CN115231904A - 一种非溶剂置换非水沉淀工艺制备陶瓷粉体的方法 - Google Patents
一种非溶剂置换非水沉淀工艺制备陶瓷粉体的方法 Download PDFInfo
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Abstract
本发明公开一种非溶剂置换非水沉淀工艺制备陶瓷粉体的方法，包括如下步骤：步骤一：将前驱体原料溶解于非水溶剂A中，制得前驱体原料的A溶液；步骤二：以某种方式促进步骤一A溶液通过非水解缩聚反应形成A溶胶；步骤三：向步骤二溶胶中加入另一非水非溶剂B，搅拌形成A溶胶的B悬浊液；步骤四：对步骤三悬浊液进行脱溶剂A并回收处理，得到前驱体沉淀的B料浆；步骤五：对步骤四的B料浆进行脱溶剂B并回收处理，获得的沉淀再经研磨和煅烧处理得到陶瓷粉体。本发明具有实用范围广，无需消耗沉淀剂或催化剂，溶剂和副产物均可以回收再利用和变废为宝，发明方案的分子经济性好等突出特点，因此具有广阔的应用前景。
Description
技术领域
本发明属于无机材料制备技术领域，具体涉及到一种非溶剂置换非水沉淀工艺制备陶瓷粉体的方法。
背景技术
陶瓷材料通常具有耐高温、耐腐蚀、耐磨损、高强度、高硬度等一系列优异特性，被广泛地用于冶金、机械、化工、交通、生物、医疗、电子、能源、环境、国防和航空航天等领域，成为人们日常生活和科技发展不可或缺的关键材料之一。陶瓷材料一般是由其对应的粉体经成型、烧结等工艺制备而成。陶瓷粉体内禀特性的优劣直接关系到陶瓷性能的好坏。因此，优质陶瓷粉体的制备是获得高性能陶瓷材料的前提和基础。同时，陶瓷粉体材料本身具有比表面积大、表面能高、活性好等特性。微细化的颗粒尺寸促使陶瓷的电子和晶体结构发生了变化，产生了陶瓷块状材料不具备的体积效应、小尺寸效应、量子尺寸效应和宏观量子隧道效应，使得其化学和物理性能得到质的改变，具备一系列优异的物理和化学性质。很多高新技术领域正在逐步引入陶瓷粉体，并成为当代高技术新量点。陶瓷粉体材料在众多领域的应用也日趋广泛。高纯、均匀、活性高、分散性好、形状规则、化学计量准确以及掺杂均匀等是高性能陶瓷材料制备及相关应用对其粉体内禀特性的要求。然而，虽然我国是陶瓷的发源地，陶瓷在我国的应用和发展有几千年的历史，但目前我国优质陶瓷粉体的消耗还主要依赖进口。因此，高品质陶瓷粉体制备新方法的开发对陶瓷材料及相关高科技领域的发展意义重大。
目前，制备陶瓷粉体的方法可以归纳为固相法、液相法和气相法三大类。液相法制备的陶瓷粉体具有设备门槛低、可精确控制产物组成等突出优点，是优质陶瓷粉体目前实验室和工业上最为广泛采用的方法。其中，沉淀法又因工艺简单、周期短，成本低，条件温和、操作易控，便于批量生产等一系列优点，成为液相化学合成高纯陶瓷粉体采用最广泛的方法。然而，传统沉淀法以水为溶剂，存在如下问题：(1)中间产物往往是氢氧化物，存在=M-OH + HO-M= → =M-O-M= + H2O的缩聚反应，这一缩聚反应被认为是造成颗粒硬团聚的根本原因，导致颗粒的分散性和均匀性较差；(2)由液相的表面张力造成的毛细管作用力被认为是造成颗粒团聚的最主要原因；水的表面张力(72.02N/m)远大于常规有机溶剂(20~35N/m)，这使得以水为溶剂制备陶瓷粉体时，颗粒往往存在团聚。(3)多数水系沉淀法获得的氢氧化物沉淀为无定形沉淀，一次颗粒细小但极易团聚、易包裹溶剂甚至其他杂质，往往需要水洗等沉淀后处理工艺。(4)不同金属离子的水系沉淀物的溶度积常数Ksp往往存在一定的差异，而且以水为主体溶剂沉淀反应过程的调控手段有限，这导致采用传统沉淀法制备复合金属氧化物陶瓷材料时，体系容易偏析，最终造成制得粉体材料的元素分布均匀性差，甚至偏离化学计量。这些问题造成传统水系沉淀法制备的陶瓷粉体难以满足高性能陶瓷材料制备及高科技领域对陶瓷粉体材料的要求。因此，开发方法制备出高纯、均匀、活性高、分散性好、形状规则的陶瓷粉体，并系统研究新型制备方法的基础理论问题是科学研究领域的一个热点问题。
