CN113045313B - 一种热固化粉末注射成型的锆钛酸铅镧压电陶瓷的制备方法 - Google Patents
一种热固化粉末注射成型的锆钛酸铅镧压电陶瓷的制备方法 Download PDFInfo
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- CN113045313B CN113045313B CN202110232626.5A CN202110232626A CN113045313B CN 113045313 B CN113045313 B CN 113045313B CN 202110232626 A CN202110232626 A CN 202110232626A CN 113045313 B CN113045313 B CN 113045313B
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- piezoelectric ceramic
- zirconate titanate
- lanthanum zirconate
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Abstract
本发明属于压电陶瓷增材制造技术领域,具体涉及一种热固化粉末注射成型的锆钛酸铅镧压电陶瓷的制备方法,先对锆钛酸铅镧压电陶瓷粉末进行改性处理,得到性能优异的压电陶瓷细粉;再将改性后的陶瓷细粉与粘结树脂、固化剂、稀释剂在真空下球磨混合,得到分散均匀、粘度适中的压电陶瓷浆料;接着将制备完成的陶瓷浆料注射到加热的模具中,经热固化成型得到陶瓷生坯;最后将陶瓷生坯经脱脂、烧结、被银、极化后得到致密的锆钛酸铅镧压电陶瓷。本发明制得的陶瓷浆料颗粒分散均匀、粘稠度低,可经粉末注射后在模具中热固化成型构件,构件强度高,易转移烧结,经烧结后的样品密度高、电学性能优异,满足压电器件使用要求。
Description
技术领域
本发明属于压电陶瓷增材制造技术领域,具体涉及一种热固化粉末注射成型的锆钛酸铅镧压电陶瓷的制备方法。
背景技术
压电陶瓷是压电材料中使用较为广泛也最具代表的一类材料,由于其内部特殊的电畴结构,以及将电信号转化为机械信号的能力,因此被用来制作出各类压电原件。压电陶瓷类别中应用较为广泛的一类是PLZT(锆钛酸铅镧)陶瓷,PLZT压电陶瓷具有较高的居里温度(380℃),易掺杂改性、稳定的压电常数、良好的品质因子及机电耦合系数以及较高的介电常数,在压电传感及驱动领域,如超能换能器能量采集等领域具有重大意义。
传统的压电陶瓷的制备方法包括热压成型法、干粉压制法、流延成型法等,但很难制备微型结构复杂高精度的陶瓷制品,制约了其在微型电子设备领域的应用。近年来,基于喷墨印刷、挤出直写的无固体模技术已经用于陶瓷部件制造。由于其在制造复杂几何形状和高分辨率方面的优势,3D打印和立体光刻来成型超小型复杂结构异型陶瓷已成为一个活跃的研究领域。但这种方法相较于前几种成型方法,加工造价高昂,成型效率低下。与之相比,注射成型法可以在不浪费其余原料的条件下,成型出高精度、复杂外形的陶瓷元件。考虑到成型效率成本与加工精度范围,注射成型是目前最有前景的陶瓷制备工艺。
树脂粘合剂的作用是粘合并均匀分散陶瓷粉体,加热后可以作为一个载体以产生充分的流动性。目前,粘合剂大体上可以分为热固性和热塑性两种,热塑性树脂有丙烯、石蜡和醋酸乙烯酯均聚物等,优点是流动性好,并且可以通过分子量和分子量分布来调节脱脂阶段的热降解过程。但是其缺点也很明显,此法制得的陶瓷注射胚普遍强度不是很高。而热固化注射成型的难点在于如何提高高固含的同时,保障流动性,且需要保障脱脂过程中不引入其他杂元素。
