CN113773071B - 一种陶瓷材料、陶瓷浆料和多层片式陶瓷电容器 - Google Patents
一种陶瓷材料、陶瓷浆料和多层片式陶瓷电容器 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 35
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Abstract
本发明公开了一种陶瓷材料、陶瓷浆料和多层片式陶瓷电容器。本发明陶瓷材料包括AQO3和M组分,其中,A为Ba、Ca、Sr中的至少一种,Q为Ti、Zr、Hf中的至少一种,M组分为KAlSi2O6、ZrW2O8、HfW2O8中的至少一种,M组分的摩尔量为AQO3摩尔量的0.3~3.6%。本发明陶瓷材料中添加特定用量的热致收缩材料M组分,能很好地改善陶瓷胚体与镍电极收缩率失配的问题,从而很好地改善MLCC产品分层开裂的问题。
Description
技术领域
本发明属于陶瓷电容器材料技术领域,涉及一种陶瓷材料、陶瓷浆料和多层片式陶瓷电容器。
背景技术
多层片式陶瓷电容器(MLCC)是将电极材料与陶瓷胚体多层交错堆叠并烧结而成的一个整体,也叫独石结构。分层开裂是影响陶瓷电容器产品性能及使用的一种重要缺陷。陶瓷胚体与镍电极层在烧结过程中,镍电极层通常收缩率大于陶瓷胚体,且先于陶瓷胚体收缩,这种收缩率的差异会导致MLCC产品内产生应力,进而导致瓷体与电极间产生开裂,所以材料收缩的温度范围及随温度变化引发的收缩率的不同是造成收缩率失配分层的根本原因。
针对MLCC产品分层开裂的问题,目前从配方角度改进的方法主要是在镍浆中加入陶瓷粉末作为共材,利用陶瓷粉末作为阻缩剂以降低镍电极收缩度,改善镍电极与陶瓷体的收缩匹配性,但是经这种方法的改善后,镍电极的收缩率仍比陶瓷体大,烧结后仍存在分层开裂风险。
发明内容
本发明的目的在于克服现有技术的不足之处而提供一种陶瓷材料、陶瓷浆料和多层片式陶瓷电容器,陶瓷材料中添加特定用量的特定种类的热致收缩材料,能很好地改善陶瓷胚体与镍电极烧结收缩率失配的问题,从而很好地改善MLCC产品分层开裂的问题。
为实现上述目的,第一方面,本发明提供了一种陶瓷材料,其包括M组分和主体成分AQO3,其中,A为Ba、Ca、Sr中的至少一种,Q为Ti、Zr、Hf中的至少一种,M组分为KAlSi2O6、ZrW2O8、HfW2O8中的至少一种,M组分的摩尔量为AQO3摩尔量的0.3~3.6%。
优选地,所述M组分的摩尔量为AQO3摩尔量的1.6~2.8%。
优选地,所述陶瓷材料还包括X组分、R组分和Z组分,其中X组分为Mg、La、Sm、Dy、Ho、Er、Y、Eu、Gd、Tm、Yb中至少一种元素的化合物;R组分为V、Mn、Cr、Co、Fe中至少一种元素的化合物;Z组分为Si、Ba、B、Zn、Al、Li中至少一种元素的化合物。优选地,所述X组分、R组分和Z组分均为含氧化合物;更优选地,所述X组分、R组分和Z组分均为氧化物、碳酸盐、氢氧化物中的至少一种。
优选地,所述X组分的摩尔量为AQO3摩尔量的0.4~2.2%,所述R组分的摩尔量为AQO3摩尔量的0.08~0.4%,所述Z组分的摩尔量为AQO3摩尔量的0.5~4.5%。
优选地,所述Z组分为玻璃料。
优选地,所述A为Ba,所述Q为Ti。
第二方面,本发明提供了一种陶瓷材料,其包括上述陶瓷材料。
