CN111635227A - 一种高频陶瓷介质材料及其制备方法和多层陶瓷电容器 - Google Patents

一种高频陶瓷介质材料及其制备方法和多层陶瓷电容器 Download PDF

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CN111635227A
CN111635227A CN202010598548.6A CN202010598548A CN111635227A CN 111635227 A CN111635227 A CN 111635227A CN 202010598548 A CN202010598548 A CN 202010598548A CN 111635227 A CN111635227 A CN 111635227A
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张军志
杨和成
贺凯强
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Xiamen Sunyear Electronics Co ltd
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Abstract

本发明提供一种高频陶瓷介质材料及其制备方法和多层陶瓷电容器，涉及陶瓷介质材料领域。本发明材料包括质量分数为93～98％的主晶相成分和2～7％的改性添加物，主晶相成分为(CaxSr1‑xMna)ZryTizO3，0.2≤x≤0.4，1.02≤y≤1.08，0.02≤z≤0.06，0.02≤a≤0.06，改性添加物选自Nb2O5、MnCO3、BaCO3、Al2O3、ZnO、SiO2、Mg(OH)2中的三种或以上。将钙、锶及锰各自的氧化物或碳酸盐、二氧化锆、二氧化钛加水球磨、干燥、1130℃～1200℃煅烧2～4h，得到主晶相成分，再加改性添加物、加水球磨、干燥得高频陶瓷介质材料。该材料具有良好的介电性能，能够在还原气氛中以较低的1160±20℃烧结，制得多层陶瓷电容器，介电常数29～35，符合COG特性要求及多层陶瓷电容器高性能、贱金属化发展趋势的要求。