发明内容
本发明的目的在于提供一种热固化粉末注射成型的锆钛酸铅镧压电陶瓷的制备方法。配制并改性锆钛酸铅镧压电陶瓷粉末,使用粉末注射机将其注射到具有可调模温的模具中,在模具中热固化成型。本发明通过优化压电陶瓷成型方法,成功制得注射坯强度高、结构精密、性能优异的锆钛酸铅镧压电陶瓷,并通过一系列性能测试,满足压电器件的使用要求。
热固化粉末注射成型的锆钛酸铅镧压电陶瓷的制备方法,包括以下步骤:
(1)改性锆钛酸铅镧压电陶瓷粉末的制备:
以Pb3O4、La2O3、ZrO2、TiO2、Nb2O5为原料制备化学式为Pb0.91La0.06(Zr0.58Ti0.42)0.975Nb0.02O3的压电陶瓷粉末,将Pb3O4(64.4%)、La2O3(3.08%)、ZrO2(21.9%)、TiO2(10.31%)和Nb2O5(0.39%)混合均匀在850℃预烧5小时得到压电陶瓷粉末。称取制备完成的陶瓷粉末,加入粉末质量1-2%的表面处理剂,倒入球磨罐中加入研磨球、研磨介质,将混合物以转速400rpm经湿法球磨24小时,球磨完成后经过烘干、过筛,得到颗粒均匀、表面活性处理的改性锆钛酸铅镧压电陶瓷细粉;
其中,表面处理剂为硬脂酸、硬脂酸铅、硬脂酸锆、硬脂酸钛中的一种或几种的混合物;
研磨球为氧化锆球,陶瓷粉末和氧化锆球按质量比为1:2混合,研磨介质为无水乙醇,陶瓷粉末与无水乙醇按体积比为1:1混合。
(2)热固化锆钛酸铅镧压电陶瓷浆料的制备:
将低粘粘结树脂、稀释剂、降粘剂按比例加入捏合机混合均匀后,加入处理得到的改性锆钛酸铅镧压电陶瓷细粉混合均匀,再通过真空脱泡处理去除浆料中气泡,最后加固化剂搅拌得到分散均匀的热固化锆钛酸铅镧压电陶瓷浆料;
其中,低粘粘结树脂为低粘度高固含丙烯酸树脂,其合成工艺为:将25-30份溶剂醋酸丁酯和丙二醇甲醚醋酸酯的混合溶液加入压力反应釜中,向反应釜中通入氮气,置换反应釜中的空气,约30min,然后关闭氮气,密封反应釜,开始加热使反应釜温度升高至160℃,均匀滴加单体引发剂混合液,5-5.5小时内滴完,滴加单体过程反应釜压力保持3-5个大气压力,继续在该温度及压力范围内保温4小时,反应结束降温至80℃以下,放空后进行过滤出料。
单体引发剂混合液按照质量份数的组成为:甲基丙烯酸甲酯30份、丙烯酸丁酯10-15份、甲基丙烯酸羟丙酯10-20份、甲基丙烯酸羟乙酯10-20份、丙烯酸1-3份、引发剂TBPB1-3份、引发剂BPO 1-2份;醋酸丁酯和丙二醇甲醚醋酸酯的质量比为1:1-1:2。
稀释剂为乙二醇丙烯酸酯、苯乙烯中的一种或两种的混合物;
降粘剂为BYK110、BYK9010中的一种或两种混合物;
固化剂为过氧化苯甲酸叔丁酯、异氰尿酸三缩水甘油酯、过氧化二苯甲酰中的一种或几种混合物;
压电陶瓷粉末约占浆料总质量的80%-90%,低粘度高固含丙烯酸树脂与稀释剂共占20%-10%,固化剂加入量是粘结树脂的1-1.5%,降粘剂加入量为压电陶瓷粉末的1-2%;低粘度高固含丙烯酸树脂与稀释剂的质量比为2:1-1:1。
捏合工艺为温度设定50℃,转速60-80转/min。
(3)锆钛酸铅镧压电陶瓷热固化成型:
将处理得到的热固化锆钛酸铅镧压电陶瓷浆料用粉末注射机注射到具有可调模温的模具中,在模具中热固化成型;
其中,使用粉末注射成型法,将配置好的浆料注射到模具中,模具温度设置150-160℃,成型时间为1mm/min,开模取出即得实验中所需陶瓷生坯。
