CN107129283A - 一种光固化3d打印用高固相含量陶瓷浆料及其制备工艺 - Google Patents

一种光固化3d打印用高固相含量陶瓷浆料及其制备工艺 Download PDF

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CN107129283A
CN107129283A CN201710335167.7A CN201710335167A CN107129283A CN 107129283 A CN107129283 A CN 107129283A CN 201710335167 A CN201710335167 A CN 201710335167A CN 107129283 A CN107129283 A CN 107129283A
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photocuring
parts
ceramic
printing
high solid
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韦华
唐明亮
汤兵
沈晓冬
叶玉秋
魏帅飞
李启铭
李传强
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Jiangsu Mint New Mstar Technology Ltd
Nanjing Tech University
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Jiangsu Mint New Mstar Technology Ltd
Nanjing Tech University
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Abstract

本发明公开了一种光固化3D打印用高固相含量陶瓷浆料，按照质量份数，包括75‑90份无机陶瓷粉体和10‑25份有机液相材料，其制备工艺，先对无机陶瓷粉体进行改性处理，再将无机陶瓷粉体加入到预混的有机液相材料中，制备成为可用于光固化3D打印成型的高固相含量陶瓷浆料；其中改性处理包括物理表面改性工艺或/和化学表面改性工艺，该浆料制备的陶瓷坯体可以烧结高密实、高表面质量的陶瓷制品，解决了现有技术中存在的中有机组分含量高，陶瓷制品密实度低、表面质量差等问题。

