CN111943690A - 一种莫来石混合粉及其制备方法和在3d打印中的应用 - Google Patents

一种莫来石混合粉及其制备方法和在3d打印中的应用 Download PDF

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CN111943690A
CN111943690A CN202010827769.6A CN202010827769A CN111943690A CN 111943690 A CN111943690 A CN 111943690A CN 202010827769 A CN202010827769 A CN 202010827769A CN 111943690 A CN111943690 A CN 111943690A
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mullite
resin
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CN111943690B (zh
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洪小刚
李永红
武永明
张海宝
曾二龙
张亚明
耿刚强
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Shanxi Jiaoshe Geotechnical Engineering Co ltd
Xi'an Sipai New Material Technology Co ltd
Shanxi Expressway Engineering Testing Co ltd
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Xi'an Sipai New Material Technology Co ltd
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Abstract

本发明公开了一种莫来石混合粉及其制备方法和在3D打印中的应用，应用过程中，将混合莫来石粉3D通过分层水雾固化的方法，再通过实现莫来石块体复杂形状的3D打印成型，最终在高温下，利用高温反应粉与莫来石粉的反应，获得一定强度的多孔莫来石体。该方法采用3D打印结合烧结的方式，制备多孔莫来石晶体，通过控制3D打印粉中的组分差异，实现形状和性能参数的精准控制。在3D打印过程，采用水作为3D打印固化剂，成型方式简单、环保。

Description

一种莫来石混合粉及其制备方法和在3D打印中的应用
【技术领域】
本发明属于多孔莫来石结构技术领域，具体涉及一种莫来石混合粉及其制备方法和在3D打印中的应用。
【背景技术】
多孔莫来石结构因其具有较小的体积密度，良好的抗热震性，较低的热容和导热率，在高温隔热、过滤、催化、离子交换等领域具有广泛的应用。目前多孔莫来石结构常采用添加造孔剂、有机泡沫浸渍法、溶胶凝胶法等方法来制备。然而，制备工艺直接决定了多孔材料的空隙结构和孔隙率，从而对性能和应用产生一定的影响。在大规模应用中，常规的粗放性的生产，对莫来石结构的精准控制程度较差，使该系列产品通常无法应用于精度较高的领域。3D打印技术是新型的先进制造技术，可较好的实现莫来石多空材料的精准制备，实现材料各种复杂形状下的高可控性。而常规的3D打印陶瓷粉技术，是采用陶瓷粉制备的浆料，利用树脂的光固化实现层状打印，实现框架材料的成型，光固化树脂价格较高并且树脂基材料环保性能的缺点限制了该系列材料在3D打印领域的大范围应用。
【发明内容】
本发明的目的在于克服上述现有技术的缺点，提供一种莫来石混合粉及其制备方法和在3D打印中的应用，该方法用于解决现有技术中光固化成本较高且树脂基材料环保性能不佳的缺陷。
为达到上述目的，本发明采用以下技术方案予以实现：
一种莫来石混合粉，由莫来石粉、低温速凝粉和高温反应粉混合制成；所述低温速凝粉由普通硅酸盐水泥、双快水泥、氯化锂、氯化铝和氯化钠组成，所述高温反应粉包括锂、铝和硅基玻璃粉。
