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CN108083811B - 一种双梯度多孔陶瓷材料及其制备方法 - Google Patents

一种双梯度多孔陶瓷材料及其制备方法 Download PDF

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CN108083811B
CN108083811B CN201711340250.XA CN201711340250A CN108083811B CN 108083811 B CN108083811 B CN 108083811B CN 201711340250 A CN201711340250 A CN 201711340250A CN 108083811 B CN108083811 B CN 108083811B
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porous ceramic
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史忠旗
杨必果
张哲健
张博
夏鸿雁
王继平
王波
王红洁
杨建锋
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Xianyang Gazelle Valley New Material Technology Co ltd
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Abstract

本发明公开的一种双梯度多孔陶瓷材料及其制备方法，属于多孔陶瓷材料制备技术领域。本发明以两种或两种以上成分及粒径均不同的陶瓷颗粒为原料，添加一定量分散剂和烧结助剂配制水系浆料，对浆料依次进行冷冻、冷冻干燥、排胶烧结等工艺，获得一种结构和成分呈双梯度的多孔陶瓷材料。与传统多孔陶瓷制备方法相比，该方法通过配制浆料时对粘度和分散剂含量等条件进行控制，使得浆料在冷冻时，大颗粒的粉末沉降聚集于底部小颗粒的粉末稳定存在于溶液中，得到自下而上的成分梯度。冷冻形成冰晶时，不同粒径的颗粒对冰层的厚度产生不同影响，制备成的材料片层间距不同，形成了自下而上的结构梯度。

