CN111233468A - 结构件用钇稳定锆粉的制备方法 - Google Patents
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Abstract
本发明属于无机新材料技术领域,具体的涉及一种结构件用钇稳定锆粉的制备方法。氧氯化锆溶液、三氯化铈溶液和三氯化钇溶液按比例混合,加入有机酸生成凝胶,加入氨水溶液中和沉淀,经洗涤、过滤脱氯,将滤饼煅烧制得前驱体粉体,加入Fe2O3经球磨、砂磨粉碎,加入粘结剂等有机添加剂混合均匀后喷雾造粒干燥制得结构件用钇稳定锆粉。本发明所述的结构件用钇稳定锆粉的制备方法,工艺简便、收率高,生产出的粉体粒度分布均匀、流动性好、收缩率稳定、易成型、生坯强度高,可以对生坯和烧成品进行切、削、打孔等精细加工来生产强度高、稳定性好、结构复杂的陶瓷制品。
Description
技术领域
本发明属于无机新材料技术领域,具体的涉及一种结构件用钇稳定锆粉的制备方法。
背景技术
近几年来,我国锆行业发展迅猛,产能居世界第一位,技术水平也跻身于世界先进行列,氧化锆(ZrO2)在陶瓷、电子、珠宝、冶金工业、催化剂、医疗、汽车尾气净化等方面得到了广泛应用。以氧化锆为原料的锆系列产品被称为21世纪最有前途的高新材料之一。
钇稳定氧化锆是通过向氧化锆中加入稳定剂氧化钇来解决氧化锆制品不稳定、易发生相变的问题,现有生产工艺主要是物理混合法、共沉淀法、水解法、水热法等,其中物理混合法因氧化钇分布不均匀导致稳定性差,强度低;共沉淀法颗粒较粗、抗老化性不好;水热法、水解法生产周期长、能耗高。生产结构件用的粉体是上述钇稳定氧化锆加入粘合剂等添加剂后造粒干燥后制成的,普遍存在生坯不宜加工、烧结温度较高、制品表面有缺陷等缺点,制约了钇稳定氧化锆在精密陶瓷结构件上的应用。
专利CN 107628643中公开了一种纳米钇稳定氧化锆粉体的制备方法,通过将氧氯化锆、氧化钇、去离子水按照质量比(50~60):(0.8~1):(10~12)混合,加热至90~110℃,保温1~3小时;加入植物胶,然后再加入乙二胺四乙酸或者柠檬酸中的至少一种,搅拌3-5h,生成胶体溶液;加入氨水溶液同时搅拌,搅拌8-10h,至pH=10.0-11.0,生成白色沉淀物,然后静置陈化24~48小时;将沉淀物洗涤,过滤,然后经喷雾干燥、气流粉碎,得到前驱体粉体;在450~600℃下煅烧5~7小时,即得到纳米钇稳定氧化锆粉体;该方法生产周期长,此种粉体制备的陶瓷制品抗老化性差。
专利CN 108975394中公开了一种钇掺杂氧化锆粉体及其制备方法,通过步骤A:将乙酸锆、乙酸钇和三氟乙酸的混合液加热至42-50℃后,进行减压蒸馏,得到凝胶;步骤B:在260~350℃氧气环境下将所述凝胶进行热解,得到钇掺杂氧化锆的前驱体;步骤C:在水蒸气环境中煅烧所述钇掺杂氧化锆的前驱体。该方法存在原料不易采购以及制备过程能耗高的缺陷。
发明内容
本发明的目的是:提供一种结构件用钇稳定锆粉的制备方法。通过该方法制备的钇稳定氧化锆粉体粒度分布均匀,分散性、稳定性、流动性好,适于干压、等静压成型,生坯强度高、可加工性好、烧结温度低,生产出的陶瓷制品性能优良,具有强度高、韧性好、颜色柔润均匀无缺陷、稳定性好等特点。
本发明所述的结构件用钇稳定锆粉的制备方法,由以下步骤组成:
(1)将氧氯化锆溶液、三氯化铈溶液和三氯化钇溶液混合,加入有机酸制备凝胶溶液;加入无机碱中和,中和产物处理后进行煅烧,制备得到前驱体粉体;
(2)向步骤(1)得到的前驱体粉体中加入Al2O3得干料,干料加水研磨得到浆料,向浆料中加入粘合剂和脱模剂进行造粒,即得到钇稳定氧化锆粉体。
其中:
步骤(1)中所述的氧氯化锆溶液以溶质氧化锆的质量计,三氯化钇溶液以溶质氧化钇的质量计,三氯化铈溶液以溶质氧化铈的质量计,氧化钇的质量占氧化锆、氧化钇和氧化铈质量和的3.0~7.0%,氧化铈的质量占氧化锆、氧化钇和氧化铈质量和的1.0~4.0%,余量为含有氧化铪的氧化锆进行混合;其中,含有氧化铪的氧化锆中氧化铪<2%。
步骤(1)中所述的有机酸为质量分数20%的2,4,5-三甲氧基苯甲酸或柠檬酸溶液中的一种;有机酸加入量以溶质质量计,为氧化锆和氧化钇两种氧化物总质量的10%。
步骤(1)中所述的于高压反应釜中加热至140-160℃,保温4-6小时,制备凝胶溶液。
步骤(1)中所述的无机碱为氨水或氢氧化钠溶液中的一种,优选氨水。
步骤(1)中所述的将中和产物在板框式过滤机上冲洗、过滤脱氯,将滤饼装入匣钵,于1100-1150℃的温度下煅烧2-3小时,制备得到前驱体粉体。
步骤(2)中所述的Al2O3加入量为干料质量的0.20-0.50%;干料是前驱体粉体和Al2O3的混合物,以质量百分数计,干料化学组成如下:Y2O3 3.0~7.0%、Al2O3 0.20~0.50%、CeO2 1.0~4.0%,余量为含有氧化铪的氧化锆。
步骤(2)中所述的加水进行研磨,加水量与干料比为1:1,首先在球磨机中粉碎至D50为1.00~1.20μm,停止粉碎,将浆料打入砂磨机中,研磨至D50为0.40~0.60μm。
步骤(2)中所述的粘合剂是聚乙烯醇、聚乙二醇、丙三醇和聚丙烯酸胺的混合物,脱模剂为水溶性蜡乳液和羧甲基纤维素钠的混合物;其中:聚乙烯醇是聚乙烯醇PVA17-99和PVA17-88的混合物。
钇稳定氧化锆粉体是干料、粘合剂和脱模剂的混合物;以质量百分数计,钇稳定氧化锆粉体包含以下原料组成:聚乙烯醇PVA17-99 0.8~1.0%,聚乙烯醇PVA17-88 0.4~0.5%,聚乙二醇PEG-400 0.3~0.5%,丙三醇0.1~0.2%,水溶性蜡乳液0.2%,聚丙烯酸铵0.1~0.2%,羧甲基纤维素钠0.2~0.4%。
步骤(2)中所述搅拌24小时,混合均匀后进行喷雾造粒、干燥,喷干塔入口温度230-250℃,出口温度130-140℃,得到钇稳定氧化锆粉体平均粒径为70~100μm。
本发明所述的结构件用钇稳定锆粉的制备方法,氧氯化锆溶液、三氯化铈溶液和三氯化钇溶液按比例混合,加入有机酸生成凝胶,加入氨水或氢氧化钠溶液中和沉淀,经洗涤、过滤脱氯,将滤饼煅烧制得前驱体粉体,加入Al2O3经球磨、砂磨粉碎,加入粘合剂和脱模剂等有机添加剂混合均匀后喷雾造粒干燥制得结构件用钇稳定锆粉。
作为一个优选的技术方案,本发明所述的结构件用钇稳定锆粉的制备方法,由以下步骤组成:
(1)前驱体的制备
将氧氯化锆溶液和三氯化钇溶液、三氯化铈溶液按氧化钇浓度3.0~7.0%、氧化铈浓度为1.0~4.0%、余量为含有氧化铪的氧化锆混合,加入一定量的有机酸溶液,在反应釜中加热到150℃,保温5小时,形成凝胶溶液,再加入氨水中和,将中和产物在板框式过滤机上冲洗、过滤脱氯,将滤饼装入匣钵,在1100-1150℃下煅烧2-3小时,生产出前驱体粉体。
(2)钇稳定锆粉的制备
在前驱体粉体中加入0.2-0.5%的Al2O3,在球磨机中粉碎至D50约1.00~1.20μm,再转移到砂磨机中,研磨至D50为0.40~0.60μm,将磨好的浆料转移到搅拌罐中,加入已经溶解好的聚乙烯醇PVA17-99(按固含量0.8~1.0%加入)、PVA17-88(按固含量0.4~0.5%加入)、聚乙二醇PEG-400(按固含量0.3~0.5%加入)、丙三醇(按固含量0.1~0.2%加入)、水溶性蜡乳液(按固含量0.2%加入)、聚丙烯酸铵(按固含量0.1~0.2%加入)、羧甲基纤维素钠(CNC,按固含量0.2~0.4%加入),搅拌24hr,混合均匀后进行喷雾造粒干燥,造粒颗粒平均粒径为70~100μm。
