CN108610060A - 一种光敏性颗粒稳定乳液及薄壁空心球的制备方法 - Google Patents

一种光敏性颗粒稳定乳液及薄壁空心球的制备方法 Download PDF

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CN108610060A
CN108610060A CN201810414616.1A CN201810414616A CN108610060A CN 108610060 A CN108610060 A CN 108610060A CN 201810414616 A CN201810414616 A CN 201810414616A CN 108610060 A CN108610060 A CN 108610060A
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杨金龙
霍文龙
张笑妍
陈雨谷
席小庆
王亚利
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New Mstar Technology Ltd (tianjin) New Mstar Technology Ltd
Tsinghua University
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Abstract

本发明公开了属于多孔陶瓷材料技术领域的一种光敏性颗粒稳定乳液及薄壁空心球的制备方法。该光敏性颗粒稳定乳液通过将油相和含有陶瓷粉体的水相浆料混合、乳化得到，其中水相、油相中至少有一相含有光敏材料，并加入相应的光引发剂；通过稀释光敏性乳液、施加外部光场引发光敏低聚物分子聚合反应得到固化的陶瓷颗粒组装空心球，经分离、烧结即得到薄壁空心球；制备得到的光敏性乳液能够应用于光固化3D打印，制得的空心球结构可控、应用广泛；本发明提供的制备方法具有简单高效、成本低廉的优点，易于工业化推广。