Description

一种双梯度多孔陶瓷材料及其制备方法
技术领域
本发明属于多孔陶瓷材料制备技术领域，具体涉及一种双梯度多孔陶瓷材料及其制备方法。
背景技术
多孔材料的透过性、发达的比表面积、吸收能量的性能、低密度以及低热传导等性能，在净化过滤、保温隔热、生物医疗、电子器件、航空航天和能源化工等各方面都有广泛的应用。陶瓷多孔材料由于优异的理化性能和机械性能，应用前景广阔。近年来，人们对多孔陶瓷材料的关注日益密切，也取得了显著的进展。以冰为模板，利用冷冻干燥技术制备多孔陶瓷材料，由于独特的层片状仿生结构吸引了国内外学者的广泛关注，此外冷冻干燥技术作为一种近净成型的环境友好型技术在当今环境问题日益严峻的情况下有本质的优势，发展潜力巨大。
双梯度多孔陶瓷材料，其中结构的梯度分布有助于选择性过滤和分离等功能的实现，而成分的梯度分布又赋予了材料特殊的性能，拓宽了其应用领域。比如，Al2O3/ZrO2双梯度多孔陶瓷材料，其中Al2O3含量高的一侧具有良好的耐磨性和高温稳定性，而ZrO2含量高的一端由于ZrO2相的相变增韧和微裂纹增韧具有良好的韧性。
中国专利《仿生梯度多孔陶瓷材料的制备方法》(申请号：201310046286.2，申请公布号CN 103145438A，申请公布日2013.06.12)公开了一种注浆成型结合多次冷冻干燥技术，制备孔隙率由内向外减小，具有内疏外密仿生结构的梯度多孔陶瓷材料。该方法通过多次冷冻来得到孔隙由内向外减小的结构梯度多孔材料。但成分和结构的双梯度尚未实现。
中国专利《双梯度多孔NiTi/羟基磷灰石复合材料的制备方法》(申请号：201610669444.3，申请公布号：CN 106270516A，申请公布日2017.01.04)公布了一种采用离心-凝胶注模技术制备空隙和NiTi含量均呈现连续分布的双梯度多孔NiTi/羟基磷灰石复合材料。利用该方法制备双梯度NiTi/羟基磷灰石复合材料，需要先对浆料进行离心处理，然后再凝胶固化，再烧结，因此制备工艺复杂，一定程度限制了其应用领域。
于景媛等发表的论文《离心-凝胶注模工艺制备双梯度多孔Al2O3-ZrO2陶瓷》，选自《功能材料》2013年第22期(44)卷第3354-3358页，采用造孔剂PMMA、纳米Al2O3和ZrO2颗粒为主要原料，利用离心-凝胶注模成型工艺制备结构和Al2O3/ZrO2相组成均呈现梯度分布的多孔Al2O3-ZrO2陶瓷。该方法不仅需要加入造孔剂、引发剂、催化剂等添加剂，而且也需要进行离心处理、凝胶固化和高温烧结的多步制备，合成工艺复杂，对设备等硬件条件要求较高，实际应用难度较大。
发明内容
为了克服上述现有技术存在的缺陷，本发明的目的在于提供一种双梯度多孔陶瓷材料及其制备方法，该方法操作简便、对设备要求低、环境友好，该方法能够制得结构呈双梯度的多孔陶瓷材料。
本发明是通过以下技术方案来实现：
本发明公开的一种双梯度多孔陶瓷材料的制备方法，包括以下步骤：
1)配制陶瓷浆料
将分散剂溶于去离子水中制得稳定的溶液，向该稳定的溶液中加入烧结助剂和两种或两种以上成分、粒径均不相同的陶瓷颗粒，球磨混料，制得陶瓷浆料；
2)浆料除气
采用真空搅拌除气法去除陶瓷浆料中的气泡；
3)冷冻
将经步骤2)除气处理后的陶瓷浆料置于冷却模具中，进行冷冻，冷冻温度为-5℃～-55℃，得到冷冻生坯；
4)真空冷冻干燥
将冷冻生坯在-55℃、1Pa的真空度下，真空冷冻干燥处理，制得层片状梯度多孔陶瓷生坯；
5)排胶和烧结
将层片状梯度多孔陶瓷生坯，自室温起，以1～3℃/min的升温速率，加热至500～800℃，排胶处理2～4h；再以10～12℃/min的升温速率，加热至1300～2100℃，保温3～5h，制得层片状梯度多孔碳化硅陶瓷。
优选地，步骤1)中，陶瓷颗粒为氧化铝、氧化锆、氮化铝、羟基磷灰石、磷酸三钙、粘土、碳化硅、氮化硅、金刚砂和堇青石中的两种或两种以上按任意比例混合而成。
优选地，步骤1)中，陶瓷浆料的固相含量为15％～45％。
优选地，步骤1)中，分散剂为羧甲基纤维素钠、聚甲基丙烯酸盐、聚乙烯亚胺、四甲基氢氧化铵或聚乙二醇，分散剂的添加量为陶瓷颗粒质量的0.3％～8％。
优选地，步骤1)中，烧结助剂为烧结助剂为Y2O3、Al2O3、Yb2O3、Lu2O3、Sm2O3、SiO2、Nd2O3和Eu2O3中的一种或几种，用量为陶瓷颗粒质量的5％～15％。
优选地，步骤1)中，球磨混料的处理时间为20～30h。
优选地，步骤3)所述的冷却模具，侧壁和基底采用低导热的硅胶材料，中心棒采用高导热的铜棒。
优选地，步骤4)所述真空冷冻干燥处理的时间为15～30h。
本发明还公开了采用上述的制备方法制得的双梯度多孔陶瓷材料。
与现有技术相比，本发明具有以下有益的技术效果：
