CN113582694A - 一种采用Isobam体系凝胶注模成型钇铝石榴石型微波介质陶瓷的方法 - Google Patents
一种采用Isobam体系凝胶注模成型钇铝石榴石型微波介质陶瓷的方法 Download PDFInfo
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Abstract
本发明公开了一种采用Isobam体系凝胶注模成型钇铝石榴石型微波介质陶瓷的方法,先按照化学通式Y 3‑x Al 5‑y R z O12准备原料,将混合物与磨球、溶剂组成预混液,将所得混合浆料置于烘箱中烘干后,置于马弗炉中煅烧,过筛后与消泡剂一起加至Isobam溶液中,注入模具成型,凝胶固化,干燥后排胶,将排胶后的素坯烧结,然后退火,得到最终的微波介质陶瓷材料。本发明采用了Isobam凝胶体系,在恒温水浴的条件下搅拌混合陶瓷浆料来代替常用球磨方法,可高效解决坯体内部致密性不一致的问题,且设备简单,工艺过程可控,极大地提高了浆料的均匀性、分散性,制备出的高质量浆料有利于得到结构均匀性好的钇铝石榴石型陶瓷材料。
Description
技术领域
本发明属于微波介质陶瓷技术领域,具体涉及一种采用Isobam体系凝胶注模成型钇铝石榴石型微波介质陶瓷的方法。
背景技术
微波介质陶瓷是指应用于微波(300MHz~300GHz)频段电路中作为介质材料并完成一种或多种功能的陶瓷,是现代通信技术中的关键基础材料,被广泛应用于介质谐振器、滤波器、介质基片、介质波导回路、微波电容、双工器、天线等微波元器件。在高频微波电路中,许多微波器件需要使用介质陶瓷材料作为基板,使得微波陶瓷介质基板材料愈来愈成为微波器件、部件与整机系统中使用的关键性基础材料。陶瓷成型方法有很多种,但总体归纳起来可分为干法成型和湿法成型两种。依据不同粉料的自身要求选取不同的成型方法。凝胶注模成型方式是通过浆料内部的化学反应形成大分子网络结构或陶瓷颗粒网络结构,从而使注入模具内的陶瓷浆料快速凝固为陶瓷坯体,相对于注浆成型有着更为稳定的结构。
凝胶注模成型由美国橡树岭国家实验室研制开发成功。它是通过聚合反应形成的高分子网络固定住粉体颗粒,制备得到高强度的陶瓷,凝胶注模成型是继注浆成型、注射成型之后发展起来的一种近净尺寸成型工艺,与其他成型技术相比较,凝胶注模成型技术具有如下优点:可实现近净尺寸成型,可制备形状复杂的部件,素坯结构均匀机械强度高。因此,该凝胶注成型技术自提出至今的二十多年时间里,凝胶注模成型技术得到了充分地发展。一部分的工作致力于现有的凝胶体系在各种材料和不同领域里的应用,另一部分的研究工作针对基于自由基聚合的凝胶体系固有的不足,发展新型凝胶体系。
在新型凝胶体系研发上,日本可乐丽(Kuraray)株式会社研发出一种水溶性共聚物Isobam,它是异丁烯与马来酸酐的交替共聚物,是一种可溶于碱性水溶液的白色粉末状聚合物。在凝胶注模成型过程中只需添加少量,既作为分散剂又作为交联剂。王锋等人(无机材料学报,2014,31 (3):305-310)以Isobam作为交联剂,聚甲基丙烯酸甲酯(PMMA)作为泡沫稳定剂和造孔剂,结合固相烧结制备出具有多级孔结构的碳化硅陶瓷,并研究了PMMA添加量、球磨机转速以及烧结温度对多孔陶瓷结构及性能的影响。舒夏等人(无机材料学报,2014,29 (3):327-330)通过采用Isobam作为交联剂添加到AIN陶瓷浆料中,可在室温空气中自发凝胶成型,制备出鳍状,高热导率的AIN陶瓷。
可见Isobam凝胶体系能满足制备高致密度陶瓷素坯的需求,同时其原料无毒,对环境友好,添加种类和用量都较少,所需设备简单,无特殊环境要求,在常温下工艺稳定,可重复性强,操作简单。然而,目前此种凝胶体系并未在制备钇铝石榴石型微波介质陶瓷中使用,而以Isobam凝胶体系制备钇铝石榴石型微波介质陶瓷,有着诸多优点,可以有效解决坯体内部致密性不一致的问题,使其投入大规模工业生产,因此采用了Isobam凝胶体系来制备钇铝石榴石型微波介质陶瓷。
