CN108298965A - 一种采用直写成型技术制备多级孔材料的方法 - Google Patents

一种采用直写成型技术制备多级孔材料的方法 Download PDF

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CN108298965A
CN108298965A CN201810022768.7A CN201810022768A CN108298965A CN 108298965 A CN108298965 A CN 108298965A CN 201810022768 A CN201810022768 A CN 201810022768A CN 108298965 A CN108298965 A CN 108298965A
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CN108298965B (zh
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王小锋
于凯
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Wenchang Huiwen Xinbo Rui Information Technology Center
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Abstract

本发明属于3D打印成型技术领域，公开了一种采用直写成型技术制备多级孔材料的方法，即首先制备粉体浆料，然后再在该浆料中添加一种或多种乳化剂，并通过乳化调节浆料的流变性能，最后采用该浆料制备多级孔材料。本发明既能够调节粉体浆料的流变性能使之符合直写成型技术的要求，又能够符合3D打印成型多级孔材料，本发明还可简便地调节多级孔材料的孔径、孔容和孔隙度。

Description

一种采用直写成型技术制备多级孔材料的方法
技术领域
本发明属于3D打印成型技术领域，具体涉及一种采用直写成型技术制备多级孔材料的方法。
背景技术
多孔材料因其热导率低、介电常数低、比表面积大、强度高、耐磨损、耐高温、抗腐蚀等一系列优良特性，广泛应用于环保、能源、化工、生物等领域。多孔材料按孔径大小可分为微孔材料(<2nm）、介孔材料(2nm ~ 50 nm)和大孔材料(>50nm)。多级孔材料是同时含有微孔、介孔或大孔等不同等级孔洞的材料。多级孔材料的孔径依次由大到小逐级分布，且每一级的孔道结构是由低一级别的孔道结构构成的孔材料。近十多年来，多级孔材料受到广泛关注，发展迅速，从纳米科学到能源、催化、分离和生命科学，其合成与应用已经成为多孔材料领域新的研究热点。
目前，多级孔材料的制备方法有聚合物模板法、胶态晶体模板法、仿生法、超临界干燥法、冷冻浇注法、自主装法和发泡法等多种。这些方法可以通过控制孔径、孔形、孔容以及联通性等，设计并合成满足特定应用需求的多级孔结构。尽管多级孔材料在合成方面取得了一定的进展，但是诸如多级孔的可控性、孔结构联通性和产品质量稳定性等与实际应用密切相关的问题对多级孔材料的研究仍然存在着巨大的挑战。
3D打印成型技术如选择性激光烧结成型、熔融成型、光固化成型和直写成型等技术，在材料结构设计、控制和快速成型等方面具有巨大的优势。其中，直写成型技术（DirectInk Writing）因其设备成本较低、成型结构优良和普适性好等优势已成为当前的研究热点。直写成型技术的关键在于获得即满足挤出时低粘度（流动）又满足挤出后高粘弹性（失去流动）的直写成型用浆料。
发明内容
本发明的目的在于提供一种采用直写成型技术制备多级孔材料的方法，以克服现有技术中的问题。
为实现上述目的，本发明提供如下技术方案：
本申请公开了一种采用直写成型技术制备多级孔材料的方法， 其包括如下步骤：
（1）将一定比例的溶剂、粉体和分散剂进行混合，制得合适的粘度和固含量的浆料，其中，所述溶剂为去离子水，固含量为0.01 wt.%~80 wt.%，分散剂加入量为0.01 wt.% ~ 10wt.%；
（2）在（1）中获得的粉体浆料中添加乳化剂后，球磨0.1~24h，静置1~7d，然后高速搅拌使浆料乳化，得到乳化粉体浆料，其中，乳化剂加入量为0.01 wt.%~50 wt.%，搅拌速度为100 rad/min-10000 rad/min；