采用本发明所述的结构件用钇稳定锆粉的制备方法制备的钇稳定锆粉,其比表面积7.5~9.0m2/g,堆积密度1.25~1.35g/ml3,1450℃烧结成陶瓷制品,密度≥6.05g/ml3,抗折强度≥80kg/mm2,色差测定L值大于85。
采用本发明所述的结构件用钇稳定锆粉的制备方法制备的钇稳定锆粉,是能用来干压或等静压成型制造各种结构陶瓷制品的钇稳定氧化锆粉。
本发明与现有技术相比,具有以下有益效果:
(1)本发明所述的结构件用钇稳定锆粉的制备方法,工艺简便、收率高,生产出的粉体粒度分布均匀、流动性好、收缩率稳定、易成型、生坯强度高,可以对生坯和烧成品进行切、削、打孔等精细加工来生产强度高、稳定性好、结构复杂的陶瓷制品。
(2)本发明所述的结构件用钇稳定锆粉的制备方法,解决了现有技术中氧化锆陶瓷制品不易成型、加工困难、强度低、韧性差、易老化等问题。
附图说明
图1是结构件用钇稳定锆粉制备工艺流程图。
具体实施方式
以下结合实施例对本发明作进一步描述。
实施例1
本实施例1所述的氧化钇含量2.8mol的结构件用钇稳定锆粉的制备方法,由以下步骤组成:
①八水合氧氯化锆溶液配制
称取氧化锆含量为36.00%的八水合二氯氧化锆(ZrOCl2·8H2O)2610kg,溶于9140L纯水中搅拌均匀,此溶液氧化锆浓度为8.0%;
②三氯化钇溶液与三氯化铈溶液的制备
将50kg三氧化二钇加入120kg浓度为30.00%的盐酸溶液中,搅拌溶解,加纯水108L,搅拌均匀,此溶液中三氯化钇浓度折合成三氧化二钇浓度为18.0%;将21.7kg三氯化铈(含7个结晶水)溶于87L纯水中,搅拌均匀,此溶液中三氯化铈浓度折合成氧浓度为20.0%;
③将配好的八水合氧氯化锆溶液、三氯化钇溶液与三氯化铈溶液注入反应釜,搅拌混合均匀,加入500kg含量20.0%的2,4,5-三甲氧基苯甲酸(苦杏仁酸)溶液,加热到145℃,保温6小时,冷至室温,加入3000kg浓度为30.0%的氨水溶液,生成沉淀,将沉淀搅拌均匀后注入板框过滤机,用纯水洗至滤出液氯离子含量小于0.005%,压滤;
④将滤饼装入刚玉匣钵,入窑炉在1130+10℃下煅烧2.5小时,生产出前驱体粉体;
⑤将298.5kg前驱体粉体、1.5kgAl2O3加入球磨机中,同时加入300m3纯水,磨至中位粒径(D50)约1.20μm时,停止粉碎,将浆料打入砂磨机中,继续研磨至中位粒径(D50)约0.45μm,转移到搅拌罐内,加入已经溶解好的聚乙烯醇PVA17-99约2.4kg(按固含量计,以下同)、PVA17-88约1.5kg、聚乙二醇PEG-400约0.9kg、丙三醇约0.6kg、水溶性蜡乳液0.6kg、聚丙烯酸铵0.6kg、羧甲基纤维素钠0.9kg,搅拌24小时,混合均匀后进行喷雾造粒干燥,喷干塔入口温度235℃,出口温度135℃,造粒颗粒平均粒径为80μm。
按此步骤生产的钇稳定锆粉,其流动性58s/100g、比表面积8.0m2/g、堆积密度1.30g/ml3、1450℃烧结密度6.05g/ml3、抗折强度95kg/mm2、1450℃收缩率77.8%、色差测试L值88,适用于等静压成型生产大型陶瓷结构件制品,其维氏硬度1400,耐磨性测试(执行标准GB/T 18301-2012)0.20cm3。
实施例2
本实施例2所述的氧化钇含量3.2mol的结构件用钇稳定锆粉的制备方法,由以下步骤组成:
①八水合氧氯化锆溶液配制
称取氧化锆含量为36.00%的八水合二氯氧化锆(ZrOCl2·8H2O)2592kg,溶于9070L纯水中搅拌均匀,此溶液氧化锆浓度为8.0%;
