CN107488034A - 一种高锆含量的喂料及其制备方法 - Google Patents

一种高锆含量的喂料及其制备方法 Download PDF

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CN107488034A
CN107488034A CN201710740134.0A CN201710740134A CN107488034A CN 107488034 A CN107488034 A CN 107488034A CN 201710740134 A CN201710740134 A CN 201710740134A CN 107488034 A CN107488034 A CN 107488034A
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zirconium
colloidal sol
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oxide powder
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周涛
贺小亮
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Nantong Tongzhou Bay New Mstar Technology Ltd
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Abstract

本发明涉及了一种高氧化锆含量的喂料及其制备方法，该喂料含有纳米氧化锆粉体、聚锆溶胶以及高分子助剂，黏度在500Pa·s～1000Pa·s范围内。该喂料的制备方法特征如下：首先是以锆盐为原料，经醇解或水解以及聚合反应制得聚锆溶胶；然后加入一定量的高分子助剂，改善溶胶的黏度和流变性能；再加入一定量的钇稳定氧化锆粉体在溶胶中，搅拌分散；最后浓缩溶胶至所需要的黏度。本发明充分利用了聚锆溶胶的具有的流变特性，可减少后续成型加工过程中的高分子的用量，且喂料中锆含量高，从而可以提高制品密度，减少烧结过程中因大量收缩而引起的变形和精度下降。同时，由于该喂料在常温下就具有较好的流变特性，可以降低注射成型温度。