Description

一种高频陶瓷介质材料及其制备方法和多层陶瓷电容器
技术领域
本发明涉及陶瓷介质材料领域，且特别涉及一种高频陶瓷介质材料及其制备方法和多层陶瓷电容器。
背景技术
片式多层陶瓷电容器已经被广泛用作微型尺寸、高容量和高可靠性的电子元件，面临更小尺寸、更高容量、更低成本和更高可靠性的市场需求。该电容器是由印好电极(内电极)的陶瓷介质膜片以错位的方式叠合起来，经一次性高温烧结形成陶瓷芯片，再在芯片的两端封上金属层(外电极)，形成一个类似独石电容的结构体。适合在空气气氛中烧结的多层陶瓷电容器，是以贵金属钯或钯银合金做内电极；并且所用的陶瓷介质材料大多含有Pd、Cd等有害金属元素。由于贵金属价格较高，面对日益激烈的市场竞争及HSF的要求，近几年多层陶瓷电容器技术的发展主要集中在产品的高容量化、贱金属化、小型化及多功能化等方面。
采用廉价金属如铜、镍或其合金替代贵金属作为内电极可使多层陶瓷电容器的材料成本得到大幅度的下降；但由于铜、镍或其合金与陶瓷材料在空气中烧结时会引起铜、镍或其合金内电极氧化失效，因此，以铜、镍或其合金作为内电极的多层陶瓷电容器必须要在还原气氛中进行烧结，因此，选用铜、镍或其合金作为内电极时，要求使用的陶瓷介质材料必须具有强的抗还原性。
发明人研究发现，对于具有EIA(电子工业协会)标准COG(一种超稳定级的介质材料，在温度从-55℃～125℃时容量变化为0±30ppm/℃，电容量随频率的变化小于±0.3ΔC，适用于高频、特高频场合)温度特性的陶瓷介质材料，通常是以(CaxSr1-x)ZryO3为主晶材料进行掺杂改性获得。在国内已有的贱金属抗还原材料相关研究中，已经公开的材料,如CN105174947A制作的COG粉料可在较低的烧结温度下(1200℃以下)成瓷，但其均是水热法合成主晶相(CaxSr1-x)ZryO3，采用后添加的方式进行掺杂，并要求掺杂物质平均粒径小于150nm，获得符合COG特性的材料，制备方法复杂，主晶相成分难以控制，获得的陶瓷介质材料存在一定的性能缺陷。
发明内容
本发明的目的在于提供一种适用于还原气氛低温烧结的多层陶瓷电容器用高频陶瓷介质材料，其具有强的抗还原性、良好的分散性、均匀性，烧结温度低。
本发明的另一目的在于提供一种适用于还原气氛低温烧结的多层陶瓷电容器用高频陶瓷介质材料的制备方法，制备方法简单、易操作，适用于工业化大规模生产。
本发明采用以下技术方案来实现目的。
本发明提供一种高频陶瓷介质材料，包括质量分数为93～98％的主晶相成分和质量分数为2～7％的改性添加物，所述主晶相成分为(CaxSr1-xMna)ZryTizO3，其中0.2≤x≤0.4，1.02≤y≤1.08，0.02≤z≤0.06，0.02≤a≤0.06，所述改性添加物选自Nb2O5、MnCO3、BaCO3、Al2O3、ZnO、SiO2、Mg(OH)2中的三种或三种以上。
进一步地，所述改性添加物中，各组分在所述高频陶瓷介质材料中的质量分数范围是：Nb2O5为0.01～1.0％；MnCO3为0～1.5％；BaCO3为0～2.0％；Al2O3为0～1.5％；ZnO为0.0～0.5％；SiO2为0.4～1.6％；Mg(OH)2为0～0.6％。
进一步地，主晶相中a＝z，所述主晶相成分为(CaxSr1-xMnz)ZryTizO3，其中0.2≤x≤0.4，1.02≤y≤1.08，0.02≤z≤0.06。
进一步地，所述高频陶瓷介质材料烧结后，其介电常数介于29～35，容温变化率为±30ppm/℃，室温介电损耗≤0.05％。
本发明还提供一种如上所述的高频陶瓷介质材料的制备方法，包括以下步骤：
S1，根据化学式(CaxSr1-xMna)ZryTizO3中金属元素的比例，称取钙、锶及锰三种金属各自的氧化物或碳酸盐、二氧化钛、二氧化锆加水进行湿法球磨，干燥，然后在空气气氛下煅烧2～4h，煅烧温度为1130℃～1200℃，得到所述主晶相成分；
S2，将所述主晶相成分和所述改性添加物混合，并加水进行湿法球磨，球磨后再干燥得到所述高频陶瓷介质材料。
进一步地，步骤S1中，所述钙、锶及锰三种金属各自的氧化物或碳酸盐，分别选取为碳酸钙、碳酸锶和碳酸锰。
进一步地，步骤S1中，碳酸钙、碳酸锶、碳酸锰、二氧化钛和二氧化锆的摩尔比为0.35:0.65:0.04:0.04:1.06。
进一步地，步骤S2中，在湿法球磨过程中，还加入占所述主晶相成分和所述改性添加物的混合物的质量比例为2～5％的表面活性剂。
进一步地，上述制备方法还包括步骤S3，将步骤S2得到的高频陶瓷介质材料制成生坯，将所述生坯在还原气氛下烧结，烧结温度为1140～1180℃，烧结时间为2～4h，得到坯体。
本发明还提供一种多层陶瓷电容器，包含上述方法制得的坯体。
本发明的有益效果是：以预先掺杂形式，将Mn、Ti掺杂于(CaxSr1-x)ZryO3，得到(CaxSr1-xMna)ZryTizO3作为主晶相材料，然后再进行改性掺杂，获得符合COG30温度特性的高频陶瓷介质材料，其介电常数29-35，该制备过程简单，获得的高频陶瓷介质材料具有良好的分散性、均匀性和稳定性。其制成的多层陶瓷电容器能够在还原气氛中以较低的1160±20℃进行烧结，烧结后的陶瓷介质材料符合COG特性要求，且与镍、铜或其合金内电极匹配良好。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
下面对本发明的一种高频陶瓷介质材料及其制备方法和多层陶瓷电容器进行具体说明。
本发明提供一种高频陶瓷介质材料，包括质量分数为93～98％的主晶相成分和质量分数为2～7％的改性添加物，主晶相成分为(CaxSr1-xMna)ZryTizO3，其中0.2≤x≤0.4，1.02≤y≤1.08，0.02≤z≤0.06，0.02≤a≤0.06，改性添加物选自Nb2O5、MnCO3、BaCO3、Al2O3、ZnO、SiO2、Mg(OH)2中的三种或三种以上。在该主晶相通过预先掺杂能够对(CaxSr1-x)ZryO3进行有效改性，提高材料的绝缘性，获取≤0.05％的介质损耗，同时降低烧结温度。