（3）设计三维立体结构，并编写直写打印成型，通过逐层叠加的方式，将乳化粉体浆料直写打印成型，获得多级孔材料胚体；
（4）将直写打印成型的多级孔材料坯体浸入油性液体中，浸泡0.1~300h，随后在控制温度和湿度的条件下进行干燥，然后将胚体置于排胶烧结炉内进行排胶、烧结，最终得到多级孔材料。
进一步地，所述步骤（1）中的所述粉体为氧化铝粉体、ZrO2粉体、AlN粉体中一种。
进一步地，所述步骤（1）中的所述分散剂为阴离子型分散剂、阳离子型分散剂中一种。
进一步地，所述步骤（1）中还包括烧结助剂MgO、烧结助剂Y2O3、烧结助剂La2O3中一种或多种。
进一步地，所述步骤（2）中的所述乳化剂包括丁酸单双甘油酯、丁酸、二羟甲基丁酸中一种或多种。
进一步地，所述步骤（3）中的打印成型的工艺参数为，压力范围为1~1000PSI，打印头移动速度为0.01~500mm/sec，成型温度范围为20~40℃，成型湿度范围为＞60%。
进一步地，所述步骤（4）中的具体的是将成型的坯体放入油性液体中浸渍0.1~300h，再置于湿度为＞60%，温度为60~72℃的条件下干燥12~28小时；再将坯体置于排胶烧结炉内，以0.5~1.5℃/min的升温速率升至600~700℃保温2~4小时进行排胶，然后继续以5~10℃/min的升温速率升至1450~1600℃烧结2~3小时。
进一步地，所述步骤（4）中的所述油性液体包括菜油、蓖麻油、液体石蜡、煤油、汽油。
与现有技术相比，本发明是一种新颖、简便地采用直写成型技术制备多级孔材料的方法，其优点在于：
1、粉体浆料的流变性能通过乳化法简单、便捷的调控即可满足直写成型的要求；
2、采用本发明的粉体浆料进行直写成型时，不容易发生堵嘴等现象，利于直写成型工艺的控制；
3、本发明制备的多级孔材料的孔径、孔容、孔隙度均可简便地调节；
4、本发明不受材料体系的限制，适用范围广，通过乳化条件可控制多级孔材料中的介孔或微孔，通过3D打印成型结构的设计和工艺条件控制多级孔材料中的大孔。
具体实施方式
下面将对本发明实施例中的技术方案进行详细的描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
制备ZrO2多级孔材料的步骤如下：
（1）将分散剂聚丙烯酸钠（5g）和YSZ（3摩尔Y2O3稳定的ZrO2）粉体（260g，D50为0.8μm）加入到50mL去离子水中进行球磨12h，然后加入乳化剂丁酸单双甘油酯（10g）球磨5h，静置24h，再高速剪切乳化10min，获得乳化的ZrO2浆料。其中，磨球为300g的氧化锆球，球磨速度为15 rad/min，剪切速度为1000 rad/min；
（2）将获得的ZrO2乳化浆料进行直写成型多级孔材料坯体。温度控制为30℃左右，湿度控制为65%。直写成型压力为30PSI；打印头移动速度为12mm/sec；
（3）将成型的坯体放入煤油中浸渍24h，再置于湿度为60%，温度为70℃的条件下干燥12小时；再将坯体置于排胶烧结炉内，以1.5℃/min的升温速率升至700℃保温3小时进行排胶，然后继续以6℃/min的升温速率升至1450℃烧结3小时。
实施例2
制备Al2O3多级孔材料的步骤如下：
（1）将聚丙烯酸（6g）和Al2O3粉体（320g，D50为0.8μm）、烧结助剂MgO（3.2g）加入到120mL去离子水中进行球磨20小时，然后加入乳化剂丁酸（5g）球磨10h，静置2d，再高速剪切乳化15min，获得乳化的Al2O3浆料。其中，磨球为350g的氧化铝球，球磨速度为20 rad/min，剪切速度为800 rad/min；
（2）将乳化Al2O3浆料进行直写成型，获得多级孔材料坯体。温度控制为23℃左右，湿度控制为70%。直写成型压力为50PSI；打印头移动速度为10mm/sec；
（3）将成型的坯体放入柴油中浸渍30h，再置于湿度为63%，温度为65℃的条件下干燥20小时；再将坯体置于排胶烧结炉内，以1℃/min的升温速率升至600℃保温2小时进行排胶，然后继续以5℃/min的升温速率升至1550℃烧结2小时。
实施例3
制备AlN多级孔材料的步骤如下：
（1）将聚丙烯酸铵（8g）和AlN粉体（350g，D50为2μm）烧结助剂Y2O3（3g）与La2O3（2.1g）加入到100mL去离子水中进行球磨18小时，然后加入乳化剂二羟甲基丁酸（2g）球磨10小时，静置2d，再高速剪切乳化15min，获得乳化的AlN浆料。其中，磨球为500g的氧化锆球，球磨速度为12 rad/min，剪切速度为2000rad/min；
