CN106747480A - 一种利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法 - Google Patents
一种利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法 Download PDFInfo
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- CN106747480A CN106747480A CN201611144381.6A CN201611144381A CN106747480A CN 106747480 A CN106747480 A CN 106747480A CN 201611144381 A CN201611144381 A CN 201611144381A CN 106747480 A CN106747480 A CN 106747480A
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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Abstract
本发明公开了一种利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法，其包括如下步骤：首先将陶瓷粉体、分散剂、金属氧化物助烧剂和水混合并充分球磨，得到颗粒表面带负电的陶瓷浆料；然后将浆料真空搅拌除气后加入酯类pH调节剂，搅拌均匀后注入模具中，在35℃～70℃放置1～5小时后脱模得到陶瓷湿坯，干燥后得到干坯；然后烧结得到陶瓷烧结体。本发明通过温度控制酯类pH调节剂分解出酸与浆料中的助烧剂反应释放高价反离子，实现陶瓷浆料的直接凝固成型。采用该方法制备的素坯均匀性好，加入助烧剂可有效降低烧结温度、提高烧结件致密度和综合力学性能，具有适合任何带负电的陶瓷浆料，环境友好，操作简单，便于规模化生产等优点。
Description
技术领域
本发明属于无机非金属陶瓷浆料固化技术领域，更具体地，涉及一种利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法。
背景技术
直接凝固注模成型工艺(Direct Coagulation Casting，DCC)是通过尿素酶催化尿素使浆料的pH值调节至等电点导致颗粒间排斥能减小，或者增加与颗粒表面电荷相反的离子(反离子)浓度，通过反离子压缩陶瓷颗粒表面的双电子层缩短颗粒间距最终实现不同陶瓷浆料的原位固化。该工艺具有有机添加剂很少、坯体不需排胶、坯体密度均匀等优点，可成型形状复杂、高可靠性的陶瓷部件。但该法成型过程中陶瓷浆料固化时间较长(1～3天)，容易产生裂纹等；制备的陶瓷湿坯强度较低(～100kPa)，不便脱模及后期处理。
根据DLVO理论及Schulze-Hardy电价规则，清华大学的杨金龙教授课题组提出了一种新型的胶态成型方法，即陶瓷高价反离子直接凝固注模成型工艺(DirectCoagulation Casting via high valence counter ions，DCC-HVCI)，利用高价反离子对陶瓷浆料明显的聚沉作用使陶瓷浆料原位固化。该方法制备的陶瓷湿坯强度较高(1～3MPa)、固化时间较短(1～6h)，不易产生裂纹，但在该方法中用以提供高价反离子的固化剂通常为碘酸钙、柠檬酸钙、柠檬酸镁和磷酸钙等无机盐粉体，其对陶瓷体系本身的影响尚不明确，且固化剂加入后混合时间较短(～15min)，固化剂与陶瓷粉体混合不均导致浆料不能够固化均匀，严重影响陶瓷烧结件的最终性能。