进一步地，在本发明较佳实施例中，改性添加物中，各组分在高频陶瓷介质材料中的质量分数范围是：Nb2O5为0.01～1.0％；MnCO3为0～1.5％；BaCO3为0～2.0％；Al2O3为0～1.5％；ZnO为0.0～0.5％；SiO2为0.4～1.6％；Mg(OH)2为0～0.6％。
更为优选地，主晶相成分为93～94％，改性添加物包括以下成分：Nb2O5为0.2％；MnCO3为1.2～1.5％；BaCO3为1.5％；Al2O3为1～1.5％；ZnO为0.3～0.5％；SiO2为1.2～1.6％；Mg(OH)2为0.4％。
通过优化改性添加物的选择和配比，能够进一步改善陶瓷介质材料的性能，得到性能更为优良的多层陶瓷电容器，例如进一步降低介电损耗，提高容温变化的稳定性。
进一步地，在本发明较佳实施例中，主晶相中a＝z，主晶相成分为(CaxSr1-xMnz)ZryTizO3，其中0.2≤x≤0.4，1.02≤y≤1.08，0.02≤z≤0.06。更为优选的，x＝0.35，y＝1.06，z＝0.04。在对(CaxSr1-x)ZryO3进行掺杂改性的过程中，掺杂的材料和用量不同，得到的主晶相在材料性能上有较大的差异。根据主晶相成分(CaxSr1-xMnz)ZryTizO3，用相应量的Mn、Ti预先掺杂(CaxSr1-x)ZryO3，改变了主晶相的微观结构、介电及绝缘性能和烧结特性等，使其能够在较低的温度下烧结，并能获得低的介质损耗。此外，能够使得主晶相能够和其它改性添加物更好地结合。
进一步地，高频陶瓷介质材料烧结后，其介电常数介于29～35，容温变化率为±30ppm/℃，室温介电损耗≤0.05％，符合COG特性要求，且能与多层陶瓷电容器内的镍、铜或其合金内电极匹配良好。
本发明还提供一种如上的高频陶瓷介质材料的制备方法，包括以下步骤：
S1，根据化学式(CaxSr1-xMna)ZryTizO3中金属元素的比例，其中0.2≤x≤0.4，1.02≤y≤1.08，0.02≤z≤0.06，0.02≤a≤0.06，称取钙、锶及锰三种金属各自的氧化物或碳酸盐、二氧化钛、二氧化锆加水进行湿法球磨，其中，按质量比1:1～2将固体物料和水混合进行湿法球磨。球磨后用喷雾干燥塔或其他方法进行干燥，然后在空气气氛下煅烧2～4h，煅烧温度为1130℃～1200℃，得到主晶相成分。
S2，将主晶相成分和改性添加物混合，并加水进行湿法球磨，其中，按质量比1:0.6～1将固体物料和水混合进行湿法球磨，将物料球磨至平均颗粒尺寸达200～400nm。。球磨后再用喷雾干燥塔或其他方法进行干燥得到高频陶瓷介质材料。
进一步地，步骤S2中，在湿法球磨过程中，还加入占主晶相成分和改性添加物的混合物的质量比例为2～5％的表面活性剂。例如加入一定量的氟碳表面活性剂能够有效增加球磨效果，增加材料的质量均一性和稳定性。
进一步地，上述制备方法还包括步骤S3，将步骤S2得到的高频陶瓷介质材料制成生坯，将生坯在还原气氛下烧结，烧结温度为1140～1180℃，烧结时间为2～4h，得到坯体。烧结温度较低，节能，且用于制作多层陶瓷电容器时，降低了高温对其他部件的影响。
本发明还提供一种多层陶瓷电容器，包含上述方法制得的坯体，多层陶瓷电容器的陶瓷介质材料介电常数为29-35，特性达到COG的要求，能与贱金属内电极很好匹配。
以下结合实施例对本发明的特征作进一步的详细描述。
实施例
(1)以高纯、超细的碳酸钙、碳酸锶、碳酸锰、二氧化钛和二氧化锆按表1的组成比例置于球磨机中进行湿法球磨，混合均匀，再用喷雾干燥塔进行干燥，分别在空气炉中于1130℃、1155℃、1180℃条件下煅烧3小时，合成(CaxSr1-xMna)ZryTizO3主晶相。
(2)表1中的SCZ1、SCZ2和SCZ3三种条件的配方，每种各做6个样品，按表2的组成比例，把(CaxSr1-xMna)ZryTizO3主晶相及各种改性添加物按配方组成的质量比称重，置于球磨机中，按质量比为固体物料：去离子水＝1：0.8的比例加入去离子水进行湿法球磨砂磨，要求物料混合均匀，使砂磨后的粉体平均颗粒尺寸达200～400nm。球磨过程还加入占主晶相成分和改性添加物的混合物的质量比例为3％的氟碳表面活性剂。砂磨完毕后用喷雾干燥塔进行干燥，最后得到粉末态的高频陶瓷介质材料。
(3)制备多层陶瓷电容器试样：表2中的1～18号样品按上述方法获得的1～18号陶瓷介质粉末材料，每号样品均按比例计算，于100g粉末中加入40-60g无水乙醇，30-45g PVB粘合剂，球磨均匀形成浆料，在经过流延获得厚度为15微米的陶瓷介质膜片生坯，用镍浆作为内电极进行叠印、等静压、切割、排胶、烧结、倒角、端铜或铜合金外部电极后得到多层陶瓷电容器；其中烧结条件是：还原气氛炉，于较低的烧结温度1150～1180℃中烧结，保温3小时，得到1～18号多层陶瓷电容器试样，测试其介电性能结果如表3，表3中的1～18号试样与表2中的1～18号样品一一对应。
表1(CaxSr1-xMna)ZryTizO3主晶相的配方表
Figure BDA0002558302990000071
表2高频陶瓷介质材料的配方表
Figure BDA0002558302990000072
Figure BDA0002558302990000081
表3介电性能测试结果表
Figure BDA0002558302990000082
如表3所示，经过上述过程制成的镍内电极多层陶瓷电容器用的抗还原性强的COG陶瓷介质材料，可以在1140℃～1180℃的烧结温度范围内，通过调整不同原料的的配比可形成室温介电常数介于29～35，容温变化率介于+30ppm/℃～-30ppm/℃之间，室温介电损耗≤0.05％的连续可调系统的介质陶瓷材料。表3中7～12号样品，即SCZ2组的参数较好。本实施例以贱金属镍、铜或其合金代替贵金属银/钯电极，降低了生产成本，高介性能满足了COG型多层陶瓷电容器抗还原的要求。
以上所描述的实施例是本发明一部分实施例，而不是全部的实施例。本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围，而是仅仅表示本发明的选定实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。