第三方面,本发明提供了一种多层片式陶瓷电容器,其包括陶瓷介质和镍内电极,所述陶瓷介质主要由上述陶瓷材料构成。
优选地,所述镍内电极包括金属镍和陶瓷阻缩剂,所述金属镍和陶瓷阻缩剂的质量比为3.5:1~7:1,进一步优选为5:1。
优选地,所述陶瓷阻缩剂为纳米颗粒,且成分与所述陶瓷材料中的主体成分AQO3相同。
与现有技术相比,本发明的有益效果为:本发明通过在MLCC的陶瓷材料中加入一定量的热致收缩材料,使得在镍电极材料与陶瓷胚体共烧过程中,能利用热致收缩材料温度升高体积收缩的特性,使陶瓷胚体产生额外的收缩作用,并且能起到提前收缩的效果,以此改善镍层收缩大而陶瓷胚体收缩滞后的问题,即改善陶瓷胚体与镍电极收缩率失配的情况,从而改善MLCC产品分层开裂的问题。
具体实施方式
为更好地说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明进一步说明。本领域技术人员应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
实施例中,所使用的实验方法如无特殊说明,均为常规方法,所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
本文中,AQO3指的是元素A和元素Q的钙钛矿结构化合物。
为解决陶瓷胚体与镍内电极在烧结过程中的收缩率差异而导致所得MLCC产品出现陶瓷介质与镍内电极间开裂的技术问题,本发明在陶瓷胚体的配方中加入一定量的特定种类的热致收缩材料,利用热致收缩材料温度升高体积收缩的特性,使陶瓷胚体产生额外的收缩作用,并且能起到提前收缩的效果,以此改善镍内电极收缩大而陶瓷胚体收缩滞后的问题,即改善陶瓷胚体与镍内电极收缩率失配的问题,从而改善MLCC产品分层开裂的问题。具体而言,本发明提供了一种陶瓷材料,其包括M组分和主体成分AQO3,其中,A为Ba、Ca、Sr中的至少一种,Q为Ti、Zr、Hf中的至少一种,M组分为KAlSi2O6、ZrW2O8、HfW2O8中的至少一种,M组分的摩尔量为AQO3摩尔量的0.3~3.6%。其中,AQO3为主成分,M组分为热致收缩材料。
如果M组分的摩尔量小于AQO3摩尔量的0.3%,由于热致收缩材料的添加量过少,导致镍内电极与陶瓷胚体之间的收缩匹配性改善不明显,进而导致MLCC分层开裂问题无明显改善。如果M组分的摩尔量大于AQO3摩尔量的3.6%,由于MLCC的分层开裂除了与烧结升温过程中镍内电极与陶瓷胚体之间的收缩匹配性相关外,在烧结后的冷却过程中,镍内电极和陶瓷胚体的热膨胀系数不同,金属镍的热膨胀系数高于陶瓷胚体,在冷却的过程中,热致收缩材料会产生额外的膨胀,进一步加剧了金属镍和陶瓷胚体之间热膨胀系数的差异,导致MLCC分层开裂比例反而升高。为了能很好的改善MLCC分层开裂的问题,选择M组分的摩尔量为AQO3摩尔量的0.3~3.6%。优选M组分的摩尔量为AQO3摩尔量的1.6~2.8%,以更好的改善MLCC分层开裂的问题。
不同成分和不同用量的热致收缩材料的加入会对MLCC电性能产生负面影响。为改善MLCC的TCC性能和K值(即介电常数),可在陶瓷材料中添加X组分、R组分和Z组分,其中X组分为Mg、La、Sm、Dy、Ho、Er、Y、Eu、Gd、Tm、Yb中至少一种元素的化合物;R组分为V、Mn、Cr、Co、Fe中至少一种元素的化合物;Z组分为Si、Ba、B、Zn、Al、Li至少一种元素的化合物。优选地,所述X组分、R组分和Z组分均为含氧化合物;更优选地,所述X组分、R组分和Z组分均为氧化物、碳酸盐、氢氧化物中的至少一种。
