CN117423549B - 一种mlcc及改善生倒粘片的mlcc制造方法 - Google Patents
一种mlcc及改善生倒粘片的mlcc制造方法 Download PDFInfo
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- CN117423549B CN117423549B CN202311351915.2A CN202311351915A CN117423549B CN 117423549 B CN117423549 B CN 117423549B CN 202311351915 A CN202311351915 A CN 202311351915A CN 117423549 B CN117423549 B CN 117423549B
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Abstract
本申请提出了一种MLCC及改善生倒粘片的MLCC制造方法。所述方法包括:将水和待排胶的陶瓷生坯按照预设比例混合;对混合的陶瓷生坯和水进行球磨处理,以使陶瓷生坯的棱角打磨成为圆角;对球磨处理后的陶瓷生坯进行滤水处理,并加入粉料混合搅拌均匀,以使陶瓷生坯的表面覆盖有粉料;对覆盖有粉料的陶瓷生坯进行排胶、烧结及倒角等处理,倒角处理可以去除沾附在陶瓷生坯表面的粉料。本申请可以避免内应力在陶瓷生坯的棱角处集中,从而避免陶瓷生坯在烧结及倒角制程中出现瓷损甚至开裂;粉料阻挡了粘结剂将陶瓷生坯粘结在一起,可以改善粘片现象以及由此导致的瓷损问题。
Description
技术领域
本申请涉及片式多层陶瓷电容器技术领域,具体涉及一种MLCC(Multi-layerCeramic Chip Capacitors,片式多层陶瓷电容器)及改善生倒粘片的MLCC制造方法。
背景技术
为了满足电子设备不断向小型化、大容量化、高可靠性和低成本的方向发展,MLCC也在随之迅速发展,并且随着技术不断进步,材料不断更新,种类不断增加,体积不断缩小,性能不断提高。小型化、大容量系列产品已趋向于标准化和通用化。多层陶瓷电容器是将内电极浆料(在烧结之前可称为内电极料片)印刷在介质层上,然后按照设计要求将印刷有内电极的介质层一层层的叠压在一起,再经过压合和切割处理,获得陶瓷生坯,再经过例如排胶、烧结等后续处理,即可获得具备所需性能的产品。由于内电极与介质层烧结收缩存在差异,会在烧结过程产生烧结内应力,并且随着多层陶瓷电容器容量的提高,内电极和介质层的层数急剧增加,导致陶瓷生坯中内电极与介质层的内应力越大,越容易导致陶瓷生坯在烧结及倒角制程中出现瓷损甚至开裂,严重影响产品的电性能及可靠性。因此降低陶瓷生坯的内应力,对改善多层陶瓷电容器(尤其是大容量的多层陶瓷电容器)的电性能及可靠性具有重要的意义。
发明内容
鉴于此,本申请提供一种MLCC及改善生倒粘片的MLCC制造方法,可以改善陶瓷生坯的内应力较大以及由此导致陶瓷生坯在烧结及倒角制程中容易出现瓷损甚至开裂的问题。
本申请提供的一种改善生倒粘片的MLCC制造方法,包括:
将水和待排胶的陶瓷生坯按照预设比例混合;
对混合的陶瓷生坯和水进行球磨处理,以使所述陶瓷生坯的棱角打磨为圆角;
对所述球磨处理后的陶瓷生坯进行滤水处理,并加入粉料混合搅拌均匀,以使所述陶瓷生坯的表面覆盖有所述粉料;
对覆盖有所述粉料的陶瓷生坯进行排胶、烧结及倒角等后续处理。
