CN107500802B - 一种氮化硅陶瓷浆料和多孔氮化硅陶瓷的制备方法 - Google Patents
一种氮化硅陶瓷浆料和多孔氮化硅陶瓷的制备方法 Download PDFInfo
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Abstract
本申请属于3D打印技术领域,具体涉及一种氮化硅陶瓷浆料和多孔氮化硅陶瓷的制备方法。本发明所提供的氮化硅陶瓷浆料包括:聚氮硅烷液体30份、氮化硅粉体14.5~83份、烧结助剂2.5~9份、光固化树脂7~40份、光引发剂0.2~0.6份和分散剂0~0.9份。本发明还提供了一种多孔氮化硅陶瓷的制备方法,包括:将上述氮化硅陶瓷浆料依次进行光固化成型、脱脂、烧结。采用本发明方案得到的多孔氮化硅陶瓷气孔率和气孔大小可控,气孔均匀排布,尺寸精度高,成型效率高,制备工艺简单优化,可促进多孔氮化硅陶瓷在医疗、化工、电子等领域的应用。
Description
技术领域
本发明属于3D打印技术领域,具体涉及一种氮化硅陶瓷浆料和多孔氮化硅陶瓷的制备方法。
背景技术
氮化硅因其具有优异的综合机械性能,良好的高温力学性能、热稳定性、和抗热震性等,一直受到人们的广泛关注。多孔氮化硅陶瓷材料是当前研究热点,多孔氮化硅陶瓷具有高气孔率、低介电常数、介电性能优异等特点,在航天航空等领域发挥着特殊作用。
目前主要制备多孔陶瓷的方法主要有添加造孔剂和凝胶注模法等,如中国专利ZL201110366340.2(多孔氮化硅陶瓷及其制备方法)公布了一种以硅粉和氮化硅粉为原料通过自蔓延法制备多孔氮化硅陶瓷的方法;中国专利ZL201410095989.9(一种多孔氮化硅陶瓷的制备方法)公布了一种融合凝胶注模耦合添加造孔剂法制备多孔氮化硅陶瓷的方法;中国专利ZL201510761777.4(一种凝胶注模成型制备微多孔氮化硅陶瓷的方法)公布了一种凝胶注模成型制备微多孔氮化硅陶瓷的方法。
然而,上述方法存在多种问题:添加造孔剂的工艺气孔率较低,气孔分布不均匀,发泡工艺条件复杂难控制;凝胶注模法的成本高,零件形状有限,无法实现复杂形状的制备。
发明内容
为了解决上述技术问题,本发明的目的在于提供一种氮化硅陶瓷浆料和多孔氮化硅陶瓷的制备方法。
本发明的具体技术方案如下:
一种氮化硅陶瓷浆料,包括以下重量组份:
优选的,所述烧结助剂为MgO、Al2O3和Re2O3中的一种或多种;
其中,Re2O3=Y2O3、La2O3、Ce2O3、Pr2O3、Nd2O3、Pm2O3、Sm2O3、Eu2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Er2O3或Tm2O3。
优选的,所述光固化树脂选自1,6-己二醇二丙烯酸酯、季戊四醇四丙烯酸酯、甲基丙烯酸羟乙酯、季戊四醇三丙烯酸酯和三羟甲基丙烷三丙烯酸酯中的一种或多种。
优选的,所述光引发剂选自2-羟基-2-甲基-1-苯基-1-丙酮、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、(2,4,6-三甲基苯甲酰基)二苯基氧化膦和2-异丙基硫杂蒽酮中的一种或多种。
本发明还提供了一种多孔氮化硅陶瓷的制备方法,包括以下步骤:
a)将上述氮化硅陶瓷浆料进行光固化成型,得到成型坯体;在所述光固化成型中,控制单层厚度为20~100μm,曝光量为30~400mJ/cm2;
b)将所述成型坯体进行加热脱脂,得到脱脂坯体;
c)将所述脱脂坯体进行烧结,得到所述多孔氮化硅陶瓷;
其中,所述烧结包括:在保护气氛条件下,将所述脱脂坯体以5℃/min的升温速率升温至800℃,接着以0.5~3℃/min的升温速率升温至1400~1800℃保温1~5h。
优选的,所述加热脱脂包括:
在真空或保护气氛条件下,将所述成型坯体以0.5~2℃/min的升温速率升温至280℃并保温1~3h,接着以1~2℃/min的速率升温至600℃并保温1~3h,再以0.5~2℃/min的速率升温至800~1000℃并保温1~5h,得到所述脱脂坯体;
优选的,步骤c)在0.1-200MPa的气压下进行。
优选的,所述保护气氛为氨气气氛、氮气气氛或氩气气氛。
综上所述,本发明所提供的氮化硅陶瓷浆料包括:聚氮硅烷液体30份、氮化硅粉体14.5~83份、烧结助剂2.5~9份、光固化树脂7~40份、光引发剂0.2~0.6份和分散剂0~0.9份。本发明还提供了一种多孔氮化硅陶瓷的制备方法,包括:将上述氮化硅陶瓷浆料依次进行光固化成型、脱脂、烧结。采用本发明方案得到的多孔氮化硅陶瓷气孔率和气孔大小可控,气孔均匀排布,尺寸精度高,成型效率高,制备工艺简单优化,可促进多孔氮化硅陶瓷在医疗、化工、电子等领域的应用。
具体实施方式
为了解决传统多孔氮化硅陶瓷制备技术中,无法精确控制多孔氮化硅陶瓷的气孔率,其气孔分布不均匀,而且工艺复杂,也无法实现形状复杂的多孔氮化硅陶瓷零件的制备等技术缺陷。本发明人在做了多种尝试之后,独创性地采用光固化成型技术制备多孔氮化硅陶瓷。
采用光固化成型技术制备多孔氮化硅陶瓷具有多种问题:与常规氧化物陶瓷相比,氮化硅陶瓷的表面特性较为复杂,不容易制备高固相含量、低粘度的陶瓷浆料,具有成型困难和造孔困难的问题;而且其固化深度浅,难以得到合适的单层固化厚度。本发明通过优化的浆料配方,选择合适的热解脱脂烧结工艺(前驱体热解过程中有气体产生,从而形成孔隙),并结合光固化成型技术制备得到具有复杂形状、气孔率合适、气孔分布均匀的氮化硅多孔陶瓷。
下面将结合本发明实施例,对本发明的技术方案进行清楚、完整地描述,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。
以下实施例中所采用的BYK-9076、BYK-163和BYK-9077均属于德国毕克助剂系列,BYK-9076为高分子量共聚物烷基铵盐,BYK-9077为含亲和基团的高分子量共聚物,BYK-163为含亲和基团的高分子量嵌段共聚物溶液。
实施例1
(1)制备浆料:将30g聚氮硅烷液体、50g氮化硅粉体和3g烧结助剂混合,然后加入10g光固化树脂和0.5g光引发剂并置于球磨机中球磨混合,得浆料1。
在本实施例中,光固化树脂为1,6-己二醇二丙烯酸酯(HDDA)和季戊四醇四丙烯酸酯(PETTA)的混合物,其混合质量比为1:1;
烧结助剂为Al2O3和Ce2O3,混合质量比为1:1;
光引发剂为苯基双(2,4,6-三甲基苯甲酰基)氧化膦(819)。
(2)成型:将浆料1置于光固化成型设备中并进行光固化处理,按照预设模型形状得到成型坯体1。
在本实施例中,控制单层厚度为20μm,曝光量为200mJ/cm2。
(3)脱脂烧结:将成型坯体1置于氨气气氛中,以0.5℃/min的速率升温至280℃并保温3h,接着以1℃/min的速率升温至600℃并保温3h,再以0.5℃/min的速率升温至1000℃并保温5h,得到脱脂坯体1;
将脱脂坯体1置于氩气环境中,气压为0.1MPa,以5℃/min的速率升温至800℃,然后以1℃/min升温至1400℃并保温2h,再以1℃/min降温至800℃后随炉冷却,得多孔氮化硅陶瓷1,气孔率为60~80%。
实施例2
(1)制备浆料:将30g聚氮硅烷液体、83g氮化硅粉体和9g烧结助剂混合,然后加入40g光固化树脂、0.6g光引发剂和0.9g分散剂并置于球磨机中球磨混合,得浆料2。
在本实施例中,光固化树脂为1,6-己二醇二丙烯酸酯(HDDA)和季戊四醇四丙烯酸酯(PETTA)的混合物,其混合质量比为2:1;