(4)锆钛酸铅镧压电陶瓷生坯后处理:将成型后的陶瓷生坯经脱脂、烧结处理、被银、极化后,即可得到致密性好、形状规则、性能良好的锆钛酸铅镧压电陶瓷。
所述脱脂在空气下进行,所述脱脂的温度为500℃-600℃,升温速率为0.5℃/min-1℃/min,当达到所设定脱脂的温度保温90min-120min以后降温至室温。所述烧结在空气下进行,升温速率为4℃/min-5℃/min,在烧结温度到达850℃时,保温90-120min;最终烧结温度设定为1200℃-1285℃,当达到最终烧结温度保温60min-120min后降温至室温。
有益效果:本发明制得的压电陶瓷浆料颗粒分散均匀、粘稠度低,可以通过粉末注射机注射到具有可调模温的模具中,在模具中热固化成型任意形状的构件、构件强度高,然后将构件用热脱脂法去除陶瓷生坯中的有机物添加剂而不产生任何缺陷,最后烧结的构件样品密度高、电学性能优异,能够满足压电器件使用要求。本发明提出的技术方案既能够克服传统成型方法成型效率较低的缺陷,又能够解决3D打印成型成本高的问题。
附图说明
图1为本发明实施例制备锆钛酸铅镧压电陶瓷工艺流程图。
图2为本发明实施例2制备的陶瓷生坯(左)和烧结陶瓷(右)的示意图。
图3为本发明实施例制备得到的锆钛酸铅镧压电陶瓷扫描电子显微镜图。
具体实施方式
本发明提供了一种热固化粉末注射成型的锆钛酸铅镧压电陶瓷的制备方法。配制并改性锆钛酸铅镧压电陶瓷粉末,使用粉末注射机将其注射到具有可调模温的模具中,在模具中热固化成型。本发明通过优化压电陶瓷成型方法,成功制得结构精密、性能优异的锆钛酸铅镧压电陶瓷,并通过一系列性能测试,满足压电器件的使用要求。
下面结合实施例对本发明技术方案作进一步详细说明。
实施例1
制备化学式为Pb0.91La0.06(Zr0.58Ti0.42)0.975Nb0.02O3的锆钛酸铅镧压电陶瓷粉末,将Pb3O4(64.4%)、La2O3(3.08%)、ZrO2(21.9%)、TiO2(10.31%)和Nb2O5(0.39%)混合均匀在850℃预烧5小时得到压电陶瓷粉末。
称取100g锆钛酸铅镧压电陶瓷粉末,并称取质量为所述粉末质量1%的表面处理剂(硬脂酸),倒入球磨罐中加入氧化锆研磨球和研磨介质无水乙醇进行球磨;转速为400rmp,时间为24小时。该过程可磨碎陶瓷颗粒降低粉末粒径,同时使表面活性剂均匀附着在陶瓷粉体表面。陶瓷粉体和氧化锆球按质量比1:2,陶瓷粉体与无水乙醇按体积比为1:1。球磨完成后经过烘干研磨,过100目细筛,得到颗粒均匀,表面活化的锆钛酸铅镧压电陶瓷细粉。改性后的锆钛酸铅镧压电陶瓷细粉能够均匀地分散在粘合树脂之中,使配置的陶瓷浆料粘度适中,较易成型。
低粘粘结树脂的合成工艺如下:将30份溶剂醋酸丁酯和丙二醇甲醚醋酸酯的混合溶液加入压力反应釜中,向反应釜中通入氮气,置换反应釜中的空气,约30min,然后关闭氮气,密封反应釜,开始加热反应釜温度至160℃,开始均匀滴加单体引发剂混合液,5.5小时内滴完,滴加单体过程反应釜压力保持3-5个大气压力,在该温度下及压力范围内保温4小时,反应结束降温至80℃以下,放空后进行过滤出料。单体引发剂混合液按照质量份数的组成为:甲基丙烯酸甲酯30份、丙烯酸丁酯10份、甲基丙烯酸羟丙酯10份、甲基丙烯酸羟乙酯20份、丙烯酸1份、引发剂TBPB 1份、引发剂BPO 2份;醋酸丁酯和丙二醇甲醚醋酸酯的质量比为1:1。