发明内容
针对现有技术的以上缺陷或改进需求，本发明的目的在于提供一种利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法，其中通过对关键的固化工艺原理、以及各个反应参数(例如，温度敏感的酯类pH调节剂的种类、添加比例、作用方式，以及陶瓷浆料的组成配比等)进行改进，与现有技术相比能够有效解决陶瓷浆料固化时间长、得到的陶瓷湿坯强度低，又或引入其他杂质、以及固化均匀性不高的问题，本发明通过温度控制酯类pH调节剂分解出酸与陶瓷浆料中的金属氧化物助烧剂发生化学反应释放出高价反离子，实现陶瓷浆料的直接凝固成型，能够避免固化过程中杂质的引入，同时避免固化剂与陶瓷粉体混合不均导致的浆料固化不均匀等问题；并且，本发明以助烧剂提供陶瓷浆料固化所需的高价反离子，不仅可以实现浆料的均匀固化，还可以有效降低烧结温度、提高陶瓷致密度和综合力学性能。
为实现上述目的，按照本发明，提供了一种利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法，其特征在于，包括以下步骤：
(1)将陶瓷粉体、分散剂、金属氧化物助烧剂和水通过球磨混合均匀，以制备陶瓷粉体颗粒表面带负电的陶瓷浆料；
(2)将所述步骤(1)得到的所述陶瓷浆料在真空条件下搅拌除气，接着，向所述陶瓷浆料中加入酯类pH调节剂，然后搅拌均匀；
(3)将所述步骤(2)得到的所述陶瓷浆料注入模具中，然后控制所述陶瓷浆料的温度，接着脱模即得到陶瓷湿坯；然后，将所述陶瓷湿坯进行干燥处理即得到陶瓷干坯；
(4)将所述步骤(3)得到的所述陶瓷干坯进行烧结处理，从而得到陶瓷烧结体。
作为本发明的进一步优选，所述步骤(1)中，所述陶瓷粉体为氧化铝、氧化锆、二氧化硅、高岭土、锆钛酸铅、氮化硅、碳化硅和碳化钛中的至少一种；优选的，所述分散剂为柠檬酸铵、聚丙烯酸铵、四甲基氢氧化铵和多聚磷酸铵中的至少一种；优选的，所述金属氧化物助烧剂为氧化镁、氧化钇、氧化铜和三氧化二铁中的至少一种。
作为本发明的进一步优选，所述步骤(1)中，所述陶瓷粉体占所述陶瓷浆料的固相体积分数为50％～60％，所述分散剂的质量为所述陶瓷粉体质量的0.1％～1.5％；优选的，所述金属氧化物助烧剂的质量为所述陶瓷粉体质量的0.02％～2.00％。
作为本发明的进一步优选，所述步骤(1)中，所述陶瓷浆料是通过球磨混合处理得到的；优选的，所述球磨混合处理的球磨速率为200～400r/min，球磨时间为0.5～1.5h。
作为本发明的进一步优选，所述步骤(2)中，所述酯类pH调节剂的添加体积为陶瓷浆料体积的0.5％～3.0％；优选的，所述酯类pH调节剂为二乙酸甘油酯、三乙酸甘油酯、乳酸乙酯和乙酸乙酯中的至少一种。
作为本发明的进一步优选，所述步骤(2)中，所述搅拌除气的时间为10～30min；加入所述酯类pH调节剂后的所述搅拌是利用玻璃棒搅拌10～30s。
作为本发明的进一步优选，所述步骤(3)中，所述模具为无孔模具；所述控制陶瓷浆料的温度具体是将注入有所述陶瓷浆料的所述模具进行水浴处理从而控制温度；优选的，所述水浴处理的水浴温度为35℃～70℃，水浴时间为1～5h。
作为本发明的进一步优选，所述步骤(3)中，所述干燥处理是将所述陶瓷湿坯在60～90℃条件下干燥24～48h。
作为本发明的进一步优选，所述步骤(4)中，所述烧结处理具体是将所述陶瓷干坯升温至1250℃～2200℃进行保温；优选的，所述升温的升温速率为3℃～6℃/min，所述保温的保温时间为4～8h。