本团队前期率先在国内外提出了采用非水沉淀工艺制备陶瓷粉体的方法，该方法通过非水溶剂溶解前驱体原料，再加入沉淀剂或通过促进剂或外场(辅助压力场或超声场)增强缩聚形成沉淀，脱除溶剂并回收后，煅烧沉淀获得陶瓷粉体。本项目申报团队已成功将该非水沉淀工艺应用于氧化锆、氧化铝、氧化钛、莫来石、钛酸钡等陶瓷粉体的制备，开发出颗粒大小可控的高分散性陶瓷粉体制备新工艺。该非水沉淀法具有工艺和设备简单，控制要求低，制备周期短，颗粒大小和形貌控制简单等突出优点。更为关键的是：非水沉淀法有效克服了水系沉淀法获得沉淀脱水缩聚和干燥过程容易造成团聚的问题；非水沉淀法的前驱体可以通过非水解异质缩聚反应实现原子级均匀混合，进而大大降低掺杂体系和复合氧化物的合成温度。同时，不同前驱体沉淀物的溶解度可以通过非水溶剂的选择和复合溶剂配比优化等手段有效调控。然而，添加沉淀剂非水沉淀法、促进剂增强缩聚非水沉淀及外场促进缩聚非水沉淀法都具有特定的反应体系要求，并不能保证多种陶瓷粉体体系的同时适用。
发明内容
本发明要解决的技术问题是提供一种制品优异、操作方便、适用范围广的非溶剂置换非水沉淀工艺制备陶瓷粉体的方法。
为解决以上技术问题，本发明的技术方案是：一种非溶剂置换非水沉淀工艺制备陶瓷粉体的方法，其特征在于包括如下步骤：
步骤一：将前驱体原料溶解于非溶剂A中，制得前驱体原料的A溶液；
步骤二：以某种方式促进步骤一A溶液通过非水解缩聚反应形成A溶胶；
步骤三：向步骤二A溶胶中加入另一非溶剂B，搅拌形成A溶胶的B悬浊液；
步骤四：对步骤三悬浊液进行脱溶剂A并回收处理，得到前驱体沉淀的B料浆；
步骤五：对步骤四的B料浆进行脱溶剂B并回收处理，获得的沉淀再经研磨和煅烧处理得到陶瓷粉体。
所述步骤一中的前驱体原料为陶瓷粉体对应元素的醇盐、低碳有机酸盐、卤化物、铵盐中的一种；非溶剂A为沸点为30～120℃除甲醇外的醇类、酯类、醚类、酮类、有机酸类中的一种；所述步骤三中的非溶剂B为沸点为80～120℃苯类、烷烃类及其复合产品油类中的一种。
所述步骤五中的陶瓷粉体为单元陶瓷氧化物或复合陶瓷氧化物。
所述单元陶瓷氧化物为氧化铝、氧化钛、氧化锆、氧化锌、氧化铁、氧化镍、氧化钇的一种；所述复合陶瓷氧化物为钛酸铝、钛酸铁、莫来石、硅酸锆、钛酸钡基复合陶瓷氧化物中的一种。
所述步骤二中促进溶液转变为溶胶的方式包括加热处理、超声处理、微波处理、辅助压力场处理中的一种。
所述加热处理的温度为40～120℃，加热时间为2～36h；所述超声处理频率为25KHz、40KHz、68KHz，超声处理功率为500～2200W，超声处理时间为15～60min；所述微波处理功率为500～1350W，微波处理时间为2～20min。
所述步骤四中脱溶剂A并回收处理的方式包括直接干燥和冷凝、减压干燥和冷凝、旋转蒸发和冷凝。
所述直接干燥温度为50～120℃，减压干燥的压力为0.01～0.09MPa、温度为35～110℃，旋转蒸发的转数为30～180转/分、温度为35～110℃。
所述步骤五中脱除溶剂B并回收处理的方式为离心、过滤、甩干、压滤、喷雾中的一种。
所述步骤五中煅烧温度为400～1500℃。
本发明提出的“非溶剂”置换非水沉淀工艺制备陶瓷粉体的方法，是一种在温和条件下简单可靠、可以广泛适用的合成方法，有机溶剂体系不仅可以避免水系沉淀法由于水的表面张力和缩聚造成的团聚，溶剂脱离回收再利用简单，同时“非溶剂”置换有效避免了添加沉淀剂非水沉淀法在多元体系中造成的不均匀沉淀、及促进剂增强缩聚非水沉淀法造成的回收溶剂重复再利用需要精馏处理等问题。同时，采用非极性“非溶剂”置换的方法制备的粉体松软，有效克服了极性基团造成的陶瓷粉体硬团聚及对粉体烧结和烧结体性能的不利影响，因此具有广阔的应用空间。
附图说明
图1为本发明的工艺流程图。
具体实施方式
下面结合附图和具体实施方式对本发明作进一步详细的说明。