称取改性后的锆钛酸铅镧压电陶瓷细粉30g,低粘粘结树脂4.5g,乙二醇丙烯酸酯(稀释剂)3g,BYK100(降粘剂)0.3g,过氧化苯甲酸叔丁酯(固化剂)0.045g,加入捏合机混合均匀,所述捏合工艺为温度50℃,转速60转/min,再与氧化锆研磨球一起倒入球磨罐中,以转速450rpm球磨4小时,得到质量分数为80%的热固化锆钛酸铅镧压电陶瓷浆料,配置的压电陶瓷浆料粘度适中,无沉降,流变性能好,可用于热固化成型。
将压电陶瓷浆料使用粉末注射成型法,注射到厚度为1mm直径为15mm的圆形模具中,放入预先设置好温度的平板硫化机内进行热固化成型,成型温度为150℃,成型时间为1mm/min,之后开模取出即得热固化成型的锆钛酸铅镧陶瓷生坯。
热固化完成后的锆钛酸铅镧陶瓷生坯需经过热处理去除各类有机添加剂,得到致密的、具有良好压电性能的陶瓷结构,热处理包括脱脂和烧结。
对制备完成的热固化陶瓷生坯放入马弗炉中进行脱脂。将生坯平铺在预先铺好陶瓷粉的陶瓷板上,并在生坯上方也均匀洒满陶瓷粉,此步骤是为了防止脱脂完成后取样时与陶瓷片与陶瓷板粘连,影响陶瓷片形貌。升温速率为2℃/min升温到850℃保温1.5小时,升温过程中每间隔100℃即保温1小时。由于热固化陶瓷浆料中含有各类有机物添加剂,因此脱脂过程极易产生分层、碎裂等缺陷,因此采取缓慢的升温速率和多保温点保温使各种有机物添加剂缓慢分解、挥发,避免剧烈反应破坏陶瓷坯体。当在最高温度保温完成后,以3℃每分钟的降温速率降至室温,即可得到无结构破坏、无有机物残留的锆钛酸铅镧压电陶瓷块体。
脱脂完成后的块体还需通过烧结致密化。本发明采用传统烧结工艺在空气下进行,升温速率为2℃/min,烧结温度为1285℃,保温1.5小时,升温过程中分别在550℃、850℃保温1小时,到达最高温度之后以3℃/min降温速率降至室温,最终得到致密的锆钛酸铅镧压电陶瓷。
陶瓷坯体热处理完成后,在压电陶瓷上下表面涂覆一层银薄膜,并在常温下油浴极化,经过被银、极化处理后即可得到具有良好压电性能的锆钛酸铅镧压电陶瓷结构。
实施例2
制备化学式为Pb0.91La0.06(Zr0.58Ti0.42)0.975Nb0.02O3的锆钛酸铅镧压电陶瓷粉末,该粉末由实施例(1)中所述方法制得。
称取100g锆钛酸铅镧压电陶瓷粉末,并称取质量为所述粉末质量2%的表面处理剂(硬脂酸铅),倒入球磨罐中加入研磨球氧化锆球和研磨介质无水乙醇进行球磨;转速为400rmp,时间为24小时。该过程可磨碎陶瓷颗粒降低粉末粒径,同时使表面活性剂均匀附着在陶瓷粉体表面,改性锆钛酸铅镧压电陶瓷。陶瓷粉体和氧化锆球按质量比1:2,陶瓷粉体与无水乙醇按体积比为1:1。球磨完成后经过烘干研磨,过100目细筛,得到颗粒均匀,表面活化的锆钛酸铅镧压电陶瓷细粉。改性后的锆钛酸铅镧压电陶瓷细粉能够均匀地分散在粘合树脂之中,使配置的陶瓷浆料粘度适中,较易成型。
低粘粘结树脂的合成工艺如下:将25份溶剂醋酸丁酯和丙二醇甲醚醋酸酯的混合溶液加入压力反应釜中,先放空反应釜,通入氮气,置换反应釜中的空气,约30min,然后关闭氮气,密封反应釜,开始加热反应釜温度至160℃,开始均匀滴加单体引发剂混合液,5小时内滴完,滴加单体过程反应釜压力保持3-5个大气压力,继续在该温度下及压力范围内保温4小时,反应结束降温至80℃以下,放空后进行过滤出料。单体引发剂混合液按照质量份数的组成为:甲基丙烯酸甲酯30份、丙烯酸丁酯15份、甲基丙烯酸羟丙酯10份、甲基丙烯酸羟乙酯20份、丙烯酸1份、引发剂TBPB 2份、引发剂BPO 2份;醋酸丁酯和丙二醇甲醚醋酸酯的质量比为1:1。