本发明的进一步改进在于：
优选的，按质量分数计，莫来石粉占比为70％～85％，低温速凝粉占比为5％～15％，高温反应粉占比为5％～15％。
优选的，按质量分数计，低温速凝粉中，普通硅酸盐水泥占比为50％～65％，双快水泥占比为10～20％，氯化锂占比为2～5％，氯化铝占比为1～8％，氯化钠占比为4～6％。
优选的，按质量分数计，高温反应粉中锂粉的质量占比为20％、铝粉的质量占比为10％和硅基玻璃粉质量占比为70％。
优选的，所述高温反应粉的粒径≤2μ粒。
一种莫来石混合粉的制备方法，将莫来石粉、低温速凝粉和高温反应粉混合后，得到混合粉，在混合粉加入树脂混合液搅拌后过筛，得到3D打印粉，为莫来石混合粉。
优选的，造粒过程中，所述树脂混合液的加入量为混合粉质量的3％。
优选的，造粒过程中，所述树脂混合液包括树脂和树脂稀释剂；树脂为酚醛树脂，环氧树脂，不饱和聚酯中的一种或几种；树脂稀释剂为树脂为酚醛树脂，环氧树脂，不饱和聚酯中的一种或几种。
一种上述的莫来石混合粉在3D打印中的应用，包括以下步骤，将莫来石混合粉分层铺粉，每铺一层粉通过细水雾进行喷淋固化，铺粉至设置高度；最后一层铺粉并固化后，进行烧结，得到烧结固化后的莫来石块体。
优选的，所述铺粉的设置厚度为300～600mm，每次喷水质量为一层铺粉质量2～3％；每次喷淋固化后等待40～70秒进行下一层的铺粉；所述烧结温度为800～950℃，烧结时间为30～60min。
与现有技术相比，本发明具有以下有益效果：
本发明公开了一种莫来石混合粉，该混合粉首次在莫来石粉中加入低温速凝粉和高温反应粉，使得该粉就别低温成型和高温固化的性能，使得该粉末能够应用大道3D打印中。此种粉可通过水进行快速固化，利用3D打印分层固化成型，制备复杂莫来石基结构。本发明提出3D打印莫来石混合粉通过自身组分的调整，可实现高精度3D打印莫来石多孔材料的成型，其过程采用水作为固化组分，展现出良好的环保效应。
本发明还公开了一种莫来石混合粉的制备方法，该制备方法采用莫来石粉，低温速凝粉，高温反应粉混合后，通过树脂造粒的方式，得到一定粒径的莫来石基3D打印粉，整个制备方法简单易得，易于扩大化生产，还具有环保、高效等优点。
本发明还公开了一种莫来石混合粉在3D打印中的应用，应用过程中，将混合莫来石粉3D通过分层水雾固化的方法，实现莫来石块体复杂形状的3D打印成型。莫来石多孔框架成型后，将莫来石多孔框架在高温下进行直接烧结，烧结过程中，高温反应粉会与莫来石粉之间发生原位烧结，将原有的低温粘结转变为高温的烧结结合，使基体中莫来石粉之间的结合强度大幅提升，获得良好使用强度的多孔莫来石体。该方法采用3D打印结合烧结的方式，制备多孔莫来石晶体，可在低温3D打印成型过程中实现莫来石坯体结构形状的精准控制，并在高温下实现原位烧结成型，可实现形状和性能参数的精准控制。在3D打印过程，采用水作为3D打印固化剂，成型方式简单、环保。
【附图说明】
图1为本发明的制备流程图。
【具体实施方式】
下面结合附图对本发明做进一步详细描述：
在本发明的描述中，需要说明的是，术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制；术语“第一”、“第二”、“第三”仅用于描述目的，而不能理解为指示或暗示相对重要性；此外，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以具体情况理解上述术语在本发明中的具体含义。
本发明公开了一种莫来石混合粉及其制备方法和在3D打印中的应用，是一种水基固化3D打印莫来石混合粉及3D打印方法，该方法包括以下步骤：
步骤1，混合并干燥
将含莫来石粉，低温速凝粉，高温反应粉按照质量比70％～85％，5％～15％和5％～15％混合，三者相加比例为100％，混合后在干燥箱中干燥24h以上，温度为80℃，制备成混合粉。
其中，莫来石粉为1500℃烧结保温2h后球磨得到的粉，粉的粒径为100～300μm，低温速凝粉是由普硅水泥，双快水泥，氯化锂，氯化铝，氯化钠组成的混合粉，其质量比分别为60～75％，10～20％，2～5％，1～8％，4～7％。