实施例1：
将1.33g 无水三氯化铝加入到50mL的无水乙醇中，搅拌制得无色透明三氯化铝的乙醇溶液。60℃加热反应6h引发非水解反应，转变为亮黄色透明溶胶。向溶胶中加入30mL煤油，搅拌形成悬浊液。80℃加热冷凝直至无水乙醇全部回收，得到煤油沉淀料浆。对其进行甩干处理得到干沉淀料，研磨后再经1200℃煅烧处理得到氧化铝陶瓷粉体。
实施例2：
将8.3mL钛酸丁酯加入到50mL乙酸中，搅拌制得无色透明钛酸丁酯的乙酸溶液。40℃加热反应36h引发非水解反应，转变为亮黄色透明溶胶。向溶胶中加入50mL正癸烷，搅拌形成悬浊液。120℃加热冷凝直至乙酸全部回收，得到正癸烷沉淀料浆。对其进行过滤处理得到干沉淀料，研磨后再经400℃煅烧处理得到氧化钛陶瓷粉体。
实施例3：
将4.6mL正硅酸乙酯加入到50mL正丁醚中，搅拌制得无色透明正硅酸乙酯的正丁醚溶液。120℃加热反应18h引发非水解反应，转变为亮黄色透明溶胶。向溶胶中加入50mL柴油，搅拌形成悬浊液。115℃加热冷凝直至正丁醚全部回收，得到柴油沉淀料浆。对其进行甩干处理得到沉淀料，研磨后再经1200℃煅烧处理得到氧化硅陶瓷粉体。
实施例4：
将7.040 g ZrCl4和8 mL Si(OC2H5)4加入到50mL二氯甲烷中，搅拌制得无色透明的硅、锆前驱体的二氯甲烷溶液。40℃加热反应36h引发非水解反应，转变为亮黄色透明溶胶。向溶胶中加入50mL二甲苯，搅拌形成悬浊液。50℃加热冷凝直至二氯甲烷全部回收，得到二甲苯沉淀料浆。对其进行喷雾处理得到沉淀料，研磨后再经1500℃煅烧处理得到硅酸锆陶瓷粉体。
实施例5：
将4.1mL 四氯化钛和10.00g 无水三氯化铝加入到50mL乙醚中，搅拌制得无色透明的铝、钛前驱体的乙醚溶液。45℃加热反应20h引发非水解反应，转变为亮黄色透明溶胶。向溶胶中加入50mL汽油，搅拌形成悬浊液。50℃加热冷凝直至乙醚全部回收，得到汽油沉淀料浆。对其进行压滤处理得到沉淀料，研磨后再经750℃煅烧处理得到钛酸铝陶瓷粉体。
实施例6：
将5.1084g乙酸钡，4.1142g乙酸锶和14.1mL钛酸丁酯加入50 mL甲酸中，搅拌制得无色透明的钡、锶、钛前驱体的甲酸溶液。80℃加热反应24h引发非水解反应，转变为亮黄色透明溶胶。向溶胶中加入50mL煤油，搅拌形成悬浊液。90℃加热冷凝直至甲酸全部回收，得到煤油沉淀料浆。对其进行压滤处理得到沉淀料，研磨后再经800℃煅烧处理得到钛酸铝陶瓷粉体。
实施例7：
将5.1084g乙酸钡，4.1142g乙酸锶和14.1mL钛酸丁酯加入50 mL甲酸中，搅拌制得无色透明的钡、锶、钛前驱体的甲酸溶液。采用超声(40KHz，1000W，40min) 促进非水解缩聚反应，转变为亮黄色透明溶胶。向溶胶中加入50mL煤油，搅拌形成悬浊液。90℃加热冷凝直至甲酸全部回收，得到煤油沉淀料浆。对其进行压滤处理得到沉淀料，研磨后再经800℃煅烧处理得到钛酸铝陶瓷粉体。
实施例8：
将5.1084g乙酸钡，4.1142g乙酸锶和14.1mL钛酸丁酯加入50 mL甲酸中，搅拌制得无色透明的钡、锶、钛前驱体的甲酸溶液。采用超声(25KHz，2200W，15min) 促进非水解缩聚反应，转变为亮黄色透明溶胶。向溶胶中加入50mL煤油，搅拌形成悬浊液。90℃加热冷凝直至甲酸全部回收，得到煤油沉淀料浆。对其进行压滤处理得到沉淀料，研磨后再经800℃煅烧处理得到钛酸铝陶瓷粉体。
实施例9：
将5.1084g乙酸钡，4.1142g乙酸锶和14.1mL钛酸丁酯加入50 mL甲酸中，搅拌制得无色透明的钡、锶、钛前驱体的甲酸溶液。采用超声(68KHz，500W，60min) 促进非水解缩聚反应，转变为亮黄色透明溶胶。向溶胶中加入50mL煤油，搅拌形成悬浊液。90℃加热冷凝直至甲酸全部回收，得到煤油沉淀料浆。对其进行压滤处理得到沉淀料，研磨后再经800℃煅烧处理得到钛酸铝陶瓷粉体。
实施例10：