称取改性后的锆钛酸铅镧压电陶瓷细粉30g,低粘粘结树脂2.5g,乙二醇丙烯酸酯(稀释剂)2.5g,BYK9010(降粘剂)0.2g,过氧化苯甲酸叔丁酯(固化剂)0.025g,加入捏合机混合均匀,所述捏合工艺为温度设定50℃,转速60转/min,再与氧化锆研磨球一起倒入球磨罐中,以转速450rpm球磨4小时,得到质量分数为85%的热固化锆钛酸铅镧压电陶瓷浆料,配置的压电陶瓷浆料粘度适中,无沉降,流变性能好,可用于热固化成型。
将压电陶瓷浆料使用粉末注射成型法,注射到厚度为1mm直径为15mm的圆形模具中,放入预先设置好温度的平板硫化机内进行热固化成型,成型温度为150℃,成型时间为1mm/min,之后开模取出即得热固化成型的锆钛酸铅镧陶瓷生坯。
热固化完成后的锆钛酸铅镧陶瓷生坯需经过热处理去除各类有机添加剂,得到致密的、具有良好压电性能的陶瓷结构,热处理包括脱脂和烧结。
对制备完成的热固化陶瓷生坯放入马弗炉中进行脱脂。将生坯平铺在预先铺好陶瓷粉的陶瓷板上,并在生坯上方也均匀洒满陶瓷粉,此步骤是为了防止脱脂完成后取样时与陶瓷片与陶瓷板粘连,影响陶瓷片形貌。升温速率为2℃/min升温到850℃保温1.5小时,升温过程中每间隔100℃即保温1小时。由于热固化陶瓷浆料中含有各类有机物添加剂,因此脱脂过程极易产生分层、碎裂等缺陷,因此采取缓慢的升温速率和多保温点保温使各种有机物添加剂缓慢分解、挥发,避免剧烈反应破坏陶瓷坯体。当在最高温度保温完成后,以3℃每分钟的降温速率降至室温,即可得到无结构破坏、无有机物残留的锆钛酸铅镧压电陶瓷块体。
脱脂完成后的块体还需通过烧结致密化。本发明采用传统烧结工艺在空气下进行,升温速率为2℃/min,烧结温度为1285℃,保温1.5小时,升温过程中分别在550℃、850℃保温1小时,到达最高温度之后以3℃/min降温速率降至室温,最终得到致密的锆钛酸铅镧压电陶瓷。
陶瓷坯体热处理完成后,在压电陶瓷上下表面涂覆一层银薄膜,并在常温下油浴极化,经过被银、极化处理后即可得到具有良好压电性能的锆钛酸铅镧压电陶瓷结构。
实施例3
制备化学式为Pb0.91La0.06(Zr0.58Ti0.42)0.975Nb0.02O3的锆钛酸铅镧压电陶瓷粉末,该粉末由实施例(1)中所述方法制得。
称取锆钛酸铅镧压电陶瓷粉末,并称取质量为所述粉末质量2%的表面处理剂(硬脂酸铅),倒入球磨罐中加入研磨球氧化锆球和研磨介质无水乙醇进行球磨;转速为400rmp,时间为24小时。该过程可磨碎陶瓷颗粒降低粉末粒径,同时使表面活性剂均匀附着在陶瓷粉体表面,改性锆钛酸铅镧压电陶瓷。陶瓷粉体和氧化锆球按质量比1:2,陶瓷粉体与无水乙醇按体积比为1:1。球磨完成后经过烘干研磨,过100目细筛,得到颗粒均匀,表面活化的锆钛酸铅镧压电陶瓷细粉。改性后的锆钛酸铅镧压电陶瓷细粉能够均匀地分散在粘合树脂之中,使配置的陶瓷浆料粘度适中,较易成型。
低粘粘结树脂的合成工艺如下:将30份溶剂醋酸丁酯和丙二醇甲醚醋酸酯的混合溶液加入压力反应釜中,先放空反应釜,通入氮气,置换反应釜中的空气,约为30min,然后关闭氮气,密封反应釜,开始加热反应釜至反应温度至160℃,开始均匀滴加单体引发剂混合液,5小时内滴完,滴加单体过程反应釜压力保持3-5个大气压力,继续在该温度下及压力范围内保温4小时,反应结束降温至80℃以下,放空后进行过滤出料。单体引发剂混合液按照质量份数的组成为:甲基丙烯酸甲酯30份、丙烯酸丁酯10份、甲基丙烯酸羟丙酯15份、甲基丙烯酸羟乙酯15份、丙烯酸1份、引发剂TBPB 2份、引发剂BPO 2份;醋酸丁酯和丙二醇甲醚醋酸酯的质量比为1:1。