通过本发明所构思的以上技术方案，与现有技术相比，由于利用温度控制酯类pH调节剂分解出酸与陶瓷浆料中的金属氧化物助烧剂发生化学反应释放出高价反离子压缩陶瓷颗粒表面的双电子层，实现陶瓷浆料的直接凝固成型。采用该方法制备的素坯均匀性好，由于助烧剂的加入还能够有效降低烧结温度、提高烧结件致密度和综合力学性能，尤其适用于带负电的陶瓷浆料的固化，并具有环境友好，操作简单，便于规模化生产等优点。
本发明先利用陶瓷粉体、分散剂、金属氧化物助烧剂和水混合得到陶瓷浆料，陶瓷浆料中陶瓷粉体颗粒表面带负电；然后，利用温度控制酯类pH调节剂分解出酸与陶瓷浆料中的金属氧化物助烧剂发生化学反应释放出高价反离子压缩陶瓷颗粒表面的双电子层，实现陶瓷浆料的直接凝固成型。本发明中的酯类pH调节剂是利用酯类发生水解反应生成相应的酸(由于起到调节pH值的作用，因此被称作酯类pH调节剂)，并且，酯类的分解速率随温度的升高而加快，从而能够利用简单的温度控制调节其分解速率；酯类pH调节剂分解出的酸与金属氧化物助烧剂反应来释放出高价反离子以增强浆料中的高价反离子浓度，通过调节温度，可有效控制酯类pH调节剂分解出酸的量，从而最终影响陶瓷浆料的固化速率。此外，本发明中未反应的酯类、以及酯的反应副产物，能通过干燥、以及烧结等高温条件去除，能够减少最终得到的陶瓷烧结体中所引入的杂质。
总体而言，通过本发明所构思的以上技术方案与现有技术相比，主要具备以下的技术优点：
1.本发明提供一种温度控制酯类pH调节剂分解出酸与陶瓷浆料中的金属氧化物助烧剂发生化学反应释放出高价反离子，实现陶瓷浆料的直接凝固成型。
2.本发明采用助烧剂提供高价反离子，避免了影响尚不明确的杂质元素的引入，既可以有效地固化陶瓷浆料，又可以降低烧结温度，提高烧结件致密度和综合力学性能。
3.本发明中陶瓷粉体与助烧剂充分混合均匀，可以实现陶瓷浆料的均匀固化，有效提高陶瓷素坯的均匀性。
4.本发明与传统直接凝固注模成型工艺相比，固化时间短，无需添加有机物，避免排胶引起的变形、开裂等缺陷。
5.本发明制备得到的陶瓷干坯密度为理论密度的51.8％～62.0％，收缩率为2.2％～3.8％，陶瓷烧结体的密度大于理论密度的99％，收缩率16％～19.2％。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
本发明提供的利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法，具体为一种通过温度控制酯类pH调节剂分解出酸，以二乙酸甘油酯为例，其化学式如方程式(1)所示，升高温度，促进二乙酸甘油酯的分解，有利于乙酸的生成：
酯类pH调节剂分解出的酸与金属氧化物助烧剂发生化学反应释放出高价金属阳离子(即高价反离子)，增加浆料中的高价反离子浓度，以实现陶瓷浆料的原位固化，以氧化镁和乙酸为例，其化学式如方程式(2)所示，生成的乙酸镁易溶于水，从而增加陶瓷浆料中的镁离子浓度：
MgO+2CH3COOH→Mg(CH3COOH)2+2H2O (2)。
综上所述，本发明通过温度控制酯类pH调节剂分解出酸与陶瓷浆料中的金属氧化物助烧剂发生化学反应释放出高价反离子压缩陶瓷颗粒表面的双电子层，实现陶瓷浆料的直接凝固成型，本发明采用的方法具有素坯均匀性较好，降低烧结温度，提高烧结件致密度和综合力学性能较好，操作简单等优点。
本发明主要包括以下步骤：
(1)将陶瓷粉体、分散剂、金属氧化物助烧剂和水通过球磨混合均匀，以制备颗粒表面带负电的陶瓷浆料，其中，陶瓷粉体的固相体积分数为50％～60％，分散剂质量占陶瓷粉体质量的0.1％～1.5％。上述陶瓷粉体的固相体积分数选择50％～60％，一方面，保证陶瓷浆料的高固相含量要求，有益于提高素坯与烧结件的致密性；另一方面，保证陶瓷浆料的低粘度要求，有益于陶瓷浆料除气和注模工艺。分散剂含量选择0.1％～1.5％有益于保证陶瓷浆料的低粘度。