将5.1084g乙酸钡，4.1142g乙酸锶和14.1mL钛酸丁酯加入50 mL甲酸中，搅拌制得无色透明的钡、锶、钛前驱体的甲酸溶液。采用1000W的微波处理100min引发非水解反应，转变为亮黄色透明溶胶。向溶胶中加入50mL煤油，搅拌形成悬浊液。减压干燥的压力为0.09MPa、温度为110℃加热冷凝直至甲酸全部回收，得到煤油沉淀料浆。对其进行压滤处理得到沉淀料，研磨后再经800℃煅烧处理得到钛酸铝陶瓷粉体。
实施例11：
将7.040 g ZrCl4和8 mL Si(OC2H5)4加入到50mL二氯甲烷中，搅拌制得无色透明的硅、锆前驱体的二氯甲烷溶液。采用500W的微波处理20min引发非水解反应，转变为亮黄色透明溶胶。向溶胶中加入50mL二甲苯，搅拌形成悬浊液。35℃、180转/分旋转蒸发冷凝直至二氯甲烷全部回收，得到二甲苯沉淀料浆。对其进行离心处理得到沉淀料，研磨后再经1300℃煅烧处理得到硅酸锆陶瓷粉体。
实施例12：
将7.040 g ZrCl4和8 mL Si(OC2H5)4加入到50mL氯仿中，搅拌制得无色透明的硅、锆前驱体的二氯甲烷溶液。1350W的微波处理2min引发非水解反应，转变为亮黄色透明溶胶。向溶胶中加入50mL煤油，搅拌形成悬浊液。减压干燥的压力为0.014MPa、温度为35℃加热冷凝直至氯仿全部回收，得到煤油沉淀料浆。对其进行压滤处理得到沉淀料，研磨后再经1400℃煅烧处理得到硅酸锆陶瓷粉体。
Claims (10)
1.一种非溶剂置换非水沉淀工艺制备陶瓷粉体的方法，其特征在于包括如下步骤：
步骤一：将前驱体原料溶解于非溶剂A中，制得前驱体原料的A溶液；
步骤二：以某种方式促进步骤一A溶液通过非水解缩聚反应形成A溶胶；
步骤三：向步骤二A溶胶中加入另一非溶剂B，搅拌形成A溶胶的B悬浊液；
步骤四：对步骤三悬浊液进行脱溶剂A并回收处理，得到前驱体沉淀的B料浆；
步骤五：对步骤四的B料浆进行脱溶剂B并回收处理，获得的沉淀再经研磨和煅烧处理得到陶瓷粉体。
2.根据权利要求1所述的方法，其特征在于：所述步骤一中的前驱体原料为陶瓷粉体对应元素的醇盐、低碳有机酸盐、卤化物、铵盐中的一种；非溶剂A为沸点为30～120℃除甲醇外的醇类、酯类、醚类、酮类、有机酸类中的一种；所述步骤三中的非溶剂B为沸点为80～120℃苯类、烷烃类及其复合产品油类中的一种。
3.根据权利要求1所述的方法，其特征在于：所述步骤五中的陶瓷粉体为单元陶瓷氧化物或复合陶瓷氧化物。
4.根据权利要求3所述的方法，其特征在于：所述单元陶瓷氧化物为氧化铝、氧化钛、氧化锆、氧化锌、氧化铁、氧化镍、氧化钇的一种；所述复合陶瓷氧化物为钛酸铝、钛酸铁、莫来石、硅酸锆、钛酸钡基复合陶瓷氧化物中的一种。
5.根据权利要求1所述的方法，其特征在于：所述步骤二中促进溶液转变为溶胶的方式包括加热处理、超声处理、微波处理、辅助压力场处理中的一种。
6.根据权利要求5所述的方法，其特征在于：所述加热处理的温度为40～120℃，加热时间为2～36h；所述超声处理频率为25KHz、40KHz、68KHz，超声处理功率为500～2200W，超声处理时间为15～60min；所述微波处理功率为500～1350W，微波处理时间为2～20min。
7.根据权利要求1所述的方法，其特征在于：所述步骤四中脱溶剂A并回收处理的方式包括直接干燥和冷凝、减压干燥和冷凝、旋转蒸发和冷凝。
8.根据权利要求7所述的方法，其特征在于：所述直接干燥温度为50～120℃，减压干燥的压力为0.01～0.09MPa、温度为35～110℃，旋转蒸发的转数为30～180转/分、温度为35～110℃。
9.根据权利要求1所述的方法，其特征在于：所述步骤五中脱除溶剂B并回收处理的方式为离心、过滤、甩干、压滤、喷雾中的一种。
10.根据权利要求1所述的方法，其特征在于：所述步骤五中煅烧温度为400～1500℃。