称取改性后的锆钛酸铅镧压电陶瓷细粉30g,低粘粘结树脂2.5g,乙二醇丙烯酸酯(稀释剂)2.5g,BYK110(降粘剂)0.2g,过氧化苯甲酸叔丁酯(固化剂)0.025g,加入捏合机混合均匀,所述捏合工艺为温度设定50℃,转速60转/min,再与氧化锆研磨球一起倒入球磨罐中,以转速450rpm球磨4小时,得到质量分数为85%的热固化锆钛酸铅镧压电陶瓷浆料,配置的压电陶瓷浆料粘度适中,无沉降,流变性能好,可用于热固化成型。
将压电陶瓷浆料使用粉末注射成型法,注射到厚度为1mm直径为15mm的圆形模具中,放入预先设置好温度的平板硫化机内进行热固化成型,成型温度为150℃,成型时间为1mm/min,之后开模取出即得热固化成型的锆钛酸铅镧陶瓷生坯。
热固化完成后的锆钛酸铅镧陶瓷生坯需经过热处理去除各类有机添加剂,得到致密的、具有良好压电性能的陶瓷结构,热处理包括脱脂和烧结。
对制备完成的热固化陶瓷生坯放入马弗炉中进行脱脂。将生坯平铺在预先铺好陶瓷粉的陶瓷板上,并在生坯上方也均匀洒满陶瓷粉,此步骤是为了防止脱脂完成后取样时与陶瓷片与陶瓷板粘连,影响陶瓷片形貌。升温速率为2℃/min升温到850℃保温1.5小时,升温过程中每间隔100℃即保温1小时。由于热固化陶瓷浆料中含有各类有机物添加剂,因此脱脂过程极易产生分层、碎裂等缺陷,因此采取缓慢的升温速率和多保温点保温使各种有机物添加剂缓慢分解、挥发,避免剧烈反应破坏陶瓷坯体。当在最高温度保温完成后,以3℃每分钟的降温速率降至室温,即可得到无结构破坏、无有机物残留的锆钛酸铅镧压电陶瓷块体。
脱脂完成后的块体还需通过烧结致密化。本发明采用传统烧结工艺在空气下进行,升温速率为2℃/min,烧结温度为1285℃,保温1.5小时,升温过程中分别在550℃、850℃保温1小时,到达最高温度之后以3℃/min降温速率降至室温,最终得到致密的锆钛酸铅镧压电陶瓷。
陶瓷坯体热处理完成后,在压电陶瓷上下表面涂覆一层银薄膜,并在常温下油浴极化,经过被银、极化处理后即可得到具有良好压电性能的锆钛酸铅镧压电陶瓷结构。
实施例4
制备改性锆钛酸铅镧压电陶瓷细粉同实施例1。
低粘粘结树脂的合成同实施例2。
称取改性后的锆钛酸铅镧压电陶瓷细粉30g,低粘粘结树脂1.65g,乙二醇丙烯酸酯(稀释剂)1.65g,BYK9010(降粘剂)0.2g,过氧化苯甲酸叔丁酯(固化剂)0.025g,加入捏合机混合均匀,所述捏合工艺为温度设定50℃,转速60转/min,再与氧化锆研磨球一起倒入球磨罐中,以转速450rpm球磨4小时,得到质量分数为90%的热固化锆钛酸铅镧压电陶瓷浆料,配置的压电陶瓷浆料粘度适中,无沉降,流变性能好,可用于热固化成型。
将压电陶瓷浆料成型、脱脂、焙烧工艺同实施例2。
对比例1
制备化学式为Pb0.91La0.06(Zr0.58Ti0.42)0.975Nb0.02O3的锆钛酸铅镧压电陶瓷粉末,该粉末由实施例(1)中所述方法制得。
称取锆钛酸铅镧压电陶瓷粉末,并称取质量为所述粉末质量40%的PVA水溶液(5%浓度)混合均匀,烘干研磨,过80目细筛,得到颗粒均匀的可压制压电陶瓷粉末,采用该粉末在6MPa压力下干压成型制成干压坯。
干压坯采用传统烧结工艺在空气下进行,升温速率为2℃/min,烧结温度为1285℃,保温1.5小时,升温过程中分别在550℃、850℃保温1小时,到达最高温度之后以3℃/min降温速率降至室温,最终得到致密的锆钛酸铅镧压电陶瓷。