在一些优选的实施方式中,X组分的摩尔量为AQO3摩尔量的0.4~2.2%,R组分的摩尔量为AQO3摩尔量的0.08~0.4%,Z组分的摩尔量为AQO3摩尔量的0.5~4.5%。当X组分、R组分和Z组分在上述特定用量下,能使MLCC的TCC性能指标处于±15%范围内,产品介电常数满足使用要求。
在一些优选的实施方式中,Z组分为玻璃料,以促进陶瓷烧结致密化。
在一些优选的实施方式中,A为Ba,Q为Ti。
本发明陶瓷材料能用于制备MLCC的陶瓷浆料,即陶瓷浆料包括溶剂和本发明陶瓷材料。溶剂的种类和用量无特别要求,可选择本领域常用的溶剂种类和用量,如溶剂种类可选择为甲苯、无水乙醇、异丙醇等中的至少一种,比如溶剂用量可选择为溶剂/陶瓷粉体=90~130wt%。
可根据需要在陶瓷浆料中添加粘合剂、增塑剂等助剂。粘合剂的种类和用量无特别要求,可选择本领域常用的粘合剂种类和用量,如粘合剂的种类可选择为PVB(聚乙烯醇缩丁醛)、PVA(聚乙烯醇)等中的至少一种,粘合剂用量可选择为粘合剂/陶瓷粉体=8~10wt%;增塑剂的种类和用量也无特别要求,可选择本领域常用的增塑剂种类和用量,如增塑剂的种类可选择为DOP、DBP等中的至少一种,增塑剂用量可选择为增塑剂/陶瓷粉体=2.5~3.5wt%。
本发明陶瓷材料能用于制备MLCC,即MLCC包括陶瓷介质和镍内电极,陶瓷介质主要由本发明陶瓷材料构成。
在一些实施方式中,陶瓷内电极包括金属镍和陶瓷阻缩剂,金属镍和陶瓷阻缩剂的质量比为3.5:1~7:1。在镍内电极中添加陶瓷阻缩剂可以缓解陶瓷生坯和镍内电极烧结的收缩匹配差异,在此基础上使用M组分会起到更好地改善开裂的效果。陶瓷阻缩剂加入过多会影响产品的电性能,这是因为烧结过程中陶瓷阻缩剂会往陶瓷介质层扩散,与介质层中的主体成分AQO3共同烧结,所以添加量过多,会引起晶粒异常长大,从而影响电性能恶化;陶瓷阻缩剂加入过少,缓解陶瓷生坯和镍内电极烧结的收缩匹配的效果变差,因此,金属镍和陶瓷阻缩剂的质量比选择为3.5:1~7:1,优选金属镍和陶瓷阻缩剂的质量比为5:1。
陶瓷阻缩剂可选择为纳米颗粒,且成分与所用陶瓷材料中的主体成分AQO3相同。陶瓷阻缩剂的种类与所用陶瓷材料中的主体成分AQO3相同,以防止其他物质的添加对MLCC的电性能造成较大的影响。
在一些实施方式中,MLCC的制备方法包括以下步骤:
(1)将AQO3、X组分、R组分、Z组分、M组分、粘合剂、增塑剂和溶剂混合制成陶瓷浆料,其中,Z组分为玻璃料;
(2)将步骤(1)所得陶瓷浆料制成陶瓷生膜;
(3)将步骤(2)所得陶瓷生膜印刷含有陶瓷阻缩剂的镍浆后,交叉层叠以获得层叠片,将层叠片压制成型后切割成所需要的尺寸,然后排胶,烧结,得到层叠芯片;
(4)通过滚筒研磨层叠芯片的角部和棱边以形成圆角,并将烧结收缩的镍电极充分裸露,即得层叠体,将层叠体两个端面涂覆铜膏,然后烧结,电镀,即得MLCC成品。
步骤(1)中,所用原料可都选择粉末状态,其中,Z组分玻璃粉末可通过以下方法制备而成:将玻璃料的Z组分加热熔融后,淬火制成玻璃碎片,然后研磨或粉碎成玻璃粉末。