Description

一种光敏性颗粒稳定乳液及薄壁空心球的制备方法
技术领域
本发明属于多孔陶瓷材料技术领域，特别涉及一种光敏性颗粒稳定乳液及薄壁空心球的制备方法。
背景技术
形状复杂、结构精细的具有多级孔结构的泡沫陶瓷的研究对国民经济及国防等领域的发展起着重要的促进作用。有研究利用直写成型技术打印颗粒稳定泡沫/乳液陶瓷，结果证实利用3D打印制备的多级孔陶瓷材料具有更好的综合性能，特别是优异的力学性能。然而，直写成型技术目前只能制备形状相对简单和具有特定宏观框架结构形状的陶瓷产品，尚无法满足形状复杂和结构精细的多级孔陶瓷材料的制备，具有一定的局限性。
另一方面，空心微珠作为一类同属多孔陶瓷材料范畴的空心粉体材料在药物缓释、石油开采、燃料电池、保温隔热等领域扮演了越来越重要的角色。目前现有技术中，陶瓷空心微珠的制备方法主要有喷雾干燥法、牺牲模板法、溶胶凝胶法、熔融法等，但是这些方法均存在制备参数受限、生产成本高昂、难以大批量生产等问题。
发明内容
本发明的目的在于提供一种光敏性颗粒稳定乳液及薄壁空心球的制备方法，具体技术方案如下：
一种光敏性颗粒稳定乳液的制备方法为将油相和含有陶瓷粉体的水相浆料混合、乳化得到，具体包括以下两种方式；
(1)水相浆料中含有水溶性光敏物质和光引发剂Ⅰ，油相为辛烷；
(2)水相浆料中含有或不含有水溶性光敏物质和光引发剂Ⅰ，油相为光敏树脂和光引发剂Ⅱ的混合物；
所述陶瓷粉体为氧化铝、氧化锆、铝溶胶或锆溶胶；
水溶性光敏物质为丙烯酰胺和亚甲基双丙烯酰胺混合水溶液，光引发剂Ⅰ为1173D光引发剂；
光敏树脂为含有丙烯酸酯基团的光敏树脂，光引发剂Ⅱ为819引发剂。
所述光敏树脂为聚氨酯丙烯酸酯低聚物、季戊四醇四丙烯酸酯低聚物、己二醇二丙烯酸酯低聚物中的一种或多种。
所述含有陶瓷粉体的水相浆料为：在固相含量为20～60wt％的水基陶瓷浆料，加入两亲分子调节其PH为4.2～5.3。
所述陶瓷粉体粒径为0.02～3μm；两亲分子为C2～C6羧酸包括丁酸、戊酸或己酸，加入量为水基陶瓷浆料质量的0.2％～1.0wt％。
含有水溶性光敏物质和光引发剂Ⅰ的水相浆料中，丙烯酰胺含量为水相浆料总质量的10～30wt％，亚甲基双丙烯酰胺、1173D光引发剂的含量均为丙烯酰胺含量的5～8wt％。
含有光敏树脂和光引发剂Ⅱ的油相中，819光引发剂的含量为光敏树脂质量的1～3wt％。
油相和含有陶瓷粉体的水相浆料混合时，水基浆料加入量为混合后溶液总体积的26～74vol％，乳化时所用乳化设备为机械搅拌机或均质机，转速为800～1500rmp。
通过调控两亲分子含量、水相油相混合比例，可以得到油包水或水包油型光敏性颗粒稳定乳液，具体为：提高戊酸含量并且减少水相在体系中的含量可以得到水包油型光敏性颗粒稳定乳液；反之得到油包水型光敏性颗粒稳定乳液。
基于所述制备方法制备得到的光敏性颗粒稳定乳液进行的薄壁空心球的制备方法包括以下步骤：
(1)稀释光敏性颗粒稳定乳液，机械搅拌将乳液分散成球形微米级的乳滴后，利用单光源照射5～10分钟引发光敏分子聚合反应后得到固化乳液；
(2)将步骤(1)得到的固化乳液固液分离后，烧结固相即得到薄壁空心球。
所述步骤(1)中稀释剂为辛烷或pH为4.2～5.3的去离子水，其中去离子PH利用盐酸调节，稀释剂体积为光敏性颗粒稳定乳液体积的5～20倍；机械搅拌转速为150～500rmp。
光敏性颗粒稳定乳液制备方法中水相浆料含有水溶性光敏物质和光引发剂Ⅰ，步骤(1)中单光源波长为365nm；水相浆料不含有水溶性光敏物质和光引发剂Ⅰ，步骤(1)中单光源波长为405nm。
光敏性颗粒稳定乳液制备方法中水相浆料含有水溶性光敏物质和光引发剂Ⅰ，所述步骤(2)固液分离后还需冷冻干燥24～48h，其中固液分离为离心分离或过滤分离。
所述步骤(2)中烧结温度为800-1500℃，保温1-3h。
所述制备方法制备得到的薄壁空心球尺寸为5～60μm，孔壁厚度为0.03～2μm。
本发明的有益效果为：
(1)本发明制备得到的光敏性颗粒稳定乳液具有光敏特性，施加一定的光场可以实现快速固化成型，能够作为一种新型前驱体用于光固化3D打印复杂形状、精细结构的多级孔陶瓷材料；
(2)本发明制备得到的光敏性颗粒稳定乳液中，陶瓷颗粒不可逆吸附在水/油或者水/气界面，进而抵制乳液中乳滴的歧化、合并、破裂现象，使其稳定存在，因此，相比于现有技术，本发明制备得到的乳液稳定性更强，有利于空心球的生成；