Claims (10)

1.一种高频陶瓷介质材料，其特征在于，包括质量分数为93～98％的主晶相成分和质量分数为2～7％的改性添加物，所述主晶相成分为(CaxSr1-xMna)ZryTizO3，其中0.2≤x≤0.4，1.02≤y≤1.08，0.02≤z≤0.06，0.02≤a≤0.06，所述改性添加物选自Nb2O5、MnCO3、BaCO3、Al2O3、ZnO、SiO2、Mg(OH)2中的三种或三种以上。
2.根据权利要求1所述的高频陶瓷介质材料，其特征在于，所述改性添加物中，各组分在所述高频陶瓷介质材料中的质量分数范围是：Nb2O5为0.01～1.0％；MnCO3为0～1.5％；BaCO3为0～2.0％；Al2O3为0～1.5％；ZnO为0.0～0.5％；SiO2为0.4～1.6％；Mg(OH)2为0～0.6％。
3.根据权利要求1所述的高频陶瓷介质材料，其特征在于，a＝z，所述主晶相成分为(CaxSr1-xMnz)ZryTizO3，其中0.2≤x≤0.4，1.02≤y≤1.08，0.02≤z≤0.06。
4.根据权利要求1所述的高频陶瓷介质材料，其特征在于，所述高频陶瓷介质材料烧结后，其介电常数介于29～35，容温变化率为±30ppm/℃，室温介电损耗≤0.05％。
5.一种如权利要求1～4任意一项所述的高频陶瓷介质材料的制备方法，其特征在于，包括以下步骤：
S1，根据化学式(CaxSr1-xMna)ZryTizO3中金属元素的比例，称取钙、锶及锰三种金属各自的氧化物或碳酸盐、二氧化钛、二氧化锆加水进行湿法球磨，干燥，然后在空气气氛下煅烧2～4h，煅烧温度为1130℃～1200℃，得到所述主晶相成分；
S2，将所述主晶相成分和所述改性添加物混合，并加水进行湿法球磨，球磨后再干燥得到所述高频陶瓷介质材料。
6.根据权利要求5所述的制备方法，其特征在于，步骤S1中，所述钙、锶及锰三种金属各自的氧化物或碳酸盐，分别选取为碳酸钙、碳酸锶和碳酸锰。
7.根据权利要求6所述的制备方法，其特征在于，步骤S1中，碳酸钙、碳酸锶、碳酸锰、二氧化钛和二氧化锆的摩尔比为0.35:0.65:0.04:0.04:1.06。
8.根据权利要求5所述的制备方法，其特征在于，步骤S2中，在湿法球磨过程中，还加入占所述主晶相成分和所述改性添加物的混合物的质量比例为2～5％的表面活性剂。
9.根据权利要求5所述的制备方法，其特征在于，所述制备方法还包括步骤S3，将步骤S2得到的高频陶瓷介质材料制成生坯，将所述生坯在还原气氛下烧结，烧结温度为1140～1180℃，烧结时间为2～4h，得到坯体。
10.一种多层陶瓷电容器，其特征在于，包含权利要求9制得的坯体。
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