Description

一种高锆含量的喂料及其制备方法
技术领域
本发明涉及无机非金属材料领域，具体涉及一种高锆含量的喂料及其制备方法。
背景技术
氧化锆具有熔点和沸点高(熔点高达2680℃)、硬度大、常温下为绝缘体，而在高温下具有导电性、化学性质稳定、耐酸碱腐蚀(除HF、热浓H2SO4、H3PO4外)、机械性能好等诸多优点，在国防、电子、高温结构、功能陶瓷、医学齿科、表面涂层、燃料电池等高科技领域有重要应用价值。而且，随着智能手机的普及5G时代的即将来临，对电磁信号不屏蔽、支持无线充电、外形美观、手感温润、韧性好、强度高等很多物理性能决定了纳米氧化锆陶瓷更适合作为手机外壳的材质，甚至会成为智能手机外壳的主流配置。未来几年纳米氧化锆材料的需求量会大幅增长，其应用也将更加广泛。
纳米氧化锆粉体要做成各种形状的陶瓷制品，需要对对其进行成型加工。目前，陶瓷注射成型技术(CIM)是应用最广的陶瓷零部件精密制造技术，是在比较成熟的聚合物注射成型的基础上发展而来的，能生产复杂形状的制品，具有尺寸精度高、机加工量少、表面光洁、成本低、适合批量生产等优点。其中，喂料配方是陶瓷注射成型技术的核心和关键。通常会在粉体中加入黏结剂等高分子，使得粉末均匀地分布在高分子基体中，成为具有一定黏度和良好流动性、适合注射成型的喂料，并且能够赋予生胚制品足够的强度，使产品在烧结前具有完整的形状并具有一定的强度。
在采用陶瓷粉末注射成型技术制备陶瓷材料的过程中，由于加入了大量的高分子材料，使得制品烧结后尺寸收缩较大，尺寸难以控制，烧结胚体中也容易产生内应力，影响烧结体性能，所以一般在不影响成型的条件下要尽可能的提高粉末的含量，以减少因大量收缩而引起的变形和精度下降。将纳米氧化锆粉体加入聚锆溶胶中，可利用聚锆本身具有的流变特性，在添加少量高分子助剂的情况下即可达到注射成型要求，从而提高了喂料中的锆含量，有利于提高产品质量。同时，由于该喂料就具有较好的流变特性，可以降低注射成型温度。
发明内容
有鉴于此，本发明针对现有技术存在之缺失，其主要目的是提供一种高锆含量的喂料及其制备方法，该喂料含有纳米氧化锆粉体、聚锆溶胶以及其它助剂，黏度在500Pa·s～1000Pa·s范围内。该喂料的制备方法如下：首先是以锆盐为原料，经醇解或水解以及聚合反应制得聚锆溶胶；然后加入一定量的高分子助剂，改善溶胶的黏度和流变性能；再加入一定量的钇稳定氧化锆粉体在溶胶中，搅拌分散；最后浓缩溶胶至所需要的黏度。本发明充分利用了聚锆溶胶的具有的流变特性，减少了后续成型加工过程中的高分子的用量，喂料中锆含量高，从而可以提高制品密度，减少烧结过程中因大量收缩而引起的变形和精度下降。
为实现上述目的，本发明采用如下之技术方案：一种高氧化锆含量的喂料，含有纳米氧化锆粉体、聚锆溶胶以及高分子助剂，比例为纳米氧化锆粉体与聚锆溶胶中的锆元素摩尔比为(1～5):1，高分子助剂的添加量为喂料中氧化锆质量的0％～8％，黏度在500Pa·s～1000Pa·s范围内。
优选的，纳米氧化锆粉体为钇稳定纳米氧化锆粉体，钇含量为3％～8％，粉体粒径为30nm～80nm。
另一方面，本发明公开了一种高氧化锆含量的喂料的制备方法，包括以下步骤：
步骤A：将锆盐和溶剂搅拌混合后加入络合剂，再在室温至60℃条件下搅拌反应2h～8h，过滤除去沉淀，再陈化20h～24h得到聚锆溶胶；
步骤B：按纳米氧化锆粉体与聚锆溶胶中的锆元素摩尔比为(1～5):1的比例将纳米氧化锆粉体加入聚锆溶胶中混合；
步骤C：按照喂料中纳米氧化锆粉体质量的0％～8％的比例加入与聚锆溶胶溶剂相容的高分子助剂混合得到混合胶水；