陶瓷坯体热处理完成后,在压电陶瓷上下表面涂覆一层银薄膜,并在常温下油浴极化,经过被银、极化处理后即可得到具有良好压电性能的锆钛酸铅镧压电陶瓷结构。
对比例2
制备改性锆钛酸铅镧压电陶瓷细粉同实施例2。
锆钛酸铅镧压电陶瓷粉末85%、聚乙二醇(由PEG20000和PEG1500的质量比为1:2混合)7.5%、聚乙烯醇缩丁醛(PVB)2.5%、聚甲醛(POM)2.5%、粉末改性剂硬脂酸铋0.85%、余量为石蜡。
将改性后的粉末和粘结剂按比例在密炼机中混合均匀,密炼机的温度设定为180℃,转速为30r/min,密炼均匀后破碎,通过双螺杆挤出机挤出造粒,温度设定为:150℃,160℃,170℃,175℃,180℃,180℃,180℃,转速150rpm,切粒、制备粉末注射专用料。
将粉末注射专用料注射成注射坯,后将注射坯加入去离子水中进行脱脂,脱脂后的样品在1280℃烧结成型制备PLZT压电陶瓷(具体步骤同实施例2)。
对比例3
制备化学式为Pb0.91La0.06(Zr0.58Ti0.42)0.975Nb0.02O3的锆钛酸铅镧压电陶瓷粉末,该粉末由实施例(1)中所述方法制得。
称取100g锆钛酸铅镧压电陶瓷粉末倒入球磨罐中加入研磨球氧化锆球和研磨介质无水乙醇进行球磨;转速为400rmp,时间为24小时。陶瓷粉体和氧化锆球按质量比1:2,陶瓷粉体与无水乙醇按体积比为1:1。球磨完成后经过烘干研磨,过100目细筛,得到颗粒均匀,未改性锆钛酸铅镧压电陶瓷细粉。
称取未改性的锆钛酸铅镧压电陶瓷细粉30g,不饱和树脂2.5g,苯乙烯(稀释剂)2.5g,BYK110(降粘剂)0.2g,过氧化苯甲酸叔丁酯(固化剂)0.025g,加入捏合机混合均匀,所述捏合工艺为温度设定50℃,转速60转/min,再与氧化锆研磨球一起倒入球磨罐中,以转速450rpm球磨4小时,得到质量分数为85%的热固化锆钛酸铅镧压电陶瓷浆料,配置的压电陶瓷浆料粘度适中,无沉降,流变性能好,可用于热固化成型。
将压电陶瓷浆料使用粉末注射成型法,注射到厚度为1mm直径为15mm的圆形模具中,放入预先设置好温度的平板硫化机内进行热固化成型,成型温度为150℃,成型时间为1mm/min,之后开模取出即得热固化成型的锆钛酸铅镧陶瓷生坯。
热固化完成后的锆钛酸铅镧陶瓷生坯需经过热处理去除各类有机添加剂,得到致密的、具有良好压电性能的陶瓷结构,热处理包括脱脂和烧结。
对制备完成的热固化陶瓷生坯放入马弗炉中进行脱脂。将生坯平铺在预先铺好陶瓷粉的陶瓷板上,并在生坯上方也均匀洒满陶瓷粉,此步骤是为了防止脱脂完成后取样时与陶瓷片与陶瓷板粘连,影响陶瓷片形貌。升温速率为2℃/min升温到850℃保温1.5小时,升温过程中每间隔100℃即保温1小时。由于热固化陶瓷浆料中含有各类有机物添加剂,因此脱脂过程极易产生分层、碎裂等缺陷,因此采取缓慢的升温速率和多保温点保温使各种有机物添加剂缓慢分解、挥发,避免剧烈反应破坏陶瓷坯体。当在最高温度保温完成后,以3℃每分钟的降温速率降至室温,即可得到无结构破坏、无有机物残留的锆钛酸铅镧压电陶瓷块体。
脱脂完成后的块体还需通过烧结致密化。本发明采用传统烧结工艺在空气下进行,升温速率为2℃/min,烧结温度为1285℃,保温1.5小时,升温过程中分别在550℃、850℃保温1小时,到达最高温度之后以3℃/min降温速率降至室温,最终得到致密的锆钛酸铅镧压电陶瓷。
陶瓷坯体热处理完成后,在压电陶瓷上下表面涂覆一层银薄膜,并在常温下油浴极化,经过被银、极化处理后即可得到具有良好压电性能的锆钛酸铅镧压电陶瓷结构。
上述各实施例和对照例的性能见表1。
表1
Claims (2)