②三氯化钇溶液与三氯化铈溶液的制备
将57kg三氧化二钇加入125kg浓度为30.00%的盐酸溶液中,搅拌溶解,加纯水135L,搅拌均匀,此溶液中三氯化钇浓度折合成三氧化二钇浓度为18.0%;将21.7kg三氯化铈(含7个结晶水)溶于87L纯水中,搅拌均匀,此溶液中三氯化铈浓度折合成三氧化二钇浓度为20.0%;
③将配好的八水合氧氯化锆溶液\三氯化钇溶液与三氯化铈溶液注入反应釜,混匀,加入500kg含量20.0%的2,4,5-三甲氧基苯甲酸(苦杏仁酸)溶液,加热到145+15℃,保温4.5小时,冷至室温,加入3000kg浓度为30.0%的氨水溶液,生成沉淀,将沉淀搅拌均匀后注入板框过滤机,用纯水洗至滤出液氯离子含量小于0.005%,压滤;
④将滤饼装入刚玉匣钵,入窑炉在1120+30℃下煅烧2.5小时,生产出前驱体粉体;
⑤将298.5kg前驱体粉体、1.5kgAl2O3加入球磨机中,同时加入300m3纯水,磨至中位粒径(D50)约1.20μm时,停止粉碎,将浆料打入砂磨机中,继续研磨至中位粒径(D50)约0.5μm,转移到搅拌罐内,加入已经溶解好的聚乙烯醇PVA17-99约3.0kg(按固含量计,以下同)、PVA17-88约1.2kg、聚乙二醇PEG-400约1.5kg、丙三醇约0.3kg、水溶性蜡乳液0.6kg、聚丙烯酸铵0.3kg、羧甲基纤维素钠0.6kg,搅拌24小时,混合均匀后进行喷雾造粒干燥,喷干塔入口温度240+10℃,出口温度135℃,造粒颗粒平均粒径为70μm。
按此步骤生产的钇稳定锆粉,其流动性60s/100g、比表面积8.0m2/g、堆积密度1.35g/ml3、1450℃烧结密度6.05g/ml3、抗折强度90kg/mm2、1450℃收缩率77.7%、色差测试L值88,用该类粉体生产的小型陶瓷结构件制品易成型、易烧结,维氏硬度1380,耐磨性测试(执行标准GB/T 18301-2012)0.21cm3。
实施例3
本实施例3所述的氧化钇含量2.1mol的结构件用钇稳定锆粉的制备方法,由以下步骤组成:
按照如下步骤生产:
①水合氧氯化锆溶液配制
称取氧化锆含量为36.00%的八水合二氯氧化锆(ZrOCl2·8H2O)2617kg,溶于9158L纯水中搅拌均匀,此溶液氧化锆浓度为18.0%;
②氯化钇溶液与三氯化铈溶液的制备
将38kg三氧化二钇加入95kg浓度为30.00%的盐酸溶液中,搅拌溶解,加纯水78L,搅拌均匀,此溶液中三氯化钇浓度折合成三氧化二钇浓度为18.0%;将43.14kg三氯化铈(含7个结晶水)溶于174L纯水中,搅拌均匀,此溶液中三氯化铈浓度折合成三氧化二钇浓度为20.0%;
③将配好的八水合氧氯化锆溶液\三氯化钇溶液与三氯化铈溶液注入反应釜,混匀,加入500kg含量20.0%的2,4,5-三甲氧基苯甲酸(苦杏仁酸)溶液,加热到150+5℃,保温5小时,冷至室温,加入3000kg浓度为30.0%的氨水溶液,生成沉淀,将沉淀搅拌均匀后注入板框过滤机,用纯水洗至滤出液氯离子含量小于0.005%,压滤;
④滤饼装入刚玉匣钵,入窑炉在1130+20℃下煅烧2.5小时,生产出前驱体粉体;
⑤将299.1kg前驱体粉体、0.9kgAl2O3加入球磨机中,同时加入300m3纯水,磨至中位粒径(D50)约1.20μm时,停止粉碎,将浆料打入砂磨机中,继续研磨至中位粒径(D50)约0.5μm,转移到搅拌罐内,加入已经溶解好的聚乙烯醇PVA17-99约2.7kg(按固含量计,以下同)、PVA17-88约1.5kg、聚乙二醇PEG-400约1.2kg、丙三醇约0.3kg、水溶性蜡乳液0.6kg、聚丙烯酸铵0.3kg、羧甲基纤维素钠1.2kg,搅拌24小时,混合均匀后进行喷雾造粒干燥,喷干塔入口温度250℃,出口温度140℃,造粒颗粒平均粒径为75μm。