(3)本发明制备得到的薄壁空心球结构可控，孔径、孔壁厚度空心球形貌可以通过光敏树脂黏度、搅拌工艺、固相含量、两亲分子含量、水相油相混合比例等参数进行有效调节；相比化学合成法而言，本发明空心球的制备方法简单高效、无污染、成本低廉，有利于工业化生产。
附图说明
图1为本发明实施例1制备得到的光敏性颗粒稳定乳液宏观图片；
图2为本发明实施例1制备得到的固化乳液中微球的微观结构；
图3为本发明实施例2制备得到的薄壁空心球微观结构；
图4为本发明实施例3制备得到的固化乳液中微球的微观结构；
图5为本发明实施例3制备得到的薄壁空心球微观结构。
具体实施方式
本发明提供了一种光敏性颗粒稳定乳液及薄壁空心球的制备方法，下面结合附图和实施例对本发明做进一步的说明。
实施例1
制备水包油型光敏性颗粒稳定乳液：
(1)水相：配制30g固相含量为52wt％的水基氧化铝陶瓷浆料，其中氧化铝平均粒径为0.5μm，加入0.1g戊酸，pH调节至4.8；
(2)油相：将35g聚氨酯丙烯酸酯和季戊四醇四丙烯酸酯以质量比3:2混合后，加入2wt％树脂质量的819光引发剂；
(3)乳化：将水相和油相混合，并用机械搅拌机在1000rmp转速下搅拌乳化，得到如图1所示的水包油型光敏性颗粒稳定乳液。
制备薄壁空心球：
(1)利用盐酸调节pH至4.8的500ml去离子水稀释上述得到的乳液，并用搅拌机在400rmp转速下搅拌5分钟，随后用405nm的单光源照射引发光敏分子聚合反应，得到固化乳液；固化乳液中微球的微观结构如图2所示；
(2)经离心或过滤分离后，在1000℃下烧结固相并保温2h，即得到薄壁空心球。
图2中微球为单分散陶瓷微球，外层为均匀分散的陶瓷壳层，内包裹固化的光敏聚合物。
实施例2
制备油包水型光敏性颗粒稳定乳液：
(1)水相：配制30g固相含量为52wt％的水基氧化铝陶瓷浆料，其中氧化铝平均粒径为0.5μm，加入0.14g戊酸，pH调节至4.6；
(2)油相：将总质量为35g的季戊四醇四丙烯酸酯和819光引发剂均匀混合，其中819光引发剂质量为季戊四醇四丙烯酸酯质量的2wt％；
(3)乳化：将水相和油相混合，并用机械搅拌机在1000rmp转速下搅拌乳化，得到油包水型光敏性颗粒稳定乳液。
制备薄壁空心球：
(1)用500ml的辛烷稀释上述得到的乳液，并用搅拌机在400rmp转速下搅拌5分钟，随后用405nm的单光源照射引发光敏分子聚合反应得到固化乳液；
(2)经离心或过滤分离后，在1000℃下烧结固相并保温3h后即得到如图3所示薄壁空心球；
从图3可以看出，上述制备得到的薄壁空心球内部还有多个球形孔结构。
实施例3
制备油包水型光敏性颗粒稳定乳液：
(1)水相：配制50g固相含量为30wt％的光敏性水基氧化铝溶胶浆料，水基浆料中丙烯酰胺、亚甲基双丙烯酰胺和光引发剂1173D的含量分别为水基浆料总质量的13wt％、1wt％、1wt％，铝溶胶纳米颗粒的粒径为30nm；加入0.2g戊酸将水基光敏浆料的pH调节至4.2；
(2)油相：将总质量为20g的季戊四醇四丙烯酸酯和819光引发剂均匀混合，其中819光引发剂质量为季戊四醇四丙烯酸酯质量的2wt％；
(3)乳化：将水相和油相混合，并用机械搅拌机在800rmp转速下搅拌乳化，得到油包水型光敏性颗粒稳定乳液。
制备薄壁空心球：
(1)利用盐酸调节pH至4.8的800ml的去离子水稀释上述得到的乳液，并用搅拌机在200rmp转速下搅拌5分钟，随后用365nm的单光源照射引发光敏分子聚合反应得到固化乳液；固化乳液中微球的微观结构如图4所示；
(2)经离心或过滤分离后，冷冻干燥36h后，在900℃下烧结固相并保温3h即得到薄壁空心球，具体如图5所示。
图2、图4均为单光源照射即光敏分子聚合反应后得到的固化乳液中固化乳滴的微观结构，从图2、图4可以看出固化乳液中微球球形度良好，尺寸为微米级；实施例1、2所用陶瓷粉体粒径分别为μm级、nm级，光固化乳液中均形成了球形度良好的陶瓷微球，即不同粒径尺寸的陶瓷粉体均适用于该体系。
图3、图5均为烧结后得到的薄壁空心球微观结构，从图3、图5可以看出，所制备得到的空心球尺寸为5～60μm，孔壁厚度为0.03～2μm；对比分析发现，水相为光敏性水基浆料时制备得到的空心球球形度更好。