步骤(2)中,陶瓷生膜的厚度可根据需要选择,如1~10μm,再如2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm等。
步骤(3)中,压制成型的处理方法可选择为等静压等,等静压的工艺条件可根据实际情况进行选择,如100Mpa/80℃等;排胶可在保护气气氛中进行,排胶的温度可选择为350-450℃等;烧结温度可依据配方进行选择,如可在1000-1280℃范围内选择。
步骤(4)中,烧铜可选择在N2+H2+H2O气氛下进行,温度可选择为700~900℃等,如700℃、800℃、900℃等。
发明人在研究过程中,采用以下测试方法对制得的多层片式陶瓷电容器进行性能测定:
(1)介电常数:按照GB/T21042-2007测试容量值,再根据C=0.00884×K×(N-1)×S/d计算介电常数,其中C为容量值(单位为pF),K为相对介电常数,N为堆叠层数,S为烧结后产品的电极面积(单位为mm2),d为烧结后产品的介质层厚度(单位为mm);
(2)介电损耗:按照GB/T21042-2007测试;
(3)TCC(电容的温度变化率):按照GB/T21042-2007测试;
(4)分层开裂比例:将多层片式陶瓷电容器产品粘附在发泡胶上,用超声波SAT检测分层开裂比例。
合格标准:2800≤介电常数≤4200,介电损耗≤7.0%,-15%≤TCC≤+15%,分层开裂比例≤10ppm。
实施例1~9与对比例1~5
实施例1~9与对比例1~5分别提供了一种多层片式陶瓷电容器,这些陶瓷电容器的制备方法包括以下步骤:
(1)将玻璃料的Z组分置于坩埚中加热至1380℃,熔融后采用水冷淬火方式制成玻璃碎片,随后用高速球磨机球磨12h制得玻璃态粉末;
(2)将步骤(1)所得玻璃态粉末、BaTiO3粉末、X组分粉末、R组分粉末、M组分粉末、PVB(聚乙烯醇缩丁醛)粘合剂、DOP(邻苯二甲酸二辛酯)、甲苯和无水乙醇混合均匀,用砂磨机砂磨分散,获得陶瓷浆料,将所得陶瓷浆料用流延机流延成膜厚为3μm陶瓷生膜,其中玻璃态粉末、X组分粉末、R组分粉末及M组分粉末的组成及用量见表1,BaTiO3粉末、PVB粘合剂、DOP、甲苯和无水乙醇的质量比为100:9.2:2.8:38.4:81.6;
(3)将步骤(2)所得陶瓷生膜上印刷含有陶瓷阻缩剂的镍浆(金属镍/陶瓷阻缩剂质量比为5:1,陶瓷阻缩剂为BaTiO3纳米颗粒)后,经过给定片数的交错叠层获得叠层片,叠层片经过100Mpa/80℃等静压后切割成指定的尺寸;
(4)经过N2环境400℃条件的排胶处理后,在1220℃保温2h进行烧结,得到层叠芯片;
(5)随后通过滚筒研磨使层叠芯片的角部和棱边形成圆角,并将烧结收缩的镍电极充分裸露,将该层叠体两个端面涂覆铜膏,并于800℃在N2+H2+H2O气氛下烧结,然后电镀,即得陶瓷电容器成品。
表1