可选地,对覆盖有所述粉料的陶瓷生坯进行排胶处理之前,所述方法还包括:对搅拌后的陶瓷生坯进行冷风烘干处理。
可选地,所述冷风烘干处理满足:温度为T,且8℃≤T≤15℃;时长为t1,且60min≤t1≤120min。
可选地,所述粉料包括锆粉和二氧化钛粉中的至少一种。
可选地,所述粉料的粒径为φ,且满足:0.01mm≤φ≤0.1mm。
可选地,所述预设比例为体积比,所述待排胶的陶瓷生坯和水的体积比为1:10~1:20。
可选地,所述陶瓷生坯为圆角的顶角的半径为R0;所述陶瓷生坯内部设置有相互间隔的多个内电极料片,所述内电极料片的顶角为圆角,且半径为R1;且满足:R0≥R1。
可选地,所述球磨处理满足:转速为S,且130rpm≤S≤170rpm;时长为t2,且30min≤t2≤300min。
可选地,在排胶处理后,所述方法还包括:对经过排胶处理的陶瓷生坯进行烧结处理,然后将烧结处理后的陶瓷生坯进行倒角(又称轻倒角),去除沾附在陶瓷生坯表面的粉料,即可获得片式多层陶瓷电容器半成品。
本申请提供的一种MLCC,采用如上任一项的方法制得。
如上所述,本申请将水和切割完待排胶的陶瓷生坯按照预设比例混合,再在一定的转速和时间下进行球磨处理,以水为媒介,在高速旋转下,陶瓷生坯之间相互碰撞,将棱角打磨光滑以变为圆角,起到了初步倒角的作用,可以避免内应力在棱角处集中,从而可以避免陶瓷生坯在烧结及倒角制程中出现瓷损甚至开裂;进行滤水处理,加入粉料混合搅拌均匀,以使陶瓷生坯的表面覆盖有粉料,粉料阻挡了粘结剂将陶瓷生坯粘结在一起,从而可以改善粘片现象以及由此导致的瓷损问题。
附图说明
图1为本申请实施例提供的一种片式多层陶瓷电容器的结构立体图;
图2为本申请实施例提供的一种各层内电极的层叠排布示意图;
图3为本申请实施例提供的一种片式多层陶瓷电容器的局部结构爆炸示意图;
图4为本申请实施例提供的一种改善生倒粘片的MLCC制造方法的流程图;
图5为本申请实施例提供的另一种改善生倒粘片的MLCC制造方法的流程图。
具体实施方式
为使本申请的目的、技术方案和优点更加清楚,下面将结合具体实施例及相应的附图,对本申请的技术方案进行清楚地描述。显然,下文所描述实施例仅是本申请的一部分实施例,而非全部的实施例。在不冲突的情况下,下述各个实施例及其技术特征可相互组合,且亦属于本申请的技术方案。
在本申请实施例的描述中,术语“中心”、“纵向”、“横向”、“长度”、“宽度”、“厚度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”、“顺时针”、“逆时针”等指示的方位或位置关系为基于附图所示的方位或位置关系,仅为便于描述相应实施例的技术方案,而非指示或暗示装置或元件必须具有特定方位、以特定方位构造和操作,不能理解为对本申请的限制。
为了更加清楚的介绍本申请的技术方案,下面先介绍多层陶瓷电容器的结构,请一并参阅图1至图3所示,所述多层陶瓷电容器1可以为MLCC,包括陶瓷主体10、端电极12以及内电极13。
多层陶瓷电容器1的形状及尺寸,本申请实施例不予限定,例如形状可以为图1至图3所示的长方体、或者矩形等类四方体。所谓类四方体可以理解为多层陶瓷电容器1的外形整体上呈矩形体,但顶角为具有预定曲率半径的圆角,形成单个顶角的线条并非为传统尖角的两条。需要说明的是,图2和图3所示的为多层陶瓷电容器1的一部分,具体为多个内电极13和多个介质层11相结合的结构,示出了内电极13和介质层11之间的层叠关系,而未示出端电极12,图中所示的内电极13和介质层11的数量仅供示例性展示。
