯乙烯、聚苯乙烯中的任意一种或多种混合。其中，更优选有机造孔剂，例如可以为有机纤维造孔剂、聚甲基丙烯酸甲酯PMMA等。
所述烧结助剂可以为玻璃粉、黏土、高岭土、氧化钙、氧化镁、氧化钛中的一种或几种。其中，玻璃粉作为氧化硅烧结助剂使用。
所述分散剂可以为表面活性剂、偶联剂、不饱和有机酸和有机低聚物中的任意一种或多种混合。其中，所述表面活性剂选自环状硅氧烷、全甲基硅氧烷、含氟硅氧烷、壬基酚聚氧乙烯醚、烷基聚醚、十二烷基苯磺酸钠、硬脂酸铝、硬脂酸锌、硬脂酸钙、聚二甲基硅氧烷中的任意一种或多种混合。所述偶联剂选自氨轻基硅烷偶联剂、γ-甲基丙烯酞氧基丙基三甲氧基硅烷偶联剂、3-缩水甘油醚氧基丙基三甲氧基硅烷、甲基丙烯酰氧基硅烷偶联剂、环氧羟基硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、锆铝酸酯偶联剂中的任意一种或多种混合。所述不饱和有机酸选自丙烯酸、丁烯酸、山梨酸、氯丙烯酸中的任意一种或多种混合。所述有机低聚物选自聚酯多元醇、聚醚多元醇、聚乙烯蜡、聚丙烯、聚乙烯蜡、聚乙二醇、双酚型环氧树脂中的任意一种或多种混合。
所述光敏树脂按重量份计，包括：活性单体0～50份、预聚物20～50份、光引发剂0～5份、光稳定剂0～3份、光吸收剂0～5份、及少量添加剂。所述预聚物为环氧树脂和丙烯酸树脂中的任意一种或两种混合，其中，所述环氧树脂为双环戊二烯苯酚型环氧树脂、自双酚二缩水油醚二环氧树脂、大豆油改性环氧树脂、缩水甘油胺类环氧树脂和缩水甘油酯类环氧树脂中的任意一种或多种混合；所述丙烯酸树脂为聚酯丙烯酸酯、聚氨酯丙烯酸酯、双酚二缩水油醚二环氧丙烯酸树脂中的任意一种或多种混合。所述活性单体为丙烯酸酯单体，优选为1，6-乙二醇二丙烯酸酯、丙烯酸异冰片酯、丙氧基化新戊二醇二丙烯酸酯、丙烯酸十八烷基酯、三环癸基二甲醇二丙烯酸酯、烷氧基化季戊四醇四丙烯酸酯、乙氧基化三轻甲基三丙烯酸酯、苯氧乙基丙烯酸酯和二缩丙二醇二丙烯酸酯中的任意一种或多种混合。所述光引发剂为自由基光引发剂和阳离子光引发剂中的任意一种或两种混合，其中，所述自由基光引发剂为1-羟基环己基苯基甲酮、2,4,6-三甲基苯甲酞基二苯氧化膦、二苯甲酮、安息香双甲醚、异丙基硫杂葱酮、硫杂蒽酮和4-二甲氨基苯甲酸乙酯中的任意一种或多种混合；所述阳离子光引发剂为4-异丁基苯基-4’-甲基苯基碘鎓六氟磷酸盐、双2,6-二氟-3-吡咯苯基二茂铁、4-(苯硫基)苯基二苯基硫鎓六氟磷酸盐中的任意一种或多种混合。
本发明中，透明液态介质与陶瓷浆料不互溶，例如可以为水、甘油、甘油与水的混合物等。泡沫塑料载体可以为泡沫球或泡沫块体等任何形状。泡沫塑料载体的尺寸可以根据所需制备陶瓷空心球的体积来确定，从而达到控制陶瓷空心球的大小。例如泡沫塑料载体可以为直径0.5mm～5mm的泡沫球体，边长为0.5mm～5mm的泡沫块体等。
陶瓷浆料固化时，采用波长为350nm～480nm的光源进行照射固化成型，有利于光在陶瓷浆料中均匀传播，有利于陶瓷浆料的均匀固化，例如可以采用365nm的卤素灯照射，405nm或460nm的LED灯照射。脱脂温度为400℃～800℃，优选在600℃下脱脂。烧结温度为800℃～1700℃，时间0.2h～5h，优选在1400℃～1600℃下烧结。在该工艺参数下进行烧结，可更好地控制孔隙率，如终烧温度低孔隙率大，终烧温度高孔隙率小，保温时间短孔隙率大，保温时间长孔隙率小；且可将各种有机物全部排除。
实施例1
按照重量份计，将50份氧化铝陶瓷微粉，平均粒径5μm，15份氧化硅烧结助剂，2份分散剂，以及20份光敏树脂混合后，搅拌成均匀稳定的陶瓷浆料，其中，所述光敏树脂为丙烯酸树脂；然后将泡沫塑料载体，例如直径为1mm的泡沫塑料球，沾取上述制得的陶瓷浆料，放入水中悬浮，采用405nm的LED灯照射，使包裹泡沫塑料载体的陶瓷浆料固化成型，固化成型后，再过滤，干燥，置于马弗炉中在600℃下脱脂，于1600℃下烧结2小时，制成致密度高、成孔均匀的氧化铝陶瓷空心球，该空心陶瓷球的致密度为98％，直径为0.9mm。
实施例2