高温反应粉为是由金属锂、铝粉和硅粉混合组成，其中锂粉的质量占比为20％，铝粉的质量占比为10％，硅基玻璃粉的质量占比为70％，高温反应粉经过机械球磨之后，平均粒度不大于2μm。
步骤2，造粒形成3D打印粉
在上述干燥后的混合粉末中加入树脂复合液进行造粒，具体的过程为，将树脂和树脂稀释剂按照质量比等比例混合，制成树脂复合液，将树脂复合液喷撒至干燥后的混合粉末中，喷洒量为混合粉末质量的3％，喷入后搅拌均匀，将搅拌的浆料过100目筛，筛余颗粒为造粒后的3D打印粉。
树脂为酚醛树脂，环氧树脂，不饱和聚酯中的一种或几种，当为几种时，几种材料等质量比例混合，树脂采用丙酮、丁醇、乙二醇的一种或几种，当为几种时，几种材料等质量比例混合作为树脂稀释剂。
步骤3，将3D打印粉分层排布，分层厚度为200～600mm，每铺一层，将细水雾进行喷淋固化，喷水量为铺粉质量的2～3％。分层铺粉及水雾固化的间隔为40～70秒。成型后，将固化好的块体在马弗炉中进行烧结，烧结温度800～950℃，保温30～60min。得到烧结固化后的莫来石块体。
下面结合具体实施例对本发明进行进一步的解释。
实施例1：
莫来石粉，低温速凝粉，高温反应粉的比例分别为70％，15％，15％，莫来石粉为1500℃烧结后球磨得到的粉，粉的粒径为150μm。三种粉在混合之后均须在干燥箱中干燥24h以上，温度为80℃。低温速凝粉是由普硅水泥，双快水泥，氯化锂，氯化铝，氯化钠组成的混合粉，其比例组分分别为65％，20％，5％，3％，7％。高温反应粉是为锂-铝-硅基玻璃粉为主成分，其中铝的质量分数位15％。玻璃粉粒径2mm。莫来石混合粉，低温速凝粉，高温反应粉是通过树脂混合液进行造粒的，树脂为酚醛树脂，环氧树脂的复合树脂，稀释剂为用丙酮，将树脂混合液喷洒至干燥后的混合粉中，洒量为混合粉末质量的3％。3D打印粉经过薄层分层排布，分层厚度为300，粉经排布之后，每铺一层将细水雾进行喷淋固化，喷水量为粉量的2％。分层铺粉及水雾固化的间隔为55秒。成型后，将固化好的块体在马弗炉中进行烧结，烧结温度800℃，烧结时间为50min。得到烧结固化后的莫来石块体，烧结后抗压强度为4Mpa，孔隙率为45％。
实施例2
莫来石粉，低温速凝粉，高温反应粉的比例分别为75％，10％，15％，莫来石粉为1500℃烧结后球磨得到的粉，粉的粒径为230μm。三种粉在混合之后均须在干燥箱中干燥24h以上，温度为80℃。低温速凝粉是由普硅水泥，双快水泥，氯化锂，氯化铝，氯化钠组成的混合粉，其比例组分分别为75％，10％，5％，3％，7％。高温反应粉是为锂-铝-硅基玻璃粉为主成分，其中铝的质量分数位18％。玻璃粉粒径0.5μm。莫来石混合粉，低温速凝粉，高温反应粉是通过树脂混合液进行造粒的，树脂为酚醛树脂，环氧树脂的复合树脂，稀释剂为用丙酮，将树脂混合液喷洒至干燥后的混合粉中，洒量为混合粉末质量的3％。3D打印粉经过薄层分层排布，分层厚度为400，粉经排布之后，将细水雾进行喷淋固化，喷水量为粉量的2.5％。分层铺粉及水雾固化的间隔为50秒。成型后，将固化好的块体在马弗炉中进行烧结，烧结温度850℃，烧结时间为40min。得到烧结固化后的莫来石块体，烧结后抗压强度为8Mpa，孔隙率为39％。
实施例3
(3)莫来石粉，低温速凝粉，高温反应粉的比例分别为80％，10％，10％，莫来石粉为1500℃烧结后球磨得到的粉，粉的粒径为230μm。三种粉在混合之后均须在干燥箱中干燥24h以上，温度为80℃。低温速凝粉是由普硅水泥，双快水泥，氯化锂，氯化铝，氯化钠组成的混合粉，其比例组分分别为73％，15％，4％，3％，5％。高温反应粉是为锂-铝-硅基玻璃粉为主成分，其中铝的质量分数位13％。玻璃粉粒径1μm莫来石混合粉，低温速凝粉，高温反应粉是通过树脂混合液进行造粒的，树脂为酚醛树脂，环氧树脂的复合树脂，稀释剂为用丙酮，将树脂混合液喷洒至干燥后的混合粉中，洒量为混合粉末质量的3％。3D打印粉经过薄层分层排布，分层厚度为400，粉经排布之后，将细水雾进行喷淋固化，喷水量为粉量的3％。分层铺粉及水雾固化的间隔为45秒。成型后，将固化好的块体在马弗炉中进行烧结，烧结温度900℃，烧结时间为60min。得到烧结固化后的莫来石块体，烧结后抗压强度为11Mpa，孔隙率为31％。