以实施例1为例,来说明各实施例和对比例中X组分、R组分、Z组分和M组分的组成和用量。实施例1中,X组分由MgO和Dy2O3组成,其中MgO的摩尔量为陶瓷浆料中BaTiO3摩尔量的0.8%,Dy2O3的摩尔量为陶瓷浆料中BaTiO3摩尔量的0.8%;R组分由V2O5、MnO和Cr2O3组成,其中V2O5的摩尔量为陶瓷浆料中BaTiO3摩尔量的0.03%,MnO的摩尔量为陶瓷浆料中BaTiO3摩尔量的0.03%,Cr2O3的摩尔量为陶瓷浆料中BaTiO3摩尔量的0.02%;Z组分由BaCO3、ZnO、B2O3和SiO2组成,其中BaCO3的摩尔量为陶瓷浆料中BaTiO3摩尔量的0.3%,ZnO的摩尔量为陶瓷浆料中BaTiO3摩尔量的0.1%,B2O3的摩尔量为陶瓷浆料中BaTiO3摩尔量的0.3%,SiO2的摩尔量为BaTiO3摩尔量的0.8%;M组分由KAlSi2O6组成,KAlSi2O6的摩尔量为陶瓷浆料中BaTiO3摩尔量的0.3%。
各实施例和对比例所得多层片式陶瓷电容器的性能测试结果见表2。
表2
综合考虑分层开裂比例和产品电性能,M组分用量(即M组分摩尔量为BaTiO3摩尔量的百分比)在0.3~3.6mol%之间,分层开裂比例低,各项电性能符合使用要求。对比例1和对比例3中,M组分添加过多,分层开裂比例增加,超过10ppm,且产品介电常数偏低。对比例2和对比例4中,M组分添加过少,分层开裂情况改善不明显。对比例5中,由于未添加M组分,分层开裂情况尤为明显,比例高达16ppm,严重影响实际生产应用。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (11)
1.一种陶瓷材料,其特征在于,包括主体成分AQO3、M组分、X组分、R组分和Z组分,其中,A为Ba、Ca、Sr中的至少一种,Q为Ti、Zr、Hf中的至少一种,M组分为KAlSi2O6、ZrW2O8、HfW2O8中的至少一种,X组分为Mg、La、Sm、Dy、Ho、Er、Y、Eu、Gd、Tm、Yb中至少一种元素的化合物;R组分为V、Mn、Cr、Co、Fe中至少一种元素的化合物;Z组分为Si、Ba、B、Zn、Al、Li中至少一种元素的化合物;所述M组分的摩尔量为AQO3摩尔量的0.3~3.6%,所述X组分的摩尔量为AQO3摩尔量的0.4~2.2%,所述R组分的摩尔量为AQO3摩尔量的0.08~0.4%,所述Z组分的摩尔量为AQO3摩尔量的0.5~4.5%。
2.根据权利要求1所述的陶瓷材料,其特征在于,所述M组分的摩尔量为AQO3摩尔量的1.6~2.8%。
3.根据权利要求1或2所述的陶瓷材料,其特征在于,所述X组分、R组分和Z组分均为含氧化合物。
4.根据权利要求1所述的陶瓷材料,其特征在于,所述X组分、R组分和Z组分均为氧化物、碳酸盐、氢氧化物中的至少一种。
5.根据权利要求3所述的陶瓷材料,其特征在于,所述Z组分为玻璃料。
6.根据权利要求1或2所述的陶瓷材料,其特征在于,所述A为Ba,所述Q为Ti。
7.一种陶瓷浆料,其特征在于,包括如权利要求1-6任一项所述的陶瓷材料。
8.一种多层片式陶瓷电容器,其特征在于,包括陶瓷介质和镍内电极,所述陶瓷介质主要由如权利要求1-6任一项所述的陶瓷材料构成。
9.根据权利要求8所述的多层片式陶瓷电容器,其特征在于,所述镍内电极包括金属镍和陶瓷阻缩剂,所述金属镍和陶瓷阻缩剂的质量比为3.5:1~7:1。
10.根据权利要求9所述的多层片式陶瓷电容器,其特征在于,所述金属镍和陶瓷阻缩剂的质量比为5:1。
11.根据权利要求9或10所述的多层片式陶瓷电容器,其特征在于,所述陶瓷阻缩剂为纳米颗粒,且成分与所述陶瓷材料中的主体成分AQO3相同。
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