发明内容
本发明为了解决现有技术中素坯分散不均匀,坯体内部致密性不一致,采用了Isobam凝胶体系,在恒温水浴的条件下搅拌混合陶瓷浆料来代替常用球磨方法,可高效解决坯体内部致密性不一致的问题,且设备简单,工艺过程可控,极大地提高了浆料的均匀性,分散性,制备出的高质量浆料有利于得到结构均匀性好的钇铝石榴石型陶瓷材料。
为实现上述目的,本发明的技术方案如下:
一种采用Isobam体系凝胶注模成型钇铝石榴石型微波介质陶瓷的方法,包括如下步骤:
Step1、配料:按照化学通式Y 3-x Al 5-y R z O12,其中R为Mg2+、Ga3+、Ti4+或Nb5+多种异价离子中的一种或多种,0≤x≤0.15,0≤y≤0.8且0.03≤z≤1.5,准备原料,制成混合物;
Step2、将所述混合物与磨球、溶剂组成预混液,混合球磨15~24 小时,得混合浆料;
Step3、将所述混合浆料置于烘箱中烘干后,置于马弗炉中煅烧,过筛100~200目作为凝胶注模成型的原料粉;
Step4、Isobam溶液中加入原料粉和消泡剂,用搅拌器在恒温情况下搅拌;
Step5、搅拌后浆料真空除气泡,搅拌均匀,注入模具成型;
Step6、凝胶固化所述素坯,干燥后排胶;
Step7、将排胶后的素坯放置在钨丝真空烧结炉中以4~6 ℃/min的升温速率升温并在真空中1605~1775 ℃下烧结8~20 小时得到样品;
Step8、将Step7中所得样品在氧气气氛炉中,以2~4 ℃/min的升温速率升温并在900~1200 ℃下退火8~12 小时,得到最终的微波介质陶瓷材料。
进一步地,Step1中,原料选自Y2O3、Al2O3、MgO、Ga2O3、TiO2、Nb2O5。优选地,原料粉体的纯度>99.99%。
进一步地,Step2中,以二氧化铝球为球磨介质,溶剂为无水乙醇,原料、磨球、无水乙醇的质量比为1:(5~7):(2~4)。
进一步地,Step3中,所述烘箱为50~60 ℃恒温烘箱,烘浆料时间24~48 小时;所述煅烧的具体过程为:从室温升温到700~900 ℃,升温速率为2~3 ℃/min,保温6~8 小时,然后降温到室温~100 ℃,降温速率为1~3 ℃/min。
进一步地,Step4中,所述Isobam溶液为由Isobam04#、Isobam104#、Isobam600#中的一种或几种粉体溶质充分溶解于去离子水中配制浓度为15~25%的溶液,Isobam粉体用量为陶瓷粉体总量的0.3~1.5wt%;所述消泡剂为低级醇类(如异丙醇、仲丁醇、正丁醇、正丙醇、异辛醇等)或有机极型化合物(如戊醇、磷酸三丁醋、聚醚乙二醇、三轻甲基丙烷聚醚、聚丙二醇醚等表面活性剂)中的一种或多种;所述消泡剂的用量为所述氧化物混合物总量的0.5~1.0wt%;所述的浆料用氨水调节pH值至8~11,该pH值范围有利于浆料达到较好的分散效果;所述的搅拌器以机电系统为动力,搅拌桨材料为聚四氟乙烯,转速400~600 r/min,时间10~30 min;所述恒温情况由恒温水浴保证,温度25~30℃。
进一步地,Step5中,所述模具的材料为聚四氟乙烯、玻璃或不锈钢。
进一步地,Step6中,所述凝胶固化具体为:在室温下自然凝胶固化,时间为3~6 小时;所述干燥具体为:室温干燥2~6 小时后,放入烘箱中由室温到50~60 ℃,升温速率为0.1~2 ℃/min,并保温2~6 小时;所述排胶具体为:室温下以升温速率为0.5~2 ℃/min升温到450 ℃,450 ℃以升温速率为0.5~3 ℃/min升温到800~900 ℃,并在800~900 ℃保温2~6小时。
与现有技术相比,本发明具有如下的有益效果:
1. 当下流行的干压成型缺点是成型产品的形状有较大限制,干压成型对大型坯体生产有困难,模具造价高且磨损大,坯体强度低,坯体内部致密性不一致,组织结构的均匀性相对较差。特别地,当成型的尺寸偏大时,素坯密度分布上有一定梯度差。而采用Isobam凝胶注模体系,即可获得均匀性好,分散性高的陶瓷浆料,同时其原料无毒,对环境友好,添加种类和用量都较少,所需设备简单,无特殊环境要求,在常温下工艺稳定,可重复性强,操作简便。