多层陶瓷电容器1的长度方向为第一方向x,多层陶瓷电容器1的高度方向为第二方向y,多层陶瓷电容器1的宽度方向为第三方向z,第一方向x、第二方向y和第三方向z两两垂直,可视为三维直角坐标系的三条坐标轴。
应理解,本申请全文所谓的垂直并非要求两者之间的夹角必须为90°,而是允许存在±10°的偏差,即所谓垂直可以理解为任意两个方向之间的夹角为80°至100°。同理,本申请全文所谓的平行也并非要求两者之间的夹角必须为0°或180°,而是允许存在±10°的偏差,即所谓的平行可以理解为任意两个方向之间的夹角为0°至10°或170°至190°。
如图2和图3所示,多个介质层11依次堆叠形成多层陶瓷电容器1的陶瓷主体10,该陶瓷主体10由陶瓷生坯通过烧结等工艺制得。多个介质层11可以为具有非线性特性的半导体材料构成,例如可以为采用多个流延的介质膜片层叠而成的结构体,每一介质膜片通过烧结等工序即可形成前述一介质层11,构成介质膜片的主体成分可以为钛酸钡、钛酸镁、钛酸钙、锆酸钙和钛酸锶中的至少一种,并含有形成具有非线性特性的副成分铋(Bi)、钴(Co)、钇(Y)、镝(Dy)、锰(Mn)、铬(Cr)、锑(Sb)等至少一种的氧化物,例如Bi2O3、Co2O3、MnO2、Sb2O3、Dy2O3、Cr2O3、Y2O3等多种添加剂。在一实施例中,钛酸钡、钛酸镁、钛酸钙、锆酸钙和钛酸锶的质量占比为α,85%≤α≤98%,以确保介质层11的特性。
内电极13和介质层11沿第二方向y依次交替层叠设置,例如,通过流延和烘干、裁切等方式形成如图3所示的位于最下方的第一个介质层11,可称为下保护盖14,然后在该第一个介质层11上形成第二个介质层11,接着在第二个介质层11上设置第一个内电极13,第三个介质层11通过相同或相似方式形成设置于第二个介质层11和第一个内电极13上,第二个内电极13设置于第三个介质层11上,依次类推,从而形成包含多个内电极13的陶瓷主体10。可选地,如图4所示,最后形成的一个介质层11位于陶瓷主体10的最上方,可以称为上保护盖15;该下保护盖14和上保护盖15的厚度可以相等,且可以均大于任一其他介质层11的厚度。
相邻两层内电极13之间通过陶瓷体(即两层内电极13之间夹设的介质层11)绝缘,沿第二方向y,这些内电极13可以整体上均呈矩形。
如图1所示,多层陶瓷电容器1设置有端电极12,端电极12与对应的内电极13连接。端电极12的宽度以及形状包括但不限于图1所示,可以根据实际所需适应性设定。在一些实施方式中,端电极12的导电材料,例如可由铜、银、金、钯、铂,或者铜、银、金、钯、铂等的合金组成。
两个端电极12分别设置于陶瓷主体10沿第一方向x的相对两侧;任意相邻两个内电极13中的一者与其中一端电极12(例如左侧的端电极12)连接,另一者与另一外电极(例如右侧的端电极12)连接。
结合图4所示,该改善生倒粘片的多层陶瓷电容器1的制造方法包括如下步骤S1至S5。
S1:将水和待排胶的陶瓷生坯按照预设比例混合。
S2:对混合的陶瓷生坯和水进行球磨处理,以使陶瓷生坯的棱角打磨为圆角。
S3:对球磨处理后的陶瓷生坯进行滤水处理,并加入粉料混合搅拌均匀,以使陶瓷生坯的表面覆盖有所述粉料。
S4:对覆盖有粉料的陶瓷生坯进行排胶、烧结及倒角处理。
在步骤S1中,待排胶的陶瓷生坯可以通过如下步骤S11~S16制得:
S11:配料
在一示例中,将陶瓷粉、粘结剂及溶剂和各种添加剂按一定比例经过一定时间的球磨或砂磨,形成均匀、稳定的瓷浆。