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834018A (zh) * | 2006-01-12 | 2006-09-20 | 景德镇陶瓷学院 | 一种合成钛酸铝超细粉的方法 |
| CN101054179A (zh) * | 2007-05-29 | 2007-10-17 | 景德镇陶瓷学院 | 非水解溶胶－凝胶法低温合成硅酸锆粉体的方法 |
| CN101823762A (zh) * | 2010-05-07 | 2010-09-08 | 景德镇陶瓷学院 | 非水解溶胶-凝胶工艺制备钛酸铝纳米粉体的方法 |
| CN102432286A (zh) * | 2011-09-02 | 2012-05-02 | 景德镇陶瓷学院 | 一种以金属铝为铝源的非水解溶胶-凝胶工艺低温制备的钛酸铝粉体及其制备方法 |
| US20150000698A1 (en) * | 2013-06-28 | 2015-01-01 | Barney Boynton | Method for cleaning up powder or other contaminants |
| CN105271337A (zh) * | 2015-10-21 | 2016-01-27 | 景德镇陶瓷学院 | 一种采用非水沉淀工艺制备氧化铝超细粉体的方法 |
| CN105502492A (zh) * | 2015-12-18 | 2016-04-20 | 景德镇陶瓷学院 | 一种新型非水沉淀法制备稳定氧化锆超细粉体的方法 |
| CN106365198A (zh) * | 2016-09-06 | 2017-02-01 | 景德镇陶瓷大学 | 一种非水沉淀工艺低温制备氧化钛纳米粉体的方法 |
-
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2023
- 2023-02-28 ZA ZA2023/03146A patent/ZA202303146B/en unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1834018A (zh) * | 2006-01-12 | 2006-09-20 | 景德镇陶瓷学院 | 一种合成钛酸铝超细粉的方法 |
| CN101054179A (zh) * | 2007-05-29 | 2007-10-17 | 景德镇陶瓷学院 | 非水解溶胶－凝胶法低温合成硅酸锆粉体的方法 |
| CN101823762A (zh) * | 2010-05-07 | 2010-09-08 | 景德镇陶瓷学院 | 非水解溶胶-凝胶工艺制备钛酸铝纳米粉体的方法 |
| CN102432286A (zh) * | 2011-09-02 | 2012-05-02 | 景德镇陶瓷学院 | 一种以金属铝为铝源的非水解溶胶-凝胶工艺低温制备的钛酸铝粉体及其制备方法 |
| US20150000698A1 (en) * | 2013-06-28 | 2015-01-01 | Barney Boynton | Method for cleaning up powder or other contaminants |
| CN105271337A (zh) * | 2015-10-21 | 2016-01-27 | 景德镇陶瓷学院 | 一种采用非水沉淀工艺制备氧化铝超细粉体的方法 |
| CN105502492A (zh) * | 2015-12-18 | 2016-04-20 | 景德镇陶瓷学院 | 一种新型非水沉淀法制备稳定氧化锆超细粉体的方法 |
| CN106365198A (zh) * | 2016-09-06 | 2017-02-01 | 景德镇陶瓷大学 | 一种非水沉淀工艺低温制备氧化钛纳米粉体的方法 |
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