将90份的氧化锆陶瓷微粉，平均粒径为0.5μm，20份的PMMA造孔剂，2份氧化钛烧结助剂，12份的分散剂，以及50份的光敏树脂(其中，50份的光敏树脂包括活性单体7份、预聚物40份、光引发剂1份、光稳定剂1份、光吸收剂1份)，混合后，使用球磨机搅拌成均匀、性能稳定的陶瓷浆料，并真空除泡，然后将直径为2mm泡沫球沾取陶瓷浆料，悬浮于水中，采用365nm的卤素灯照射，使得包裹泡沫球的陶瓷浆料均匀固化成型，然后进行过滤，干燥，再于600℃下脱脂，1500℃下烧结4小时，制成致密度高、性能好的氧化锆陶瓷空心球，该陶瓷空心球的致密度为95％，直径为1.6mm。
实施例3
将60份的以1:1混合的氧化铝和氧化锆的混合陶瓷微粉，1份有机纤维造孔剂，10份氧化镁烧结助剂，5份的分散剂以及20份的光敏树脂混合后，搅拌成均匀稳定的陶瓷浆料，然后将特征尺寸为3mm的泡沫块体沾取陶瓷浆料，悬浮于水中，采用460nm的LED灯照射，固化成型后过滤，干燥，再于600℃脱脂，1400℃下烧结5小时，制成致密度99.5％、直径2.6mm的复合陶瓷空心球。
将上述实施例1-3所制备的陶瓷空心球进行性能测试，性能测试结果如表1所示。其中，空心球直径直接采用千分尺测量，孔隙率采用压汞仪测量，测出孔隙率再换算成致密度。
表1
实施例1 实施例2 实施例3
空心球直径mm 0.9 1.6 2.6
孔隙率％ 2 5 0.5
致密度％ 98 95 99.5
由上表可知，采用本发明的制备方法可以制备任意大小的陶瓷空心球，其孔隙率和孔隙大小也可根据需要进行调整，该方法所制备的陶瓷空心球的致密性好，成孔均匀。

Claims (10)

1.一种陶瓷空心球的制备方法，其特征在于，包括以下步骤：将原料进行混合并搅拌均匀，得到陶瓷浆料，其中，所述原料按重量份计，包含：
然后用泡沫塑料载体沾取所述陶瓷浆料，得到包裹浆料的泡沫塑料载体，将包裹浆料的泡沫塑料载体悬浮于透明液态介质中，其中，所述透明液态介质与陶瓷浆料不互溶，通过光源照射固化包裹泡沫塑料载体的陶瓷浆料；接着进行过滤，干燥，脱脂，于800℃～1700℃下烧结0.2h～5h，得到陶瓷空心球。
2.如权利要求1所述的陶瓷空心球的制备方法，其特征在于，所述陶瓷微粉包括氧化铝、氧化硅、氧化锆、碳化硅、氮化硅、羟基磷灰石、玻璃粉中的一种或几种。
3.如权利要求2所述的陶瓷空心球的制备方法，其特征在于，所述陶瓷微粉的粒径小于50μm。
4.如权利要求1所述的陶瓷空心球的制备方法，其特征在于，所述造孔剂包括碳酸铵、碳酸氢铵、氯化铵、氮化硅、煤粉、碳粉、锯末、萘、淀粉、聚乙烯醇、尿素、甲基丙烯酸甲酯、聚氯乙烯、聚苯乙烯中的任意一种或多种混合。
5.如权利要求1所述的陶瓷空心球的制备方法，其特征在于，所述烧结助剂包括玻璃粉、黏土、高岭土、氧化钙、氧化镁、氧化钛中的一种或几种。
6.如权利要求1所述的陶瓷空心球的制备方法，其特征在于，所述分散剂包括表面活性剂、偶联剂、不饱和有机酸和有机低聚物中的任意一种或多种混合。
7.如权利要求1所述的陶瓷空心球的制备方法，其特征在于，所述光敏树脂按重量份计，包括：活性单体0～50份、预聚物20～50份、光引发剂0～5份、光稳定剂0～3份、光吸收剂0～5份。
8.如权利要求7所述的陶瓷空心球的制备方法，其特征在于，所述活性单体为丙烯酸酯单体；所述预聚物为环氧树脂和丙烯酸树脂中的任意一种或两种混合；所述光引发剂为自由基光引发剂和阳离子光引发剂中的任意一种或两种混合。
9.如权利要求1-8任一项所述的陶瓷空心球的制备方法，其特征在于，所述透明液态介质为水和甘油中的一种或者两种的混合物。
10.如权利要求1-8任一项所述的陶瓷空心球的制备方法，其特征在于，固化时，采用波长为350nm～480nm的光源进行照射。
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CN111004026A (zh) * 2019-12-26 2020-04-14 中国人民解放军军事科学院国防工程研究院工程防护研究所 一种用于人防工程的镁橄榄石基泡沫陶瓷球壳的制备方法
CN111807811A (zh) * 2020-06-18 2020-10-23 江苏省陶瓷研究所有限公司 多孔陶瓷及其制备方法
CN111807811B (zh) * 2020-06-18 2022-03-11 江苏省陶瓷研究所有限公司 多孔陶瓷及其制备方法
CN113501698A (zh) * 2021-08-18 2021-10-15 广州中创建筑科技有限公司 一种轻骨料混凝土
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