陶瓷粉作为最主要的材料决定了片式多层陶瓷电容器的基本特性,具体可以包括前述主体成分和副成分。粘结剂是高分子树脂,作用是使陶瓷粉之间维持一定的距离并提供强度。溶剂可以是甲苯和乙醇按照一定比例混合而成。分散剂是为了避免陶瓷粉表面静电作用而发生的粘连及团聚,以保证瓷浆能形成稳定分散的悬浮液的一种表面活性剂。添加剂用于调节陶瓷粉本身的电特性、满足产品信赖性方面的某些要求、保证烧结能够较好地进行。
S12:流延
在一示例中,将瓷浆通过流延机的浇注口,使其涂布在绕行的有机硅薄膜上,从而形成一层均匀的瓷浆薄层,再通过热风区,通过加热干燥方式将瓷浆中绝大部分溶剂挥发,从而形成具有一定厚度、密度且厚度均匀的薄膜。
成型过程中流延挤出方式可以根据实际情况适应性而定。
S13:印刷
在一示例中,可以通过丝网版将内电极浆料印刷到介质膜片上,并进行烘干处理,内电极浆料烘干成型后可称为内电极料片。印刷类型包括如下至少一种:1.凸版印刷,在凸出部分蘸内电极浆料之后加压印刷。2.凹版印刷,在整个板上蘸内电极浆料之后只在凹进部分留内电极浆料进行印刷。3.平板印刷,利用水和油的排斥作用,版面蘸内电极浆料进行印刷。4.丝网印刷,通过丝网孔排出内电极浆料后印刷成型。
S14:叠层
将印刷有内电极料片的介质膜片一张一张按一定错位整齐叠合在一起使之形成厚度一致的巴块。叠层时底部和顶面还需要加上陶瓷膜保护片,以增加机械强度和提高绝缘性能。
S15:层压
层压主要流程:巴块装密封袋→进层压机→加压加温层压→冷却→拆袋。各阶段的具体操作,可参阅现有技术,此处不予以赘述。
在一示例中,将叠层后的巴块通过均匀温度的静水均压的方式,使巴块中各叠层的介质膜片彼此紧密结合,以提高烧结后瓷体的致密性,使其更加紧密结合在一起的过程。该道制程中除了压力、时间、温度等关键品质因数(CTQ)外,压力的均匀性越高,层压效果越好,本申请可选地将巴块放置于水中进行均压。进一步可选地,进行切片抽测以确认层压效果。
S16:切割
将层压后的巴块按照设计要求,使用片式薄刀片按设计尺寸对巴块进行横向及纵向切割,使其成为完全分离的多个陶瓷生坯。
切割原理:刀片对巴块进行下切时,刀座推动刀片向下运动,刀锋接触巴块上部,刀座继续推动刀片向下铡压,当刀片在刀座及惯性的作用下到达承载巴块的基材(例如PET基材)表面时,刀座向上提升,从而完成一次切割。
由上述步骤S11~S16可知,待排胶的陶瓷生坯内部含有粘结剂。
在步骤S2中,在一定的转速和时间下进行球磨处理,以水为媒介,在高速旋转下,陶瓷生坯之间相互碰撞,将各个陶瓷生坯的棱角打磨光滑以变为圆角,起到了初步倒角的作用,可以避免内应力在棱角处集中,从而可以避免陶瓷生坯在烧结及倒角制程中出现瓷损甚至开裂。
其中,所述棱角不仅包括陶瓷生坯的各个顶角,例如图1至图3所示的六个顶角,还包括陶瓷生坯的各条棱。于此,结合图1至图3所示的方位,所谓圆角可以理解为:至少沿x-z方向的截面具有圆形弧线的夹角(顶角),以及沿x-y方向的截面和沿y-z方向的截面也可以为具有圆形弧线的夹角。所谓圆角的半径可以理解为:圆形弧线所在圆的半径。
在步骤S2结束之后,各个陶瓷生坯暴露的表面面积更大,内部的粘接剂更多的暴露于陶瓷生坯的表面。于此,在步骤S3中,进行滤水处理,加入粉料混合搅拌均匀,以使陶瓷生坯的表面覆盖有粉料,粉料阻挡了粘结剂将陶瓷生坯粘结在一起,从而可以改善粘片现象以及由此导致的瓷损问题。