烧结助剂为Al2O3和Ce2O3,混合质量比为1:1;
光引发剂为(2,4,6-三甲基苯甲酰基)二苯基氧化膦(TPO);
分散剂为BYK163。
(2)成型:将浆料2置于光固化成型设备中并进行光固化处理,按照预设模型形状得到成型坯体2。
在本实施例中,控制单层厚度为20μm,曝光量为120mJ/cm2。
(3)脱脂烧结:将成型坯体2置于氮气气氛中,以2℃/min的速率升温至280℃并保温3h,接着以0.5℃/min的速率升温至600℃并保温3h,再以0.5℃/min的速率升温至1000℃并保温5h,得到脱脂坯体2;
将脱脂坯体2置于氮气环境中,气压为10MPa,以5℃/min的速率升温至800℃,然后以2℃/min升温至1800℃并保温2.5h,再以2℃/min降温至800℃后随炉冷却,得多孔氮化硅陶瓷2,气孔率为5~20%。
实施例3
(1)制备浆料:将30g聚氮硅烷液体、14.5g氮化硅粉体和2.5g烧结助剂混合,然后加入7g光固化树脂、0.2g光引发剂和0.2g分散剂并置于球磨机中球磨混合,得浆料3。
在本实施例中,光固化树脂为三羟甲基丙烷三丙烯酸酯(TMPTA)、季戊四醇三丙烯酸酯(PETA)的混合物,其混合质量比为3:1;
烧结助剂为Al2O3和La2O3,混合质量比为1:2;
光引发剂为819;
分散剂为BYK163和BYK9077,混合质量比为1:1。
(2)成型:将浆料3置于光固化成型设备中并进行光固化处理,按照预设模型形状得到成型坯体3。
在本实施例中,控制单层厚度为50μm,曝光量为300mJ/cm2。
(3)脱脂烧结:将成型坯体3置于空气中,以1℃/min的速率升温至280℃并保温2h,接着以1℃/min的速率升温至600℃并保温2h,再以1℃/min的速率升温至900℃并保温3h,得到脱脂坯体3;
将脱脂坯体3置于氨气环境中,气压为5MPa,以5℃/min的速率升温至800℃,然后以2℃/min升温至1750℃并保温2.5h,再以2℃/min降温至800℃后随炉冷却,得多孔氮化硅陶瓷3,气孔率为50~70%。
实施例4
(1)制备浆料:将30g聚氮硅烷液体、36.9g氮化硅粉体和4.1g烧结助剂混合,然后加入10g光固化树脂、0.2g光引发剂和0.4g分散剂并置于球磨机中球磨混合,得浆料4。
在本实施例中,光固化树脂为1,6-己二醇二丙烯酸酯(HDDA)、季戊四醇四丙烯酸酯(PETTA)的混合物,其混合质量比为4:1;
烧结助剂为Al2O3和Lu2O3,混合质量比为1:2;
光引发剂为2-羟基-2-甲基-1-苯基-1-丙酮(1173);
分散剂为BYK9076。
(2)成型:将浆料4置于光固化成型设备中并进行光固化处理,按照预设模型形状得到成型坯体4。
在本实施例中,控制单层厚度为50μm,曝光量为300mJ/cm2。
(3)脱脂烧结:将成型坯体4置于氮气中,以1℃/min的速率升温至280℃并保温3h,接着以2℃/min的速率升温至600℃并保温3h,再以1.5℃/min的速率升温至900℃并保温3h,得到脱脂坯体4;
将脱脂坯体4置于氨气环境中,气压为0.1MPa,以5℃/min的速率升温至800℃,然后以1℃/min升温至1750℃并保温3h,再以1℃/min降温至800℃后随炉冷却,得多孔氮化硅陶瓷4,气孔率为40~50%。
实施例5
(1)制备浆料:将30g聚氮硅烷液体、27g氮化硅粉体和3g烧结助剂混合,然后加入20g光固化树脂、0.2g光引发剂和0.3g分散剂并置于球磨机中球磨混合,得浆料5。
在本实施例中,光固化树脂为1,6-己二醇二丙烯酸酯(HDDA)、季戊四醇四丙烯酸酯(PETTA)的混合物,其混合质量比为4:1;
烧结助剂为Al2O3和Nd2O3,混合质量比为1:1;
光引发剂为2-异丙基硫杂蒽酮(ITX);