（2）将获乳化AlN浆料进行直写成型，获得多级孔材料坯体。温度控制为32℃左右，湿度控制为76%。直写成型压力为40PSI；打印头移动速度为120mm/sec；
（3）将成型的坯体放入菜油中浸渍36h，再置于湿度为82%，温度为62℃的条件下干燥38小时；再将坯体置于真空排胶烧结炉内，以0.8℃/min的升温速率升至650℃保温4小时进行排胶，然后继续以7℃/min的升温速率升至1580℃真空烧结3小时。
实施例4
制备ZrO2多级孔材料的步骤如下：
（1）将分散剂聚丙烯酸钠（8g）和YSZ（3摩尔Y2O3稳定的ZrO2）粉体（300g，D50为0.8μm）加入到100mL去离子水中进行球磨8h，然后加入乳化剂丁酸（12g）球磨6h，静置48h，再高速剪切乳化20min，获得乳化的ZrO2浆料。其中，磨球为600g的氧化锆球，球磨速度为20 rad/min，剪切速度为2000 rad/min；
（2）将获得的ZrO2乳化浆料进行直写成型多级孔材料坯体。温度控制为23℃左右，湿度控制为60%。直写成型压力为50PSI；打印头移动速度为35mm/sec；
（3）将成型的坯体放入汽油中浸渍48h，再置于湿度为64%，温度为72℃的条件下干燥18小时；再将坯体置于排胶烧结炉内，以1℃/min的升温速率升至600℃保温4小时进行排胶，然后继续以5℃/min的升温速率升至1480℃烧结3小时。
实施例5
制备Al2O3多级孔材料的步骤如下：
（1）将聚丙烯酸（18g）和Al2O3粉体（400g，D50为0.8μm）、烧结助剂MgO（4g）加入到150mL去离子水中进行球磨22小时，然后加入乳化剂二羟甲基丁酸（10g）球磨8h，静置1d，再高速剪切乳化20min，获得乳化的Al2O3浆料。其中，磨球为500g的氧化铝球，球磨速度为40 rad/min，剪切速度为3000 rad/min；
（2）将乳化Al2O3浆料进行直写成型，获得多级孔材料坯体。温度控制为25℃左右，湿度控制为65%。直写成型压力为80PSI；打印头移动速度为50mm/sec；
（3）将成型的坯体放入液体石蜡中浸渍24h，再置于湿度为73%，温度为60℃的条件下干燥48小时；再将坯体置于排胶烧结炉内，以0.5℃/min的升温速率升至700℃保温2小时进行排胶，然后继续以8℃/min的升温速率升至1560℃烧结2小时。
实施例6
制备AlN多级孔材料的步骤如下：
（1）将聚丙烯酸铵（10g）和AlN粉体（450g，D50为2μm）烧结助剂Y2O3（5g）加入到150mL去离子水中进行球磨20小时，然后加入乳化剂丁酸单双甘油酯（8g）球磨5小时，静置2d，再高速剪切乳化20min，获得乳化的AlN浆料。其中，磨球为500g的氧化锆球，球磨速度为10 rad/min，剪切速度为4000rad/min；
（2）将获乳化AlN浆料进行直写成型，获得多级孔材料坯体。温度控制为30℃左右，湿度控制为78%。直写成型压力为100PSI；打印头移动速度为140mm/sec；
（3）将成型的坯体放入蓖麻油中浸渍48h，再置于湿度为80%，温度为60℃的条件下干燥48小时；再将坯体置于真空排胶烧结炉内，以1℃/min的升温速率升至630℃保温3小时进行排胶，然后继续以10℃/min的升温速率升至1600℃真空烧结2小时。
基于前期针对高固含量、低粘度的浆料相关的基础研究工作，我们降低浆料的固含量，同时添加乳化剂，获得了满足直写成型要求的乳化陶瓷颗粒浆料。本发明将该浆料用于直写成型技术并合成多级孔材料。本发明采用3D打印成型技术控制多级孔材料中的大孔，同时采用乳化法控制多级孔材料中的介孔或微孔，从而解决多级孔材料合成中的可控性、联通性和稳定性等问题。
需要说明的是，在本文中，诸如术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括一个……”限定的要素，并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。
以上所述仅是本申请的具体实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本申请的保护范围。