Description

一种光固化3D打印用高固相含量陶瓷浆料及其制备工艺
技术领域
本发明涉及3D打印材料技术领域，特别涉及一种光固化3D打印用高固相含量陶瓷浆料及其制备工艺。
背景技术
3D打印技术(又称增材制造技术)是一种以材料累加为基本特征，以直接制造零部件为目标，具有广阔发展前景的快速制造技术，被誉为制造业的一场革命。3D打印技术被广泛应用于产品原型、摸具制造以及艺术创作、珠宝制作等领域，以替代这些领域传统的精细加工工艺。除此之外，该技术在鞋类、建筑、工程和施工、汽车、航空航天、牙科和医疗产业、教育、地理信息系统、土木工程、武器制造、生物工程以及其他多个领域都有广泛应用的巨大潜力。
材料是3D打印的瓶颈也是关键。目前，金属、高分子材料的3D打印受到广泛研究和应用。无机陶瓷材料因为其高耐温、高硬度、多功能性等优点，是重要的结构和功能材料，在工业和民用方面都有极其重要的应用。目前，无机陶瓷材料的3D打印主要采用激光选择烧结工艺(SLS)。该种工艺制备的陶瓷制品，密实度低(低于80％)，应用受到极大限制。光固化3D打印(SLA)陶瓷制品可以获得很高的密实度(98％)，并且表面质量高(粗糙度～0.4μm)，抗弯强度也能达到500MPa以上，逐渐受到重视。由于陶瓷光固化3D打印工艺对原材料(浆料)的要求极高，如具有大的无机固含量和低的表面能等。原料固含量高从而使得3D打印的生坯烧结过程收缩率低，制品密实度高；表面能低有利于打印过程中材料的层状铺叠。目前，光固化3D打印用的陶瓷浆料还未见工业化生产，现有实验室制备的浆料的固含量最高只有75％，还无法达到高致密陶瓷的制备要求，陶瓷的尺寸精度和表面质量与SLS相比也没有明显提升。。
发明内容
本发明所要解决的技术问题是提供一种光固化3D打印用高固相含量陶瓷浆料及其制备工艺，该浆料制备的陶瓷坯体可以烧结高密实、高表面质量的陶瓷制品，解决了现有技术中存在的中有机组分含量高，陶瓷制品密实度低、表面质量差等问题，能够推动具有复杂结构的高质量3D打印陶瓷制品的工业化应用，以解决现有技术中导致的上述多项缺陷。
为实现上述目的，本发明提供以下的技术方案：一种光固化3D打印用高固相含量陶瓷浆料，按照质量份数，包括75-90份无机陶瓷粉体和10-25份有机液相材料；所述无机陶瓷粉体由氧化铝、氧化硅、氧化锆、碳化硅、氮化硅等一种或多种经过预先物理表面改性或化学表面改性的无机粉体材料组成；所述有机液相材料按照质量份数比，由以下原料组成：95-98.5份液态光敏树脂，0.5-2.0份悬浮分散剂、0.5-1.0份消泡剂，0.5-2.0份的流变改性剂。
优选的，所述液态光敏树脂为环氧丙烯酸光敏树脂、聚氨酯丙烯酸树脂中的一种；所述悬浮分散剂为聚乙二醇、聚丙烯酸铵、改性氨基磺酸分散剂的一种或多种混合物；所述消泡剂为二甲基硅油、聚硅氧烷、聚二甲基硅氧烷、聚醚改性硅等的一种或多种混合物；所述流变改性剂为丙烯酸流变改性剂。
一种光固化3D打印用高固相含量陶瓷浆料的制备工艺，先对无机陶瓷粉体进行改性处理，再将无机陶瓷粉体加入到预混的有机液相材料中，在真空搅拌机进行搅拌混合0.5-2.0小时，制备成为可用于光固化3D打印成型的高固相含量陶瓷浆料；其中改性处理包括物理表面改性工艺或/和化学表面改性工艺。
优选的，所述物理表面改性工艺，将无机粉体材料与浓度为1-10％的十二烷基硫酸钠、十二烷基苯磺酸钠、烷基酚聚氧乙烯醚、脂肪酸聚氧乙烯酯等一种或几种表面活性剂混合溶液进行充分混合，然后快速烘干；表面活性剂的用量为粉体材料质量的1.0-10.0％。
优选的，所述化学表面改性工艺，将无机粉体材料加入浓度为1-10％硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、硼酸酯偶联剂等一种或多种耦合剂的混合溶液中，在30-90℃下反应0.5-5.0小时，然后烘干；耦合剂的用量为粉体材料质量的1.0-10.0％。
采用以上技术方案的有益效果是：本发明一种光固化3D打印用高固相含量陶瓷浆料及其制备工艺，通过对无机粉体颗粒进行表面改性，使得颗粒表面包裹憎水层，能够与光敏树脂产生紧密结合，促进了无机粉体在树脂中的分散性、均匀性和稳定性，可以大幅度减少树脂的用量，从而提高生坯的无机粉体含量，进而提高烧结陶瓷制品的密实度；通过添加流变改性剂，降低了浆料的表面张力，降低了浆体与3D打印机刮板之间的粘结性，有利于提高3D打印过程每层浆料铺刮时的层厚精度和表面质量，进而提高打印生坯的精度和表面质量。
具体实施方式
下面详细说明本发明的优选实施方式。
实施例1
光固化3D打印高密实度氧化铝陶瓷的光敏陶瓷浆料的制备
氧化铝陶瓷粉体材料表面改性
将100份最大粒径≤5μm，d0.5为0.7μm的超细氧化铝粉体材料与溶解了5份十二烷基磺酸钠溶液中并搅拌，然后在60℃下烘干得到表面吸附改性的氧化铝粉体材料。
配制有机液相材料
将0.5份二甲基硅油、2.0份聚乙二醇、0.5份丙烯酸流变改性剂依次加到97份环氧丙烯酸光敏树脂中并充分搅拌混合制得有机液相材料。
制备光敏氧化铝浆料
将75份经过表面改性的氧化铝粉体材料逐渐加入到25份预混的有机液相材料中，在真空搅拌机进行搅拌混合1.0小时，制备成为可用于光固化3D打印成型的光敏氧化铝陶瓷浆料。该浆料通过光固化3D打印工艺制备可以烧结为密实度为95％左右、结构复杂的氧化铝陶瓷制品。
实施例2
光固化3D打印高密实度氧化锆陶瓷用光敏陶瓷浆料的制备
氧化锆陶瓷粉体材料表面改性
将5份硅烷偶联剂γ-缩水甘油醚氧丙基三甲氧基硅烷溶解于一定量水中制备成浓度为10％、温度为50℃的溶液；将100份最大粒径≤5μm，d0.5为500nm的氧化锆粉体材料加入到偶联剂溶液中，强烈搅拌1.5小时后，过滤烘干获得表面改性的氧化锆粉体。
配制有机液相材料
将0.5份二甲基硅油、1.0份聚丙烯酸铵、1.0份丙烯酸流变改性剂依次加到97.5份环氧丙烯酸光敏树脂中并充分搅拌混合制得有机液相材料。
制备光敏氧化锆陶瓷浆料
将90份经过表面改性的氧化锆粉体材料逐渐加入到10份预混的有机液相材料中，在真空搅拌机进行搅拌混合2.0小时，制备成为可用于光固化3D打印成型的光敏氧化锆陶瓷浆料。该浆料通过光固化3D打印工艺制备可以烧结为密实度为98％左右、结构复杂的氧化锆陶瓷制品。
实施例3
光固化3D打印高密实度氧化硅陶瓷用光敏陶瓷浆料的制备
氧化硅陶瓷粉体材料表面改性
将2份硅烷偶联剂六甲基二硅氧烷溶解于一定量水中制备成浓度为5％、温度为70℃的溶液；将100份最大粒径≤5μm，d0.5为1μm的球形氧化硅粉体材料加入到偶联剂溶液中，强烈搅拌1.0小时后，过滤烘干获得表面改性的氧化硅粉体。
配制有机液相材料
将1.0份聚二甲基硅氧烷、1.0份聚乙二醇、2.0份丙烯酸流变改性剂依次加到96份聚氨酯丙烯酸树脂中并充分搅拌混合制得有机液相材料。
制备光敏氧化硅浆料
将75份经过表面改性的氧化硅粉体材料逐渐加入到25份预混的有机液相材料中，在真空搅拌机进行搅拌混合2.0小时，制备成为可用于光固化3D打印成型的光敏氧化硅陶瓷浆料。该浆料通过光固化3D打印工艺制备可以烧结为密实度为95％左右、结构复杂的氧化硅陶瓷制品。
实施例4
光固化3D打印高密实度碳化硅陶瓷用光敏陶瓷浆料的制备
碳化硅陶瓷粉体材料表面改性
将10份氨基硅烷偶联剂溶解于甲苯中；将100份最大粒径≤5μm，d0.5为500nm的碳化硅微粉加入到偶联剂溶液中，在90℃下搅拌5.0小时后，过滤烘干获得表面改性的碳化硅粉体。
配制有机液相材料
将1.0份聚二甲基硅油、1.0份聚乙二醇、1.0份丙烯酸流变改性剂依次加到97份聚氨酯丙烯酸树脂中并充分搅拌混合制得有机液相材料。
制备光敏碳化硅浆料
将85份经过表面改性的碳化硅粉体材料逐渐加入到15份预混的有机液相材料中，在真空搅拌机进行搅拌混合2.0小时，制备成为可用于光固化3D打印成型的光敏碳化硅陶瓷浆料。该浆料通过光固化3D打印工艺制备的可以烧结为密实度为97％左右、结构复杂的碳化硅陶瓷制品。
以上所述仅是本发明的优选实施方式，应当指出，对于本领域的普通技术人员来说，在不脱离本发明创造构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。