具体的，陶瓷粉体优选为氧化铝、氧化锆、二氧化硅、高岭土、锆钛酸铅、氮化硅、碳化硅和碳化钛中的一种或多种，分散剂可选用柠檬酸铵、聚丙烯酸铵、四甲基氢氧化铵或多聚磷酸铵的一种或多种，金属氧化物助烧剂优选为氧化镁、氧化钇、氧化铜或三氧化二铁中的一种或多种。
进一步的，所述的金属氧化物助烧剂加入量优选为陶瓷粉体质量的0.02％～2.00％，在该范围内，既可以达到陶瓷浆料固化所需的高价反离子浓度要求，又可以避免助烧剂加入量过大引起的浆料粘度增大问题。
进一步的，所述的球磨速率为200～400r/min，球磨时间为0.5～1.5h，在该球磨工艺下制备的陶瓷浆料的均匀性较好且浆料的制备效率较高。
(2)将步骤(1)中球磨后得到的陶瓷浆料真空条件下搅拌除气10～30min，通过搅拌除气10～30min既可有效去除陶瓷浆料中的气泡，又可避免烧结过程中气孔和裂纹的产生，有利于增加烧结件的致密性；然后加入酯类pH调节剂，利用玻璃棒搅拌均匀，酯类pH调节剂可选为二乙酸甘油酯、三乙酸甘油酯、乳酸乙酯或乙酸乙酯中的一种或多种，酯类pH调节剂添加的体积为陶瓷浆料体积的0.5％～3.0％。上述酯类pH调节剂的分解速率随温度的升高而加快(水浴过程中随着温度的升高，酯类pH调节剂的分解速率不断加快)，通过调节温度控制酯类pH调节剂分解出酸。
具体的，玻璃棒均匀搅拌时间10～30s，缓慢搅拌至酯类pH调节剂分散均匀且不带入气泡到浆料中。
(3)将步骤(2)中得到的陶瓷浆料注入无孔模具中，水浴处理时，通过温度控制酯类pH调节剂分解出酸与金属氧化物助烧剂发生化学反应释放出高价反离子压缩陶瓷颗粒表面双电子层，实现陶瓷浆料的固化成型，脱模后得到陶瓷湿坯，在60～90℃条件下干燥24～48h，在该工艺下可缓慢有效地排除湿坯中的水分，得到干坯。
进一步的，所述水浴温度为35～70℃，水浴时间为1～5h，在该工艺下可实现酯类pH调节剂的有效分解，分解所得的酸与金属氧化物助烧剂充分反应释放出高价反离子压缩陶瓷颗粒表面双电子层，以实现陶瓷浆料的固化成型，并可有效改善成型素坯成分不均的现象。
(4)将步骤(3)得到的陶瓷干坯置于烧结炉中，升温至1250℃～2200℃后保温，得到陶瓷烧结体。其中，升温速率为3℃～6℃/min，保温时间优选为4～8h。在该工艺下既可有效避免干坯在烧结过程中由于升温速率过快引起的变形和开裂现象，又有益于保温过程中的颗粒重排和物质充分扩散，然后得到陶瓷烧结体。
以下为具体实施例：
实施例1：
0.7wt％氧化镁、2.0vol％二乙酸甘油酯固化0.2wt％柠檬酸铵分散的50vol％氧化铝浆料。
将50克氧化铝粉体、0.35克氧化镁、0.1克柠檬酸铵和12.6克水混合，在250r/min的球磨速率下球磨1.0小时后制备得固相体积分数为50％的颗粒表面带负电的陶瓷浆料，然后真空条件下搅拌除气20分钟，再加入0.68毫升二乙酸甘油酯，玻璃棒搅拌30秒后注模，在70℃温度下放置1小时后脱模，在90℃下干燥24小时，再以3℃/min的升温速率升温到1550℃保温4小时烧结。得到陶瓷干坯的相对理论密度为51.3％，收缩率为2.4％；得到陶瓷烧结件的相对理论密度为99.2％，收缩率为17.2％。
实施例2：
1.5wt％氧化镁、0.5vol％三乙酸甘油酯固化0.8wt％四甲基氢氧化铵分散的55vol％氧化锆浆料。
将50克氧化锆粉体、0.75克氧化镁、0.4克四甲基氢氧化铵和7.0克水混合，在400r/min的球磨速率下球磨0.5小时后制备得固相体积分数为55％的颗粒表面带负电的陶瓷浆料，然后真空条件下搅拌除气20分钟，再加入0.15毫升三乙酸甘油酯，玻璃棒搅拌15秒后注模，在35℃温度下放置5小时后脱模，在60℃下干燥48小时，再以6℃/min的升温速率升温到1450℃保温6小时烧结。得到陶瓷干坯的相对理论密度为56.7％，收缩率为2.4％；得到陶瓷烧结件的相对理论密度为99.4％，收缩率为18.4％。