在一示例中,所述粉料可以为锆粉和二氧化钛粉中的至少一种。可选地,所述锆粉、二氧化钛粉等的粒径为φ,且满足:0.01mm≤φ≤0.1mm;将待排胶的陶瓷生坯和水的体积比为1:10~1:20;所述球磨处理满足:转速为S,且130rpm≤S≤170rpm;时长为t2,且30min≤t2≤300min;通过加入该粒径的锆粉、二氧化钛粉等粉料,可以确保在球磨后,锆粉、二氧化钛粉等可以较为均匀且充分的覆盖于陶瓷生坯的表面。
在步骤S4中,排胶可以理解为对陶瓷生坯进行热处理,排除粘结剂等有机物。例如,对于镍电极作为内电极的MLCC,采用空气排胶,温度可以在250℃左右,或者采用氮气排胶,温度约为400℃-500℃。
在步骤S4结束排胶处理之后,本申请还可以执行如下步骤S51至S54:
S51:烧结
在一示例中,烧结过程是在气氛炉中进行,烧结温度可以在1100℃~1350℃之间。由于是高温烧结,为了防止氧化等,烧结炉里面可以填充氮气或者氢气。烧结过程中,炉膛内的温度变化均匀,并在一个热动态平衡中进行,例如空气应充分流动,以陶瓷主体的晶相生长均匀与致密。
S52:倒角
倒角,也叫研磨。经过烧结成瓷的陶瓷主体的棱角分明,在进行倒角处理后,有利于与外部电极(或称端电极)的连接。在一示例中,倒角工序是将陶瓷主体与水和磨介质装在倒角罐里,通过球磨、行星磨等方式运动,除去陶瓷主体表面的杂物、毛刺,使其表面及棱角光滑,同时也使端面的内电极充分暴露。
对经过排胶处理的陶瓷生坯进行烧结处理,然后将烧结处理后的陶瓷生坯进行倒角处理,倒角处理相当于进行了打磨抛光处理,可以去除沾附在烧结后的陶瓷生坯表面的锆粉、二氧化钛粉等粉料,即可获得无烧结粘片、无开裂或瓷损的片式多层陶瓷电容器半成品。
S53:封端及烧端
在一示例中,通过封端机,将端浆涂覆在经倒角处理后的陶瓷主体外露内部电极的端部上,并与暴露的内电极连接,然后进行烘干,接着在高温650℃~850℃左右的环境中,烧结炉里面可以填充氮气,使端电极浆料中的有机黏合剂充分燃烧,玻璃体熔融并浸润铜粉,使端头固化并与陶瓷主体和内电极形成良好的连接。
S54:电镀和测试
对烧端后的端电极进行电镀,在一示例中,在含有镍和锡金属离子的电解质溶液中,将多层陶瓷电容器的端电极作为阴极,通过一定的低压直流电,分别不断在阴极沉积为一层镍和锡。
上述步骤S52,以及在传统工艺中在对陶瓷生坯执行烧结制程后进行的倒角制程,由于是对烧结后的陶瓷主体进行倒角,因此可称为熟倒或轻倒角。而本申请的步骤S2是在烧结制程之前进行的研磨,因此可称为生倒。在生倒制程中,陶瓷生坯之间相互碰撞,将棱角打磨光滑以变为圆角,起到了初步倒角的作用,可以避免内应力在陶瓷生坯的棱角处集中,从而可以避免陶瓷生坯在后续的烧结及熟倒制程中出现瓷损甚至开裂。
在步骤S4之前,即对陶瓷生坯进行排胶处理之前,如图5所示,本申请的方法还可以包括:步骤31:对搅拌后的陶瓷生坯进行冷风烘干处理。
在冷风烘干处理的过程中,冷风的温度较低,不仅不会增大甚至还可以降低生倒制程后陶瓷生坯表面的温度,从而降低粘结剂的粘性,可以进一步降低陶瓷生坯之间粘结的概率,进一步改善粘片现象以及由此导致的瓷损问题。
在一示例中,所述冷风烘干处理满足:温度为T,且8℃≤T≤15℃;时长为t1,且60min≤t1≤120min。
请继续参阅图1至图3,经过上述步骤S2和S3之后,所述陶瓷生坯(图中经过烧结等制程形成为陶瓷主体10)为圆角的顶角的半径为R0。
内电极料片(图中经过烧结等制程形成为内电极13)设置有圆角,具体地,未与外电极12连接的自由端两个顶角,所述两个顶为圆角,且半径为R1,所谓圆角可以理解为:至少沿x-z方向的截面具有圆形弧线的夹角(即顶角),所谓圆角的半径可以理解为:圆形弧线所在圆的半径。