本发明公开的双梯度多孔陶瓷材料的制备方法，以两种或两种以上成分及粒径均不同的陶瓷颗粒为原料，添加一定量分散剂和烧结助剂配制水系浆料，对浆料依次进行冷冻、冷冻干燥、排胶烧结等工艺，获得一种结构和成分呈双梯度的多孔陶瓷材料。与传统多孔陶瓷制备方法相比，该方法通过配制浆料时对粘度和分散剂含量等条件进行控制，使得浆料在冷冻时，大颗粒的粉末沉降聚集于底部小颗粒的粉末稳定存在于溶液中，得到自下而上的成分梯度。冷冻形成冰晶时，不同粒径的颗粒对冰层的厚度产生不同影响，制备成的材料片层间距不同，形成了自下而上的结构梯度。该方法操作简便、对设备要求低、环境友好。
经本发明制得的结构和成分呈双梯度的双梯度多孔陶瓷材料有助于选择性过滤和分离等功能的实现，并且有效拓展了其应用领域。
附图说明
图1为实施实例1中所制备的双梯度多孔陶瓷材料的宏观图片；
图2为实施实例1中制备的双梯度多孔陶瓷材料的XRD分析。
具体实施方式
下面结合具体的实施例对本发明做进一步的详细说明，所述是对本发明的解释而不是限定。
实施例1
一种双梯度多孔陶瓷材料的制备方法，包括以下步骤：
(1)选取SiC(50μm)、SiC(20μm)和Al2O3(0.5μm)作为原料，将SiC(50μm)、SiC(20μm)和Al2O3以质量比1:1:1混合，并加入0.6wt％的分散剂羧甲基纤维素钠，加入去离子水制备固相含量为20vol％的浆料，球磨30小时；
(2)将球磨后的浆料在真空中搅拌除气20分钟后倒入硅胶模具中；
(3)在-50℃冷冻浆料，大约15分钟；
(4)利用冷冻干燥机将冷冻的坯体在-55℃，1Pa的条件下进行真空冷冻干燥，处理时间为15h，获得生坯；
(5)将生坯在电阻炉中在600℃下保温2小时除去有机物，然后置于空气炉中烧结3小时，生坯的烧结温度为1400℃，制得双梯度多孔陶瓷材料。
制得的双梯度多孔陶瓷材料的宏观形貌如图1所示，微观形貌如图2所示，从图1和图2中可以看出，制备的双梯度多孔陶瓷材料，其上部为氧化铝，中部为粒径较小的SiC颗粒，下部为大粒径的SiC颗粒。因此，利用本发明可以实现双梯度多孔陶瓷材料的制备，有效的拓宽了多孔陶瓷的制备技术及应用领域。
实施例2
一种双梯度多孔陶瓷材料的制备方法，包括以下步骤：
(1)选取ZrO2(20μm)和Al2O3(10μm)作为原料，将两种ZrO2和Al2O3以质量比1:1.5混合，并加入0.4wt％的分散剂聚甲基丙烯酸钠，加入去离子水制备固相含量为30vol％的浆料，球磨30小时；
(2)将球磨后的浆料在真空中搅拌除气20分钟后倒入硅胶模具中；
(3)在-30℃冷冻浆料，大约22分钟；
(4)利用冷冻干燥机将冷冻的坯体在-55℃，1Pa的条件下进行真空冷冻干燥，处理时间为20h，获得生坯；
(5)将生坯在电阻炉中在800℃下保温2小时除去有机物，然后置于真空炉中烧结3小时，生坯的烧结温度为1600℃，获得双梯度多孔陶瓷材料。
实施例3
一种双梯度多孔陶瓷材料的制备方法，包括以下步骤：
(1)选取Si3N4(5μm)和Al2O3(0.5μm)作为原料，将Si3N4(5μm)和Al2O3以质量比1:2混合，并加入1wt％的分散剂聚乙二醇和5wt％的烧结助剂Y2O3，加入去离子水制备固相含量为40vol％的浆料，球磨30小时；
(2)将球磨后的浆料在真空中搅拌除气20分钟后倒入硅胶模具中；
(3)在-40℃冷冻浆料，大约18分钟；
(4)利用冷冻干燥机将冷冻的坯体在-55℃，1Pa的条件下进行真空冷冻干燥，处理时间为25h，获得生坯；
(5)将生坯在电阻炉中在500℃下保温2小时除去有机物，然后置于气压炉中烧结3小时，生坯的烧结温度为1850℃，获得双梯度多孔陶瓷材料。
实施例4
一种双梯度多孔陶瓷材料的制备方法，包括以下步骤：
(1)选取ZrO2(20μm)、SiC(20μm)和Al2O3(0.5μm)作为原料，将ZrO2(20μm)、SiC(20μm)和Al2O3以质量比1:1:1混合，并加入1wt％的分散剂羧甲基纤维素钠，加入去离子水制备固相含量为25vol％的浆料，球磨30小时；
2)将球磨后的浆料在真空中搅拌除气20分钟后倒入硅胶模具中；
(3)在-5℃冷冻浆料，大约25分钟；
(4)利用冷冻干燥机将冷冻的坯体在-55℃，1Pa的条件下进行真空冷冻干燥，处理时间为30h，获得生坯；
(5)将生坯在电阻炉中在700℃下保温2小时除去有机物，然后置于空气炉中烧结3小时，生坯的烧结温度为1600℃，获得双梯度多孔陶瓷材料。
实施例5
一种双梯度多孔陶瓷材料的制备方法，包括以下步骤：
(1)选取粘土(20μm)和Al2O3(0.5μm)作为原料，将粘土(20μm)和Al2O3以质量比1:2混合，并加入1wt％的分散剂聚乙二醇，加入去离子水制备固相含量为35vol％的浆料，球磨30小时；
(2)将球磨后的浆料在真空中搅拌除气20分钟后倒入硅胶模具中；
(3)在-10℃冷冻浆料，大约22分钟；
(4)利用冷冻干燥机将冷冻的坯体在-55℃，1Pa的条件下进行真空冷冻干燥，处理时间为20h，获得生坯；
(5)将生坯在电阻炉中在700℃下保温2小时除去有机物，然后置于空气炉中烧结3小时，生坯的烧结温度为1600℃，获得双梯度多孔陶瓷材料。