2. Isobam凝胶体系能满足制备高致密度陶瓷素坯的需求,并且采用Isobam凝胶注模体系制备的陶瓷素坯内部致密性分布均匀,在一定程度上提升了微波介质陶瓷的介电性能。
附图说明
图1是采用Isobam体系凝胶注模成型钇铝石榴石型微波介质陶瓷的流程图。
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晰,结合具体实施例,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,但不应以此限制本发明的保护范围。
实施例1
一种采用Isobam体系凝胶注模成型钇铝石榴石型微波介质陶瓷的制备方法,包括如下步骤:
Step1、将Y2O3、Al2O3、MgO、SiO2、TiO2,分别按照54.7%、42.6%、2.2%、0.3%、0.2%的质量比进行备料;
Step2、将所述氧化物混合物与磨球、溶剂组成预混液,以二氧化铝球为球磨介质,以无水乙醇为溶剂,按照混合料:磨球:乙醇的重量比为1:5:2进行研磨15小时,最后得到混合均匀的混合物;
Step3、将所述混合浆料置于50 ℃的烘箱中烘24 小时后,用马弗炉中煅烧,从室温升温到700 ℃,升温速率为2 ℃/min后,保温6 小时,然后降温到室温,降温速率为1 ℃/min。过筛200目三遍作为凝胶注模成型的原料粉;
Step4、Isobam溶液中加入原料粉和消泡剂,用搅拌器在恒温情况下搅拌;所述Isobam溶液为由Isobam04#、Isobam104#、Isobam600#中的一种或几种粉体溶质充分溶解于去离子水中配制浓度为15~25%的溶液,Isobam粉体用量为陶瓷粉体总量的0.3~1.5wt%;所述的消泡剂包括低级醇类(如异丙醇、仲丁醇、正丁醇、正丙醇、异辛醇等)或有机极型化合物(如戊醇、磷酸三丁醋、聚醚乙二醇、三轻甲基丙烷聚醚、聚丙二醇醚等表面活性剂)中的一种或多种;所述消泡剂的用量为所述氧化物混合物总量的0.5~1.0wt%;所述的浆料用氨水调节pH值至8~11,该pH值范围有利于浆料达到较好的分散效果;
Step5、将搅拌后的混合浆料在真空度为0.1 Mpa下真空除气泡30 s,浆料搅拌均匀后注入聚四氟乙烯模具中成型;
Step6、室温下自然凝胶固化3 小时后,凝胶成型,再室温下干燥2 小时后,放入烘箱中干燥由室温升温到55 ℃,升温速率为0.1 ℃/min,并保温2 小时得到素坯;素坯自然条件下降温到室温,然后再排胶,先从室温以速率为0.5 ℃/min升温到450 ℃,450 ℃以0.5 ℃/min升温速率升温到800 ℃,并在800 ℃保温4 小时;
Step7、将排胶后的素坯放置在钨丝真空烧结炉中以4 ℃/min的升温速率升温并在真空中1605 ℃下烧结8 小时得到样品;
Step8、将Step7中所得样品在氧气气氛炉中,以2 ℃/min的升温速率升温并在900℃下退火8 小时,得到最终的微波介质陶瓷材料。
实施例2
一种采用Isobam体系凝胶注模成型钇铝石榴石微波介质陶瓷的制备方法,包括如下步骤:
Step1、将Y2O3、Al2O3、MgO、SiO2、TiO2,分别按照55.5%、36.2%、3.4%、2.7%、2.2%的质量比进行备料;
Step2、将所述氧化物混合物与磨球,溶剂组成预混液,以二氧化铝球为球磨介质,以无水乙醇为溶剂,按照混合料:磨球:乙醇的重量比为1:7:4进行研磨24小时,最后得到混合均匀的混合物;
Step3、将所述混合浆料置于60 ℃的烘箱中烘48 小时后,用马弗炉中煅烧,从室温升温到900 ℃,升温速率为3 ℃/min后,保温8 小时,然后降温到100 ℃,降温速率为3℃/min。过筛200目三遍作为凝胶注模成型的原料粉;