本示例通过将内电极料片的自由端的顶角设置有圆角,增大内电极料片分别与对应的外电极12边缘之间的距离,既可以降低内应力以避免烧结及倒角时出现瓷损,还可以对于在烧结等制程后制得的片式多层陶瓷电容器,在接电运行时降低陶瓷主体10(例如陶瓷主体10与所述圆角对应的顶角)被击穿以及由此导致负载失效的风险;另外,圆角可以避免尖端放电,进一步有利于降低陶瓷主体10与该圆角对应的顶角被击穿以及由此导致负载失效的风险。
在一示例中,内电极料片的圆角的半径R1大于陶瓷生坯的圆角的半径R0,即R0≥R1。例如,0.05mm≦R1≦0.1mm,0.2mm≦R0≦0.5mm。
本申请实施例还提供一种MLCC,采用如上任一实施例的方法制得。
本申请实施例还提供一种电子设备,该电子设备包括上述任一实施例的片式多层陶瓷电容器,片式多层陶瓷电容器设置于电子设备的电路中。
电子设备可以以各种具体形式来实施,例如,智能手机、可穿戴设备、无人机、电动车、电动清洁工具、储能产品、电动汽车、电动自行车、电动导航工具等电子产品。本领域技术人员可理解的是,除特别用于移动目的元件之外,根据本申请实施例的构造也能够应用于固定类型的电子设备。
由于电子设备具有通过前述任一实施例的方法制得的片式多层陶瓷电容器,因此,该电子设备能够产生对应实施例的方法具有的有益效果。
以上所述仅为本申请的部分实施例,并非因此限制本申请的专利范围,对于本领域普通技术人员而言,凡是利用本说明书及附图内容所作的等效结构变换,均同理包括在本申请的专利保护范围内。
尽管本文采用术语“第一、第二”等描述各种信息,但这些信息不应限于这些术语。这些术语仅用来将同一类型的信息彼此区分开。另外,单数形式“一”、“一个”和“该”旨在也包括复数形式。术语“或”和“和/或”被解释为包括性的,或意味着任一个或任何组合。仅当元件、功能、步骤或操作的组合在某些方式下内在地互相排斥时,才会出现该定义的例外。
Claims (5)
1.一种改善生倒粘片的MLCC制造方法,其特征在于,包括:
将水和待排胶的陶瓷生坯按照预设比例混合,所述预设比例为体积比,所述待排胶的陶瓷生坯和水的体积比为1:10~1:20;
对混合的陶瓷生坯和水进行球磨处理,以使所述陶瓷生坯的棱角打磨为圆角,所述陶瓷生坯为圆角的顶角的半径为R0,所述陶瓷生坯内部设置有相互间隔的多个内电极料片,所述内电极料片的顶角为圆角,且半径为R1;且满足:R0≥R1;
对所述球磨处理后的陶瓷生坯进行滤水处理,并加入粉料混合搅拌均匀,以使所述陶瓷生坯的表面覆盖有所述粉料;
对搅拌后的陶瓷生坯进行冷风烘干处理,所述冷风烘干处理满足:温度为T,且8℃≤T≤15℃;时长为t1,且60min≤t1≤120min;
对所述冷风烘干处理后且覆盖有所述粉料的陶瓷生坯进行排胶、烧结及倒角处理。
2.根据权利要求1所述的方法,其特征在于,所述粉料包括锆粉和二氧化钛粉中的至少一种。
3.根据权利要求2所述的方法,其特征在于,所述粉料的粒径为φ,且满足:0.01mm≤φ≤0.1mm。
4.根据权利要求1所述的方法,其特征在于,所述球磨处理满足:转速为S,且130rpm≤S≤170rpm;时长为t2,且30min≤t2≤300min。
5.一种MLCC,其特征在于,采用如权利要求1至4中任一项的方法制得。
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