按此步骤生产的钇稳定锆粉,其流动性60s/100g、比表面积8.0m2/g、堆积密度1.35g/ml3、1450℃烧结密度6.05g/ml3、抗折强度120kg/mm2、1450℃收缩率77.7%、色差测试L值86,用该类粉体生产的陶瓷板制品易成型、生坯强度高、烧结不变形,维氏硬度1350,耐磨性测试(执行标准GB/T 18301-2012)0.21cm3。
Claims (10)
1.一种结构件用钇稳定锆粉的制备方法,其特征在于:由以下步骤组成:
(1)将氧氯化锆溶液、三氯化铈溶液和三氯化钇溶液混合,加入有机酸制备凝胶溶液;加入无机碱中和,中和产物处理后进行煅烧,制备得到前驱体粉体;
(2)向前驱体粉体中加入Al2O3得干料,干料加水研磨得到浆料,向浆料中加入粘合剂和脱模剂进行造粒,即得到钇稳定氧化锆粉体。
2.根据权利要求1所述的结构件用钇稳定锆粉的制备方法,其特征在于:步骤(1)中所述的氧氯化锆溶液以溶质氧化锆的质量计,三氯化钇溶液以溶质氧化钇的质量计,三氯化铈溶液以溶质氧化铈的质量计,氧化钇的质量占氧化锆、氧化钇和氧化铈质量和的3.0~7.0%,氧化铈的质量占氧化锆、氧化钇和氧化铈质量和的1.0~4.0%,余量为含有氧化铪的氧化锆进行混合。
3.根据权利要求1所述的结构件用钇稳定锆粉的制备方法,其特征在于:步骤(1)中所述的有机酸为质量分数20%的2,4,5-三甲氧基苯甲酸或柠檬酸溶液中的一种;有机酸加入量以溶质质量计,为氧化锆和氧化钇两种氧化物总质量的10%。
4.根据权利要求1所述的结构件用钇稳定锆粉的制备方法,其特征在于:步骤(1)中所述的于高压反应釜中加热至140-160℃,保温4-6小时,制备凝胶溶液。
5.根据权利要求1所述的结构件用钇稳定锆粉的制备方法,其特征在于:步骤(1)中所述的无机碱为氨水或氢氧化钠中的一种。
6.根据权利要求1所述的结构件用钇稳定锆粉的制备方法,其特征在于:步骤(1)中所述的将中和产物在板框式过滤机上冲洗、过滤脱氯,将滤饼装入匣钵,于1100-1150℃的温度下煅烧2-3小时,制备得到前驱体粉体。
7.根据权利要求1所述的结构件用钇稳定锆粉的制备方法,其特征在于:干料是前驱体粉体和Al2O3的混合物,步骤(2)中所述的Al2O3加入量为干料质量的0.20-0.50%;以质量百分数计,干料化学组成如下:Y2O3 3.0~7.0%、Al2O3 0.20~0.50%、CeO2 1.0~4.0%,余量为含有氧化铪的氧化锆。
8.根据权利要求1所述的结构件用钇稳定锆粉的制备方法,其特征在于:步骤(2)中所述的干料加水进行研磨,首先在球磨机中粉碎至D50为1.00~1.20μm,停止粉碎,将浆料打入砂磨机中,研磨至D50为0.40~0.60μm。
9.根据权利要求1所述的结构件用钇稳定锆粉的制备方法,其特征在于:步骤(2)中所述的粘合剂是聚乙烯醇、聚乙二醇、丙三醇和聚丙烯酸胺的混合物,脱模剂为水溶性蜡乳液和羧甲基纤维素钠的混合物;其中:聚乙烯醇是聚乙烯醇PVA17-99和PVA17-88的混合物。
10.根据权利要求1所述的结构件用钇稳定锆粉的制备方法,其特征在于:钇稳定氧化锆粉体是干料、粘合剂和脱模剂的混合物;以质量百分数计,钇稳定氧化锆粉体包含以下原料组成:聚乙烯醇PVA17-99 0.8~1.0%,聚乙烯醇PVA17-88 0.4~0.5%,聚乙二醇PEG-4000.3~0.5%,丙三醇0.1~0.2%,水溶性蜡乳液0.2%,聚丙烯酸铵0.1~0.2%,羧甲基纤维素钠0.2~0.4%。
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