实施例3：
1.0wt％氧化钇、3.0vol％乙酸乙酯固化0.2wt％四甲基氢氧化铵分散的50vol％氮化硅浆料。
将50克氮化硅粉体、0.5克氧化钇、0.1克四甲基氢氧化铵和15.7克水混合，在200r/min的球磨速率下球磨1.5小时后制备得固相体积分数为50％的颗粒表面带负电的陶瓷浆料，然后真空条件下搅拌除气10分钟，再加入0.47毫升乙酸乙酯，玻璃棒搅拌10秒后注模，在60℃温度下放置1小时后脱模，在80℃下干燥24小时，再以3℃/min的升温速率升温到1800℃保温8小时烧结。得到陶瓷干坯的相对理论密度为57.2％，收缩率为2.3％；得到陶瓷烧结件的相对理论密度为99.0％，收缩率为19.2％。
实施例4：
1.2wt％氧化铜、2.0vol％二乙酸甘油酯固化1.5wt％聚丙烯酸铵分散的50vol％高岭土浆料。
将50克高岭土粉体、0.6克氧化钇、0.75克聚聚丙烯酸铵和18.8克水混合，在300r/min的球磨速率下球磨1.0小时后制备得固相体积分数为50％的颗粒表面带负电的陶瓷浆料，然后真空条件下搅拌除气25分钟，再加入0.38毫升二乙酸甘油酯，玻璃棒搅拌30秒后注模，在70℃温度下放置1.5小时后脱模，在80℃下干燥48小时，再以5℃/min的升温速率升温到1580℃保温4小时烧结。得到陶瓷干坯的相对理论密度为62.0％，收缩率为2.9％；得到陶瓷烧结件的相对理论密度为99.1％，收缩率为18.7％。
实施例5：
0.5wt％氧化铁、1.5vol％乳酸乙酯固化0.3wt％柠檬酸铵分散的52vol％碳化硅浆料。
将50克碳化硅粉体、0.25克氧化铁、0.15克柠檬酸铵和14.4克水混合，在280r/min的球磨速率下球磨1.0小时后制备得固相体积分数为52％的颗粒表面带负电的陶瓷浆料，然后真空条件下搅拌除气30分钟，再加入0.22毫升乳酸乙酯，玻璃棒搅拌30秒后注模，在50℃温度下放置2.5小时后脱模，在70℃下干燥48小时，再以4℃/min的升温速率升温到1800℃保温8小时烧结。得到陶瓷干坯的相对理论密度为53.2％，收缩率为2.6％；得到陶瓷烧结件的相对理论密度为99.0％，收缩率为18.2％。
实施例6：
1.0wt％氧化镁、1.5vol％二乙酸甘油酯固化0.4wt％柠檬酸铵分散的60vol％氧化铝浆料。
将50克氧化铝粉体、0.5克氧化镁、0.2克柠檬酸铵和8.3克水混合，在250r/min的球磨速率下球磨1.5小时后制备得固相体积分数为60％的颗粒表面带负电的陶瓷浆料，然后真空条件下搅拌除气15分钟，再加入0.15毫升二乙酸甘油酯，玻璃棒搅拌15秒后注模，在70℃温度下放置1小时后脱模，在80℃下干燥24小时，再以3℃/min的升温速率升温到1550℃保温4小时烧结。得到陶瓷干坯的相对理论密度为56.1％，收缩率为2.2％；得到陶瓷烧结件的相对理论密度为99.3％，收缩率为17.9％。
本领域的技术人员容易理解，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、等同替换和改进等，均应包含在本发明的保护范围之内。
Claims (9)
1.一种利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法，其特征在于，包括以下步骤：
(1)将陶瓷粉体、分散剂、金属氧化物助烧剂和水通过球磨混合均匀，以制备陶瓷粉体颗粒表面带负电的陶瓷浆料；