Step4、Isobam溶液中加入原料粉和消泡剂,用搅拌器在恒温情况下搅拌。所述Isobam溶液为由Isobam04#、Isobam104#、Isobam600#中的一种或几种粉体溶质充分溶解于去离子水中配制浓度为15~25%的溶液,Isobam粉体用量为陶瓷粉体总量的0.3~1.5wt%;所述的消泡剂包括低级醇类(如异丙醇、仲丁醇、正丁醇、正丙醇、异辛醇等)或有机极型化合物(如戊醇、磷酸三丁醋、聚醚乙二醇、三轻甲基丙烷聚醚、聚丙二醇醚等表面活性剂)中的一种或多种;所述消泡剂的用量为所述氧化物混合物总量的0.5~1.0wt%;所述的浆料用氨水调节pH值至8~11,该pH值范围有利于浆料达到较好的分散效果;
Step5、搅拌后浆料真空除气泡,搅拌均匀,注入模具成型;
Step6、室温下自然凝胶固化6 小时后,凝胶成型,再室温下干燥6 小时后,放入烘箱中干燥,由室温升温到60 ℃,升温速率为2 ℃/min,并保温6 小时得到素坯。素坯自然条件下降温到室温,然后再排胶,先从室温以速率为2 ℃/min升温到450 ℃,450 ℃以3 ℃/min升温速率升温到900 ℃,在900 ℃保温6 小时;
Step7、将排胶后的素坯放置在钨丝真空烧结炉中以6 ℃/min的升温速率升温并在真空中1775 ℃下烧结20 小时得到样品;
Step8、将Step7中所得样品在氧气气氛炉中,以4 ℃/min的升温速率升温并在1200 ℃下退火12 小时,得到最终的微波介质陶瓷材料。
实施例3
一种采用Isobam体系凝胶注模成型钇铝石榴石型微波介质陶瓷的制备方法,包括如下步骤:
Step1、将Y2O3、AlO3、MgO、SiO2、TiO2,分别按照56.8%、40.6%、0.5%、0.3%、1.8%的质量比进行备料;
Step2、将所述氧化物混合物与磨球,溶剂组成预混液,以二氧化铝球为球磨介质,以无水乙醇为溶剂,按照混合料:磨球:乙醇的重量比为1:6:3进行研磨20 小时,最后得到混合均匀的混合物;
Step3、将所述混合浆料置于55 ℃的烘箱中烘36 小时后,用马弗炉中煅烧,从室温升温到800 ℃,升温速率为2.5 ℃/min后,保温7 小时,然后降温到50 ℃,降温速率为2℃/min。过筛200目三遍作为凝胶注模成型的原料粉;
Step4、Isobam溶液中加入原料粉和消泡剂,用搅拌器在恒温情况下搅拌。所述Isobam溶液为由Isobam04#、Isobam104#、Isobam600#中的一种或几种粉体溶质充分溶解于去离子水中配制浓度为15~25%的溶液,Isobam粉体用量为陶瓷粉体总量的0.3~1.5wt%;所述的消泡剂包括低级醇类(如异丙醇、仲丁醇、正丁醇、正丙醇、异辛醇等)或有机极型化合物(如戊醇、磷酸三丁醋、聚醚乙二醇、三轻甲基丙烷聚醚、聚丙二醇醚等表面活性剂)中的一种或多种;所述消泡剂的用量为所述氧化物混合物总量的0.5~1.0wt%;所述的浆料用氨水调节pH值至8~11,该pH值范围有利于浆料达到较好的分散效果;
Step5、搅拌后浆料真空除气泡,搅拌均匀,注入模具成型;
Step6、室温下自然凝胶固化4.5 小时后,凝胶成型,再室温下干燥4 小时后,放入烘箱中干燥由室温升温到55 ℃,升温速率为1 ℃/min,并保温4 小时得到素坯。素坯自然条件下降温到室温,然后再排胶,先从室温以速率为1 ℃/min升温到450 ℃,450 ℃以2℃/min升温速率升温到850 ℃,在850 ℃保温6 小时;
Step7、将排胶后的素坯放置在钨丝真空烧结炉中以5 ℃/min的升温速率升温并在真空中1690 ℃下烧结14 小时得到样品;
Step8、将Step7中所得样品在氧气气氛炉中,以3 ℃/min的升温速率升温并在1050 ℃下退火10 小时,得到最终的微波介质陶瓷材料。
Claims (7)
1.一种采用Isobam体系凝胶注模成型钇铝石榴石型微波介质陶瓷的方法,其特征在于:包括如下步骤:
Step1、配料:按照化学通式Y 3-x Al 5-y R z O12,其中R为Mg2+、Ga3+、Ti4+或Nb5+多种异价离子中的一种或多种,0≤x≤0.15、0≤y≤0.8且0.03≤z≤1.5,准备原料,制成混合物;
Step2、将所述混合物与磨球、溶剂组成预混液,混合球磨15~24 小时,得混合浆料;
Step3、将所述混合浆料置于烘箱中烘干后,置于马弗炉中煅烧,过筛100~200目作为凝胶注模成型的原料粉;
Step4、向Isobam溶液中加入原料粉和消泡剂,用搅拌器在恒温条件下搅拌;
Step5、搅拌后浆料真空除气泡,搅拌均匀,注入模具成型;
Step6、凝胶固化所得的素坯,干燥后排胶;
Step7、将排胶后的素坯放置在钨丝真空烧结炉中以4~6 ℃/min的升温速率升温并在真空中1605~1775 ℃下烧结8~20 小时得到样品;
Step8、将Step7中所得样品在氧气气氛炉中,以2~4 ℃/min的升温速率升温并在900~1200 ℃下退火8~12 小时,得到最终的微波介质陶瓷材料。
2.根据权利要求1所述的方法,其特征在于:Step1中,原料选自Y2O3、Al2O3、MgO、Ga2O3、TiO2、Nb2O5。
3.根据权利要求1所述的方法,其特征在于:Step2中,磨球为二氧化铝球,溶剂为无水乙醇,所述混合物、磨球、无水乙醇的质量比为1:(5~7):(2~4)。
4.根据权利要求1所述的方法,其特征在于:Step3中,所述烘箱为50~60 ℃恒温烘箱,烘浆料时间为24~48 小时;所述煅烧的具体过程为:从室温升温到700~900 ℃,升温速率为2~3 ℃/min,保温6~8 小时,然后降温到室温~100 ℃,降温速率为1~3 ℃/min。
5.根据权利要求1所述的方法,其特征在于:Step4中,所述Isobam溶液为由Isobam04#、Isobam104#、Isobam600#中的一种或几种粉体溶质充分溶解于去离子水中配制浓度为15~25%的溶液;所述消泡剂为低级醇类或有机极型化合物中的一种或多种;得到的浆料用氨水调节pH值至8~11;所述的搅拌器以机电系统为动力,搅拌桨材料为聚四氟乙烯,转速400~600 r/min,时间10~30 min;所述恒温条件采用恒温水浴,温度25~30℃。
6.根据权利要求1所述的方法,其特征在于:Step5中,所述模具的材料为聚四氟乙烯、玻璃或不锈钢。
7.根据权利要求1所述的方法,其特征在于:Step6中,所述凝胶固化具体为:在室温下自然凝胶固化,时间为3~6 小时;所述干燥具体为:室温干燥2~6 小时后,放入烘箱中由室温到50~60 ℃,升温速率为0.1~2 ℃/min,并保温2~6 小时;所述排胶具体为:室温下以升温速率为0.5~2 ℃/min升温到450 ℃,450 ℃以升温速率为0.5~3 ℃/min升温到800~900℃,并在800~900 ℃保温2~6 小时。
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CN111253153A (zh) * | 2020-01-22 | 2020-06-09 | 新沂市锡沂高新材料产业技术研究院有限公司 | 一种基于Isobam凝胶体系制备增韧大尺寸超薄YAG透明陶瓷素坯的方法 |
CN112341184A (zh) * | 2020-11-09 | 2021-02-09 | 新沂市锡沂高新材料产业技术研究院有限公司 | 一种基于Isobam凝胶态浸涂技术的波导结构激光透明陶瓷光纤的制备方法 |
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CN115010474A (zh) * | 2022-07-05 | 2022-09-06 | 江苏锡沂高新材料产业技术研究院有限公司 | 一种采用Isobam凝胶体系注模成型制备熔融石英陶瓷的方法 |
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