步骤D：将步骤C得到的混合胶水升温至30℃～50℃减压蒸馏去除溶剂至其粘度在500Pa·s～1000Pa·s范围内。
优选的，步骤A中的锆盐和溶剂混合摩尔比为n(ZrO2):n(溶剂)＝1:(10～50)，搅拌混合温度为10℃～80℃，锆盐和络合剂的混合摩尔比为n(ZrO2):n(络合剂)＝1:(1～2)。
优选的，步骤A中所述的锆盐为碱式碳酸锆、氧氯化锆、无水四氯化锆、无水醋酸氧锆中的一种。
优选的，步骤A中所述的溶剂为甲醇、乙醇、异丙醇、水中的一种或它们的组合。
优选的，步骤B中所述的络合剂为冰醋酸、醋酸钠、醋酸钾、乙酰丙酮、乙酰乙酸乙酯中的一种。
优选的，步骤A中所述的高分子助剂为聚乙烯醇(PVA)、聚乙烯吡咯烷酮(PVP)、聚乙二醇(PEG)、聚丙烯酸(PAA)、聚环氧乙烷(PEO)、羟乙基纤维素(HEC)中的一种。
本发明的有益效果为：与现有的注射成型喂料相比，本发明将纳米氧化锆粉体加入聚锆溶胶中，可利用聚锆本身具有的流变特性，在不添加或少量添加少量高分子助剂的情况下即可达到注射成型要求，减少高分子助剂的用量。另一方面，由于高分子助剂含量少，喂料中锆含量高，减少制品烧结过程中的尺寸收缩和变形，有利于提高陶瓷制品的精度和良率。同时，由于该喂料在常温下就具有较好的流变特性，可以降低注射成型温度。
附图说明
图1为高锆含量的喂料的制备方法示意图。
具体实施方式
下面对本发明作进一步详细描述：
本发明采用如下之技术方案：一种高氧化锆含量的喂料，该喂料含有纳米氧化锆粉体、聚锆溶胶以及高分子助剂，氧化锆粉体与聚锆溶胶中的锆元素摩尔比为(1～5):1，高分子助剂的添加量为喂料中氧化锆质量的0％～8％，黏度在500Pa·s～1000Pa·s范围内。
在本实施例中所述的纳米氧化锆粉体为钇稳定纳米氧化锆粉体，钇含量为3％～5％，粉体粒径为20nm～80nm。
另一方面，本发明公开了一种高氧化锆含量的喂料的制备方法，包括以下步骤：
步骤A：将锆盐和溶剂搅拌混合后加入络合剂，再在室温至60℃条件下搅拌反应2h～8h，过滤除去沉淀，再陈化20h～24h得到聚锆溶胶；在本实例中锆盐和溶剂混合摩尔比为n(ZrO2):n(溶剂)＝1:(10～50)，搅拌混合温度为10℃～80℃，锆盐和络合剂的混合摩尔比为n(ZrO2):n(络合剂)＝1:(1～2)。在本实例中优选的锆盐为碱式碳酸锆、氧氯化锆、无水四氯化锆中的一种。在本实例中优选的溶剂为甲醇、乙醇、异丙醇、水中的一种或它们的组合。
步骤B：按纳米氧化锆粉体与聚锆溶胶中的锆元素摩尔比为(1～5):1的比例将纳米氧化锆粉体加入聚锆溶胶中混合；在本实例中络合剂为冰醋酸、醋酸钠、醋酸钾、乙酰丙酮、乙酰乙酸乙酯中的一种。
步骤C：按照喂料中纳米氧化锆粉体质量的0％～8％的比例加入与聚锆溶胶溶剂相容的高分子助剂混合得到混合胶水；在本实例中优选的高分子助剂为聚乙烯醇(PVA)、聚乙烯吡咯烷酮(PVP)、聚乙二醇(PEG)、聚丙烯酸(PAA)、聚环氧乙烷(PEO)中的一种。
步骤D：将步骤C得到的混合胶水升温至30℃～50℃减压蒸馏去除溶剂至其粘度在500Pa·s～1000Pa·s范围内。
以下是本发明的实施例：
实施例1
称取碱式碳酸锆308g(n(ZrO2)为2mol)，加入到360g去离子水(20mol)中，搅拌，并加入冰醋酸120g(2mol)。在室温下充分搅拌反应8h，陈化一段时间，得到醋酸聚锆溶胶。加入钇稳定纳米氧化锆粉体246g(2mol)，搅拌分散，使得氧化锆粉体均匀分散。升温至50℃，减压蒸馏除去部分水，浓缩至黏度为1000Pa·s左右的喂料。