Claims (8)

1.一种采用直写成型技术制备多级孔材料的方法，其特征在于，其包括如下步骤：
（1）将一定比例的溶剂、粉体和分散剂进行混合，制得合适的粘度和固含量的浆料，其中，所述溶剂为去离子水，固含量为0.01 wt.%~80 wt.%，分散剂加入量为0.01 wt.% ~ 10wt.%；
（2）在（1）中获得的粉体浆料中添加乳化剂后，球磨0.1~24h，静置1~7d，然后高速搅拌使浆料乳化，得到乳化粉体浆料，其中，乳化剂加入量为0.01 wt.%~50 wt.%，搅拌速度为100 rad/min-10000 rad/min；
（3）设计三维立体结构，并编写直写打印成型，通过逐层叠加的方式，将乳化粉体浆料直写打印成型，获得多级孔材料胚体；
（4）将直写打印成型的多级孔材料坯体浸入油性液体中，浸泡0.1~300h，随后在控制温度和湿度的条件下进行干燥，然后将胚体置于排胶烧结炉内进行排胶、烧结，最终得到多级孔材料。
2.根据权利要求1所述的一种采用直写成型技术制备多级孔材料的方法，其特征在于，所述步骤（1）中的所述粉体为氧化铝粉体、ZrO2粉体、AlN粉体中一种。
3.根据权利要求1所述的一种采用直写成型技术制备多级孔材料的方法，其特征在于，所述步骤（1）中的所述分散剂为阴离子型分散剂、阳离子型分散剂中一种。
4.根据权利要求1所述的一种采用直写成型技术制备多级孔材料的方法，其特征在于，所述步骤（1）中还包括烧结助剂MgO、烧结助剂Y2O3、烧结助剂La2O3中一种或多种。
5.根据权利要求1所述的一种采用直写成型技术制备多级孔材料的方法，其特征在于，所述步骤（2）中的所述乳化剂包括丁酸单双甘油酯、丁酸、二羟甲基丁酸中一种或多种。
6.根据权利要求1所述的一种采用直写成型技术制备多级孔材料的方法，其特征在于，所述步骤（3）中的打印成型的工艺参数为，压力范围为1~1000PSI，打印头移动速度为0.01~500mm/sec，成型温度范围为20~40℃，成型湿度范围为＞60%。
7.根据权利要求1所述的一种采用直写成型技术制备多级孔材料的方法，其特征在于，所述步骤（4）中的具体的是将成型的坯体放入油性液体中浸渍0.1~300h，再置于湿度为＞60%，温度为60~72℃的条件下干燥12~28小时；再将坯体置于排胶烧结炉内，以0.5~1.5℃/min的升温速率升至600~700℃保温2~4小时进行排胶，然后继续以5~10℃/min的升温速率升至1450~1600℃烧结2~3小时。
8.根据权利要求1所述的一种采用直写成型技术制备多级孔材料的方法，其特征在于，所述步骤（4）中的所述油性液体为菜油、蓖麻油、液体石蜡、煤油、汽油中一种。
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