实施例4
莫来石粉，低温速凝粉，高温反应粉的比例分别为85％，10％，15％，莫来石粉为1500℃烧结后球磨得到的粉，粉的粒径为300μm。三种粉在混合之后均须在干燥箱中干燥24h以上，温度为80℃。低温速凝粉是由普硅水泥，双快水泥，氯化锂，氯化铝，氯化钠组成的混合粉，其比例组分分别为75％，15％，3％，2％，5％。高温反应粉是为锂-铝-硅基玻璃粉为主成分，其中铝的质量分数位13％。玻璃粉粒径0.8μm莫来石混合粉，低温速凝粉，高温反应粉是通过树脂混合液进行造粒的，树脂为酚醛树脂，环氧树脂的复合树脂，稀释剂为用丙酮，将树脂混合液喷洒至干燥后的混合粉中，洒量为混合粉末质量的3％。3D打印粉经过薄层分层排布，分层厚度为200，粉经排布之后，将细水雾进行喷淋固化，喷水量为粉量的2.8％。分层铺粉及水雾固化的间隔为40秒。成型后，将固化好的块体在马弗炉中进行烧结，烧结温度950℃，烧结时间为30min。得到烧结固化后的莫来石块体，烧结后抗压强度为15Mpa，孔隙率为23％。
实施例4-实施例10详见下表，下述实施例中未提及的部分均与实施例1相同。
表1实施例4-实施例10
Figure BDA0002636850760000071
Figure BDA0002636850760000081
在低温成型和高温烧结两个阶段分别得到了不同的烧结体。在3D打印固化后，制品形状完整。在烧结处理后，实现原位成型，尺寸未发生明显变化。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种莫来石混合粉，其特征在于，由莫来石粉、低温速凝粉和高温反应粉混合制成；所述低温速凝粉由普通硅酸盐水泥、双快水泥、氯化锂、氯化铝和氯化钠组成，所述高温反应粉包括锂、铝和硅基玻璃粉。
2.根据权利要求1所述的一种莫来石混合粉，其特征在于，按质量分数计，莫来石粉占比为70％～85％，低温速凝粉占比为5％～15％，高温反应粉占比为5％～15％。
3.根据权利要求1所述的一种莫来石混合粉，其特征在于，按质量分数计，低温速凝粉中，普通硅酸盐水泥占比为50％～65％，双快水泥占比为10～20％，氯化锂占比为2～5％，氯化铝占比为1～8％，氯化钠占比为4～6％。
4.根据权利要求1所述的一种莫来石混合粉，其特征在于，按质量分数计，高温反应粉中锂粉的质量占比为20％、铝粉的质量占比为10％和硅基玻璃粉质量占比为70％。
5.根据权利要求1所述的一种莫来石混合粉，其特征在于，所述高温反应粉的粒径≤2μ粒。
6.一种莫来石混合粉的制备方法，其特征在于，将莫来石粉、低温速凝粉和高温反应粉混合后，得到混合粉，在混合粉加入树脂混合液搅拌后过筛，得到3D打印粉，为莫来石混合粉。
7.根据权利要求6所述的一种莫来石混合粉的制备方法，其特征在于，造粒过程中，所述树脂混合液的加入量为混合粉质量的3％。
8.根据权利要求6所述的一种莫来石混合粉的制备方法，其特征在于，造粒过程中，所述树脂混合液包括树脂和树脂稀释剂；树脂为酚醛树脂，环氧树脂，不饱和聚酯中的一种或几种；树脂稀释剂为树脂为酚醛树脂，环氧树脂，不饱和聚酯中的一种或几种。
9.一种权利要求1所述的莫来石混合粉在3D打印中的应用，其特征在于，包括以下步骤，将莫来石混合粉分层铺粉，每铺一层粉通过细水雾进行喷淋固化，铺粉至设置高度；最后一层铺粉并固化后，进行烧结，得到烧结固化后的莫来石块体。
10.根据权利要求9所述的莫来石混合粉在3D打印中的应用，其特征在于，所述铺粉的设置厚度为300～600mm，每次喷水质量为一层铺粉质量2～3％；每次喷淋固化后等待40～70秒进行下一层的铺粉；所述烧结温度为800～950℃，烧结时间为30～60min。
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