分散剂为BYK9067。
(2)成型:将浆料5置于光固化成型设备中并进行光固化处理,按照预设模型形状得到成型坯体5。
在本实施例中,控制单层厚度为100μm,曝光量为350mJ/cm2。
(3)脱脂烧结:将成型坯体5置于氨气中,以1℃/min的速率升温至280℃并保温2h,接着以1℃/min的速率升温至600℃并保温3h,再以0.5℃/min的速率升温至1000℃并保温5h,得到脱脂坯体5;
将脱脂坯体5置于氩气环境中,气压为1MPa,以5℃/min的速率升温至800℃,然后以2℃/min升温至1750℃并保温1h,再以2℃/min降温至800℃后随炉冷却,得多孔氮化硅陶瓷5,气孔率为30~40%。
实施例6
(1)制备浆料:将30g聚氮硅烷液体、61.75g氮化硅粉体和3.25g烧结助剂混合,然后加入35g光固化树脂、0.6g光引发剂和0.6g分散剂并置于球磨机中球磨混合,得浆料6。
在本实施例中,光固化树脂为1,6-己二醇二丙烯酸酯(HDDA)、季戊四醇四丙烯酸酯(PETTA)的混合物,其混合质量比为4:1;
烧结助剂为MgO;
光引发剂为819和TPO,混合质量比为1:1;
分散剂为BYK9077和BYK9076,混合质量比为1:1。
(2)成型:将浆料6置于光固化成型设备中并进行光固化处理,按照预设模型形状得到成型坯体6。
在本实施例中,控制单层厚度为20μm,曝光量为200mJ/cm2。
(3)脱脂烧结:将成型坯体6置于氨气中,以1.5℃/min的速率升温至280℃并保温2.5h,接着以1℃/min的速率升温至600℃并保温2.5h,再以1.5℃/min的速率升温至950℃并保温3.5h,得到脱脂坯体6;
将脱脂坯体6置于氨气环境中,气压为10MPa,以5℃/min的速率升温至800℃,然后以1℃/min升温至1650℃并保温2h,再以1℃/min降温至800℃后随炉冷却,得多孔氮化硅陶瓷6,气孔率为25~40%。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (7)
2.根据权利要求1所述的制备方法,其特征在于,所述烧结助剂为MgO、Al2O3和Re2O3中的一种或多种;
其中,Re2O3=Y2O3、La2O3、Ce2O3、Pr2O3、Nd2O3、Pm2O3、Sm2O3、Eu2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Er2O3或Tm2O3。
3.根据权利要求1所述的制备方法,其特征在于,所述光固化树脂选自1,6-己二醇二丙烯酸酯、季戊四醇四丙烯酸酯、甲基丙烯酸羟乙酯、季戊四醇三丙烯酸酯和三羟甲基丙烷三丙烯酸酯中的一种或多种。
4.根据权利要求1所述的制备方法,其特征在于,所述光引发剂选自2-羟基-2-甲基-1-苯基-1-丙酮、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、(2,4,6-三甲基苯甲酰基)二苯基氧化膦和2-异丙基硫杂蒽酮中的一种或多种。
5.根据权利要求1所述的制备方法,其特征在于,所述加热脱脂包括:
在真空或保护气氛条件下,将所述成型坯体以0.5~2℃/min的升温速率升温至280℃并保温1~3h,接着以1~2℃/min的速率升温至600℃并保温1~3h,再以0.5~2℃/min的速率升温至800~1000℃并保温1~5h,得到所述脱脂坯体。
6.根据权利要求1所述的制备方法,其特征在于,步骤c)在0.1-200MPa的气压下进行。
7.根据权利要求1或5所述的制备方法,其特征在于,所述保护气氛为氨气气氛、氮气气氛或氩气气氛。
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