实施例2
称取八水氧氯化锆322g((n(ZrO2)为1mol)，溶解在1000g甲醇(31mol)中。在搅拌中加入乙酰丙酮150g(1.5mol)与锆盐在40℃条件下反应6h。在反应过程中加入乙二胺120g(2mol)，除去反应生成的盐酸，得到盐酸乙二胺沉淀。过滤除去沉淀，滤液陈化一段时间得到乙酰丙酮聚锆溶胶。称取15g聚乙烯醇(PVA)加入到乙酰丙酮聚锆溶胶中，搅拌溶解。加入钇稳定氧化锆粉体369g(3mol)，搅拌分散，使得氧化锆粉体均匀分散。升温至30℃，减压蒸馏除去部分甲醇，浓缩至黏度为800Pa·s左右的喂料。
实施例3
称取八水氧氯化锆322g((n(ZrO2)为1mol)，溶解在1000g乙醇(22mol)中。在搅拌中加入乙酰丙酮150g(1.5mol)与锆盐在50℃条件下反应6h。在反应过程中加入乙二胺120g(2mol)，除去反应生成的盐酸，得到盐酸乙二胺沉淀。过滤除去沉淀，滤液陈化一段时间得到乙酰丙酮聚锆溶胶。称取25g聚环氧乙烷(PEO)加入到乙酰丙酮聚锆溶胶中，搅拌溶解。加入钇稳定氧化锆粉体369g(3mol)，搅拌分散，使得氧化锆粉体均匀分散。升温至40℃，减压蒸馏除去部分乙醇，浓缩至黏度为600Pa·s左右的喂料。
实施例4
称取八水氧氯化锆322g((n(ZrO2)为1mol)，溶解在1200g(20mol)异丙醇中，缓慢滴加30％的双氧水(n(H2O2)为3mol)除去生成的氯气。加入乙酰乙酸乙酯260g(2mol)，在60℃条件下搅拌反应6h，陈化一段时间，得到聚乙酰乙酸乙酯合锆溶胶。称取59g聚环氧乙烷(PEG)加入到聚乙酰乙酸乙酯合锆溶胶中，搅拌溶解。加入钇稳定氧化锆粉体615g(5mol)，搅拌分散，使得氧化锆粉体均匀分散。升温至50℃，减压蒸馏除去部分异丙醇，浓缩至黏度为500Pa·s左右的喂料。
实施例5
称取无水四氯化锆233g(1mol)溶解在1000g(31mol)无水甲醇中，形成四氯化锆甲醇溶液。另称取醋酸钾196g(2mol)溶解在1000g(31mol)无水甲醇中，形成醋酸钾甲醇溶液。将醋酸钾甲醇溶液加入到四氯化锆甲醇溶液中，室温下搅拌反应2h，有沉淀生成。反应结束后，减压抽滤除去沉淀。加入35g聚丙烯酸(PAA)，搅拌溶解。加入钇稳定氧化锆粉体369g(3mol)，搅拌分散，使得氧化锆粉体均匀分散。升温至30℃，减压蒸馏除去部分甲醇，浓缩至黏度为700Pa·s左右的喂料。
实施例6
称取无水四氯化锆233g(1mol)溶解在1000g(31mol)无水甲醇中，形成四氯化锆甲醇溶液。另称取醋酸钠164g(2mol)溶解在1000g(31mol)无水甲醇中，形成醋酸钠甲醇溶液。将醋酸钠甲醇溶液加入到四氯化锆甲醇溶液中，室温下搅拌反应2h，有沉淀生成。反应结束后，减压抽滤除去沉淀。加入40g聚乙烯吡咯烷酮(PVP)，搅拌溶解。加入钇稳定氧化锆粉体492g(4mol)，搅拌分散，使得氧化锆粉体均匀分散。升温至30℃，减压蒸馏除去部分甲醇，浓缩至黏度为650Pa·s左右的喂料。
以上描述仅为本申请的较佳实施例以及对所运用技术原理的说明。本领域技术人员应当理解，本申请中所涉及的发明范围，并不限于上述技术特征的特定组合而成的技术方案，同时也应涵盖在不脱离所述发明构思的情况下，由上述技术特征或其等同特征进行任意组合而形成的其它技术方案。例如上述特征与本申请中公开的(但不限于)具有类似功能的技术特征进行互相替换而形成的技术方案。