1.一种热固化粉末注射成型的锆钛酸铅镧压电陶瓷,其特征在于,所述压电陶瓷的制备方法步骤如下:
(1)改性锆钛酸铅镧压电陶瓷粉末的制备
按照质量百分数,将Pb3O4 64.4%、La2O3 3.08% 、ZrO2 21.9%、TiO2 10.31%和Nb2O5 0.39%混合均匀在850℃预烧5小时得到预烧压电陶瓷粉末;将预烧压电陶瓷粉末和表面处理剂倒入球磨罐中,加入研磨介质无水乙醇和氧化锆研磨球,以转速400rpm经湿法球磨24小时,烘干后用研钵碾碎,得到改性锆钛酸铅镧压电陶瓷粉末;
其中,所述表面处理剂为硬脂酸、硬脂酸铅、硬脂酸锆、硬脂酸钛中的一种或几种的混合物;
所述预烧压电陶瓷粉末和氧化锆球质量比为1:2,预烧压电陶瓷粉末与无水乙醇的体积比为1:1;
(2)热固化锆钛酸铅镧压电陶瓷浆料的制备
将低粘度高固含丙烯酸树脂、稀释剂、降粘剂按比例加入50℃捏合机,转速60-80转/min混合均匀后,加入处理得到的改性锆钛酸铅镧压电陶瓷细粉混合均匀,再通过真空脱泡处理去除浆料中的气泡,最后加固化剂搅拌得到分散均匀的热固化锆钛酸铅镧压电陶瓷浆料;
所述低粘度高固含丙烯酸树脂的合成方法为:将25-30份溶剂醋酸丁酯和丙二醇甲醚醋酸酯的混合溶液加入压力反应釜中,通入氮气,置换反应釜中的空气,然后关闭氮气,密封反应釜,将反应釜加热至160℃,均匀滴加单体引发剂混合液,5-5.5小时内滴完,滴加单体过程中反应釜压力保持 3-5个大气压力,在该温度下及压力范围内保温 4小时,反应结束降温至 80℃以下,放空后进行过滤出料得到低粘度高固含丙烯酸树脂;
单体引发剂混合液按照质量份数的组成为:甲基丙烯酸甲酯30份、丙烯酸丁酯10-15份、甲基丙烯酸羟丙酯10-20份、甲基丙烯酸羟乙酯10-20份、丙烯酸1-3份、引发剂TBPB 1-3份、引发剂BPO 1-2份;醋酸丁酯和丙二醇甲醚醋酸酯的质量比为1:1-1:2;
所述稀释剂为乙二醇丙烯酸酯、苯乙烯中的一种或两种的混合物;降粘剂为BYK110、BYK9010中的一种或两种混合物;所述固化剂为过氧化苯甲酸叔丁酯、异氰尿酸三缩水甘油酯、过氧化二苯甲酰中的一种或几种混合物;
所述改性锆钛酸铅镧压电陶瓷粉末占浆料总质量的80%-90%,低粘度高固含丙烯酸树脂与稀释剂共占20%-10%,固化剂加入量是低粘度高固含丙烯酸树脂的1-1.5%,降粘剂加入量为改性锆钛酸铅镧压电陶瓷粉末的1-2%,低粘度高固含丙烯酸树脂与稀释剂的质量比为2:1-1:1;
(3)锆钛酸铅镧压电陶瓷热固化成型
将处理得到的热固化锆钛酸铅镧压电陶瓷浆料用粉末注射机注射到具有可调模温的模具中,在模具中热固化成型;
(4)锆钛酸铅镧压电陶瓷生坯后处理
将成型后的陶瓷生坯经脱脂、烧结处理、被银、极化后,即可得到致密性好、形状规则、性能良好的锆钛酸铅镧压电陶瓷;
脱脂在空气下进行,脱脂的温度为500℃-600℃,升温速率为0.5℃/min-1℃/min,达到设定脱脂温度保温90min-120min以后降温至室温;
烧结在空气下进行,升温速率为4℃/min-5℃/min,在烧结温度到达850℃时,保温90-120 min;最终烧结温度设定为1200℃-1285℃,当达到最终烧结温度保温60min-120min后降温至室温。
2.根据权利要求1所述的热固化粉末注射成型的锆钛酸铅镧压电陶瓷,其特征在于:步骤(3)注射成型模具温度设置150-160℃,成型时间为1 mm/min。
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