(2)将所述步骤(1)得到的所述陶瓷浆料在真空条件下搅拌除气，接着，向所述陶瓷浆料中加入酯类pH调节剂，然后搅拌均匀；
(3)将所述步骤(2)得到的所述陶瓷浆料注入模具中，然后控制所述陶瓷浆料的温度，接着脱模即得到陶瓷湿坯；然后，将所述陶瓷湿坯进行干燥处理即得到陶瓷干坯；
(4)将所述步骤(3)得到的所述陶瓷干坯进行烧结处理，从而得到陶瓷烧结体。
2.如权利要求1所述利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法，其特征在于，所述步骤(1)中，所述陶瓷粉体为氧化铝、氧化锆、二氧化硅、高岭土、锆钛酸铅、氮化硅、碳化硅和碳化钛中的至少一种；
优选的，所述分散剂为柠檬酸铵、聚丙烯酸铵、四甲基氢氧化铵和多聚磷酸铵中的至少一种；
优选的，所述金属氧化物助烧剂为氧化镁、氧化钇、氧化铜和三氧化二铁中的至少一种。
3.如权利要求1所述利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法，其特征在于，所述步骤(1)中，所述陶瓷粉体占所述陶瓷浆料的固相体积分数为50％～60％，所述分散剂的质量为所述陶瓷粉体质量的0.1％～1.5％；优选的，所述金属氧化物助烧剂的质量为所述陶瓷粉体质量的0.02％～2.00％。
4.如权利要求1所述利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法，其特征在于，所述步骤(1)中，所述陶瓷浆料是通过球磨混合处理得到的；优选的，所述球磨混合处理的球磨速率为200～400r/min，球磨时间为0.5～1.5h。
5.如权利要求1所述利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法，其特征在于，所述步骤(2)中，所述酯类pH调节剂的添加体积为陶瓷浆料体积的0.5％～3.0％；优选的，所述酯类pH调节剂为二乙酸甘油酯、三乙酸甘油酯、乳酸乙酯和乙酸乙酯中的至少一种。
6.如权利要求1所述利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法，其特征在于，所述步骤(2)中，所述搅拌除气的时间为10～30min；加入所述酯类pH调节剂后的所述搅拌是利用玻璃棒搅拌10～30s。
7.如权利要求1所述利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法，其特征在于，所述步骤(3)中，所述模具为无孔模具；所述控制陶瓷浆料的温度具体是将注入有所述陶瓷浆料的所述模具进行水浴处理从而控制温度；优选的，所述水浴处理的水浴温度为35℃～70℃，水浴时间为1～5h。
8.如权利要求1所述利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法，其特征在于，所述步骤(3)中，所述干燥处理是将所述陶瓷湿坯在60～90℃条件下干燥24～48h。
9.如权利要求1所述利用温控缓释助烧剂中金属离子固化陶瓷浆料的方法，其特征在于，所述步骤(4)中，所述烧结处理具体是将所述陶瓷干坯升温至1250℃～2200℃进行保温；优选的，所述升温的升温速率为3℃～6℃/min，所述保温的保温时间为4～8h。
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| CN114133247A (zh) * | 2021-12-24 | 2022-03-04 | 武汉理工大学 | 一种改性SiC基太阳能热发电用储热陶瓷及其制备方法 |
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