Claims (8)

1.一种高氧化锆含量的喂料，其特征在于，该喂料含有纳米氧化锆粉体、聚锆溶胶以及高分子助剂，比例为纳米氧化锆粉体与聚锆溶胶中的锆元素摩尔比为(1～5):1，高分子助剂的添加量为喂料中氧化锆质量的0％～8％，粘度在500Pa·s～1000Pa·s范围内。
2.根据权利要求1所述的高氧化锆含量的喂料，其特征在于，纳米氧化锆粉体为钇稳定纳米氧化锆粉体，钇含量为3％～8％，粉体粒径为30nm～80nm。
3.一种高氧化锆含量的喂料的制备方法，包括以下步骤：
步骤A：将锆盐和溶剂搅拌混合后加入络合剂，再在室温至60℃条件下搅拌反应2h～8h，过滤除去沉淀，再陈化20h～24h得到聚锆溶胶；
步骤B：按纳米氧化锆粉体与聚锆溶胶中的锆元素摩尔比为(1～5):1的比例将纳米氧化锆粉体加入聚锆溶胶中混合；
步骤C：按照喂料中纳米氧化锆粉体质量的0％～8％的比例加入与聚锆溶胶溶剂相容的高分子助剂混合得到混合胶水；
步骤D：将步骤C得到的混合胶水升温至30℃～50℃减压蒸馏去除溶剂至其粘度在500Pa·s～1000Pa·s范围内。
4.根据权利要求3所述的高氧化锆含量的喂料的制备方法，其特征在于，步骤A中的锆盐和溶剂混合摩尔比为n(ZrO2):n(溶剂)＝1:(10～50)，搅拌混合温度为10℃～80℃，锆盐和络合剂的混合摩尔比为n(ZrO2):n(络合剂)＝1:(1～2)。
5.根据权利要求4所述的聚锆溶胶制备方法，其特征在于，步骤A中所述的锆盐为碱式碳酸锆、氧氯化锆、无水四氯化锆、无水醋酸氧锆中的一种。
6.根据权利要求5所述的聚锆溶胶制备方法，其特征在于，步骤A中所述的溶剂为甲醇、乙醇、异丙醇、水中的一种或它们的组合。
7.根据权利要求6所述的聚锆溶胶制备方法，其特征在于，步骤B中所述的络合剂为冰醋酸、醋酸钠、醋酸钾、乙酰丙酮、乙酰乙酸乙酯中的一种。
8.权利要求7所述的制备方法，其特征在于，步骤A中所述的高分子助剂为聚乙烯醇(PVA)、聚乙烯吡咯烷酮(PVP)、聚乙二醇(PEG)、聚丙烯酸(PAA)、聚环氧乙烷(PEO)、羟乙基纤维素(HEC)中的一种。
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1519406A (zh) * 2003-01-24 2004-08-11 中国科学院上海硅酸盐研究所 注射成型氧化锆制品的制作方法
CN101767988A (zh) * 2009-01-01 2010-07-07 黄石晨信光电有限责任公司 纳米ZrO2陶瓷插针毛坯及其制备方法
CN102923770A (zh) * 2012-09-10 2013-02-13 杭州培瑞科技有限公司 一种钇稳定纳米二氧化锆粉体的制备方法
CN103979982A (zh) * 2014-05-13 2014-08-13 中南大学 两步加入锆溶胶的锆质定径水口制备方法
CN104045360A (zh) * 2014-06-20 2014-09-17 廖文宏 一种精密陶瓷饰品的成型加工方法
CN105541324A (zh) * 2015-12-15 2016-05-04 东莞信柏结构陶瓷股份有限公司 手机外壳的制备方法
CN106313271A (zh) * 2016-09-14 2017-01-11 西安工业大学 一种制造氧化锆陶瓷义齿的工艺

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1519406A (zh) * 2003-01-24 2004-08-11 中国科学院上海硅酸盐研究所 注射成型氧化锆制品的制作方法
CN101767988A (zh) * 2009-01-01 2010-07-07 黄石晨信光电有限责任公司 纳米ZrO2陶瓷插针毛坯及其制备方法
CN102923770A (zh) * 2012-09-10 2013-02-13 杭州培瑞科技有限公司 一种钇稳定纳米二氧化锆粉体的制备方法
CN103979982A (zh) * 2014-05-13 2014-08-13 中南大学 两步加入锆溶胶的锆质定径水口制备方法
CN104045360A (zh) * 2014-06-20 2014-09-17 廖文宏 一种精密陶瓷饰品的成型加工方法
CN105541324A (zh) * 2015-12-15 2016-05-04 东莞信柏结构陶瓷股份有限公司 手机外壳的制备方法
CN106313271A (zh) * 2016-09-14 2017-01-11 西安工业大学 一种制造氧化锆陶瓷义齿的工艺

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
李树尘: "《材料工艺学》", 30 September 2000, 化学工业出版社 *
毕见强等: "《特种陶瓷工艺与性能》", 31 March 2008, 哈尔滨工业大学出版社 *
河北师范大学研究生教育学院: "《探索的历程-河北师范大学第四届研究生学术活动月优秀论文集》", 30 November 2007, 河北人民出版社 *
胡德昌等: "《现代工程材料手册》", 29 February 1992, 宇航出版社 *

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