Claims (10)

1.一种光敏性颗粒稳定乳液的制备方法，其特征在于，将油相和含有陶瓷粉体的水相浆料混合、乳化得到，具体包括以下两种方式；
(1)水相浆料中含有水溶性光敏物质和光引发剂Ⅰ，油相为辛烷；
(2)水相浆料中含有或不含有水溶性光敏物质和光引发剂Ⅰ，油相为光敏树脂和光引发剂Ⅱ的混合物；
所述陶瓷粉体为氧化铝、氧化锆、铝溶胶或锆溶胶；
水溶性光敏物质为丙烯酰胺和亚甲基双丙烯酰胺水溶液，光引发剂Ⅰ为1173D光引发剂；
光敏树脂为含有丙烯酸酯基团的光敏树脂，光引发剂Ⅱ为819引发剂。
2.根据权利要求1所述的制备方法，其特征在于，所述光敏树脂为聚氨酯丙烯酸酯低聚物、季戊四醇四丙烯酸酯低聚物、己二醇二丙烯酸酯低聚物中的一种或多种。
3.根据权利要求1所述的制备方法，其特征在于，所述含有陶瓷粉体的水相浆料为：在固相含量为20～60wt％的水基陶瓷浆料，加入两亲分子调节其PH为4.2～5.3。
4.根据权利要求3所述的制备方法，其特征在于，所述陶瓷粉体粒径为0.02～3μm；两亲分子为C2～C6羧酸，加入量为水基陶瓷浆料质量的0.2％～1.0wt％。
5.根据权利要求1所述的制备方法，其特征在于，含有水溶性光敏物质和光引发剂Ⅰ的水相浆料中，丙烯酰胺含量为水相浆料总质量的10～30wt％，亚甲基双丙烯酰胺、1173D光引发剂的含量均为丙烯酰胺含量的5～8wt％。
6.根据权利要求1所述的制备方法，其特征在于，含有光敏树脂和光引发剂Ⅱ的油相中，819光引发剂的含量为光敏树脂质量的1～3wt％。
7.根据权利要求1所述的制备方法，其特征在于，油相和含有陶瓷粉体的水相浆料混合时，水基浆料加入量为混合后溶液总体积的26～74vol％，乳化时所用乳化设备为机械搅拌机或均质机，转速为800～1500rmp。
8.一种基于权利要求1-7任一项所述制备方法制备得到的光敏性颗粒稳定乳液进行的薄壁空心球的制备方法，其特征在于，所述制备包括以下步骤：
(1)稀释光敏性颗粒稳定乳液，机械搅拌后利用单光源照射后得到固化乳液；
(2)固液分离后，烧结固相即得到薄壁空心球。
9.根据权利要求8所述的薄壁空心球的制备方法，其特征在于，所述步骤(1)中稀释剂为辛烷或pH为4.2～5.3的去离子水，稀释剂体积为光敏性颗粒稳定乳液体积的5～20倍；
光敏性颗粒稳定乳液制备方法中水相浆料含有水溶性光敏物质和光引发剂Ⅰ，单光源波长为365nm；水相浆料不含有水溶性光敏物质和光引发剂Ⅰ，单光源波长为405nm。
10.根据权利要求8所述的薄壁空心球的制备方法，其特征在于，光敏性颗粒稳定乳液制备方法中水相浆料含有水溶性光敏物质和光引发剂Ⅰ，所述步骤(2)固液分离后还需冷冻干燥24～48h。
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