Claims (9)

1.一种双梯度多孔陶瓷材料的制备方法，其特征在于，包括以下步骤：
1)配制陶瓷浆料
将分散剂溶于去离子水中制得稳定的溶液，向该稳定的溶液中加入烧结助剂和两种或两种以上成分、粒径均不相同的陶瓷颗粒，球磨混料，制得陶瓷浆料；配制陶瓷浆料时，通过对粘度和分散剂含量进行控制，使得浆料在冷冻时，大颗粒的粉末沉降聚集于底部小颗粒的粉末稳定存在于溶液中，得到自下而上的成分梯度；
2)浆料除气
采用真空搅拌除气法去除陶瓷浆料中的气泡；
3)冷冻
将经步骤2)除气处理后的陶瓷浆料置于冷却模具中，进行冷冻，冷冻温度为-5℃～-55℃，得到冷冻生坯；
4)真空冷冻干燥
将冷冻生坯在-55℃、1Pa的真空度下，真空冷冻干燥处理，制得层片状梯度多孔陶瓷生坯；
5)排胶和烧结
将层片状梯度多孔陶瓷生坯，自室温起，以1～3℃/min的升温速率，加热至500～800℃，排胶处理2～4h；再以10～12℃/min的升温速率，加热至1300～2100℃，保温3～5h，制得双梯度多孔陶瓷材料。
2.根据权利要求1所述的双梯度多孔陶瓷材料的制备方法，其特征在于，步骤1)中，陶瓷颗粒为氧化铝、氧化锆、氮化铝、羟基磷灰石、磷酸三钙、粘土、碳化硅、氮化硅、金刚砂和堇青石中的两种或两种以上。
3.根据权利要求1所述的双梯度多孔陶瓷材料的制备方法，其特征在于，步骤1)中，陶瓷浆料的固相含量为15％～45％。
4.根据权利要求1所述的双梯度多孔陶瓷材料的制备方法，其特征在于，步骤1)中，分散剂为羧甲基纤维素钠、聚甲基丙烯酸盐、聚乙烯亚胺、四甲基氢氧化铵或聚乙二醇，分散剂的添加量为陶瓷颗粒质量的0.3％～8％。
5.根据权利要求1所述的双梯度多孔陶瓷材料的制备方法，其特征在于，步骤1)中，烧结助剂为烧结助剂为Y2O3、Al2O3、Yb2O3、Lu2O3、Sm2O3、SiO2、Nd2O3和Eu2O3中的一种或几种，用量为陶瓷颗粒质量的5％～15％。
6.根据权利要求1所述的双梯度多孔陶瓷材料的制备方法，其特征在于，步骤1)中，球磨混料的处理时间为20～30h。
7.根据权利要求1所述的双梯度多孔陶瓷材料的制备方法，其特征在于，步骤3)所述的冷却模具，侧壁和基底采用低导热的硅胶材料，中心棒采用高导热的铜棒。
8.根据权利要求1所述的双梯度多孔陶瓷材料的制备方法，其特征在于，步骤4)所述真空冷冻干燥处理的时间为15～30h。
9.采用权利要求1～8中任意一项所述的制备方法制得的双梯度多孔陶瓷材料。
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