Claims (5)

1.一种光固化3D打印用高固相含量陶瓷浆料，其特征在于，按照质量份数，包括75-90份无机陶瓷粉体和10-25份有机液相材料；所述无机陶瓷粉体由氧化铝、氧化硅、氧化锆、碳化硅、氮化硅等一种或多种经过预先物理表面改性或化学表面改性的无机粉体材料组成；所述有机液相材料按照质量份数比，由以下原料组成：95-98.5份液态光敏树脂，0.5-2.0份悬浮分散剂、0.5-1.0份消泡剂，0.5-2.0份的流变改性剂。
2.根据权利要求1所述光固化3D打印用高固相含量陶瓷浆料，其特征在于，所述液态光敏树脂为环氧丙烯酸光敏树脂、聚氨酯丙烯酸树脂中的一种；所述悬浮分散剂为聚乙二醇、聚丙烯酸铵、改性氨基磺酸分散剂的一种或多种混合物；所述消泡剂为二甲基硅油、聚硅氧烷、聚二甲基硅氧烷、聚醚改性硅等的一种或多种混合物；所述流变改性剂为丙烯酸流变改性剂。
3.一种光固化3D打印用高固相含量陶瓷浆料的制备工艺，其特征在于，先对无机陶瓷粉体进行改性处理，再将无机陶瓷粉体加入到预混的有机液相材料中，在真空搅拌机进行搅拌混合0.5-2.0小时，制备成为可用于光固化3D打印成型的高固相含量陶瓷浆料；其中改性处理包括物理表面改性工艺或/和化学表面改性工艺。
4.根据权利要求3所述光固化3D打印用高固相含量陶瓷浆料的制备工艺，其特征在于，所述物理表面改性工艺，将无机粉体材料与浓度为1-10％的十二烷基硫酸钠、十二烷基苯磺酸钠、烷基酚聚氧乙烯醚、脂肪酸聚氧乙烯酯等一种或几种表面活性剂混合溶液进行充分混合，然后快速烘干；表面活性剂的用量为粉体材料质量的1.0-10.0％。
5.根据权利要求3所述光固化3D打印用高固相含量陶瓷浆料的制备工艺，其特征在于，所述化学表面改性工艺，将无机粉体材料加入浓度为1-10％硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂、硼酸酯偶联剂等一种或多种耦合剂的混合溶液中，在30-90℃下反应0.5-5.0小时，然后烘干；耦合剂的用量为粉体材料质量的1.0-10.0％。
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CN114750411A (zh) * 2022-06-16 2022-07-15 季华实验室 材料挤出式3d打印方法
CN115925445A (zh) * 2022-12-16 2023-04-07 辽宁省轻工科学研究院有限公司 3d打印用黑色氧化铝陶瓷粉体的改性方法
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CN116655358A (zh) * 2023-06-16 2023-08-29 江西金石三维智能制造科技有限公司 一种dlp用氧化铝微结构件材料及其制备方法

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