CN116655373A - 一种低电容电压系数的x7r瓷粉及其制备方法和应用 - Google Patents

一种低电容电压系数的x7r瓷粉及其制备方法和应用 Download PDF

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CN116655373A
CN116655373A CN202210157662.4A CN202210157662A CN116655373A CN 116655373 A CN116655373 A CN 116655373A CN 202210157662 A CN202210157662 A CN 202210157662A CN 116655373 A CN116655373 A CN 116655373A
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barium titanate
powder
mixed
voltage coefficient
ceramic
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王根水
李智强
闫世光
董显林
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Shanghai Institute of Ceramics of CAS
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Abstract

本发明涉及一种低电容电压系数的X7R瓷粉及其制备方法和应用。所述低电压系数的X7R瓷粉，由纳米钛酸钡为主晶相，以及包覆在纳米钛酸钡表面的复合改性氧化物组成；所述复合改性氧化物的组成为Dy2O3、Ho2O3、MgO、MnO、SiO2、CaO和BaO。

Description

一种低电容电压系数的X7R瓷粉及其制备方法和应用
技术领域
本发明涉及一种用于偏压特性优良其满足X7R温度稳定特性的X7R瓷粉及其制备方法和应用，具体涉及一种用化学包覆法制备以贱金属内电极的超细晶温度稳定型贱金属内电极MLCC(BME-MLCC)的介电层介质材料，属于电子功能陶瓷材料领域。
背景技术
多层陶瓷电容器(Multilayer Ceramic Capacitor，简称MLCC)是将陶瓷胚体与内电极交替叠层，共烧为一个整体，适合于片式化表面组装，可提高电路组装密度，缩小整机体积，因此特点广泛应用于机器人部件、医疗设备、汽车部件等各种应用中。MLCC包含两种主要类型Ⅰ类和Ⅱ类：Ⅰ类MLCC高稳定性、准确性和低损耗，提供最可靠的电压、温度和频率；Ⅱ类高介电常数，提供更出色的容积效率。对于Ⅱ类MLCC而言，其比电容大，电容量随温度呈非线性变化，损耗较大，常在电子设备中用于旁路、耦合或用于其它对损耗和电容量稳定性要求不高的电路中。根据国际电子工业协会EIA标准，X7R温度稳定型MLCC是指在-55℃～125℃之内，容温变化率TCC(ΔC/C25℃)≤±15％，介电损耗(DF)≤2.5％，此外还有X5R(-55℃～85℃，TCC≤±15％，DF≤2.5％)。常用的Ⅱ类MLCC介质材料有两种，一种是含Pd、Cd的铁电体组成，另一种是以BaTiO3基的铁电体组成。后者由于对环境无污染，并且机械强度和可靠性优于前者，有更广阔的前景。近几年MLCC技术的发展主要集中在微型化、高容量化和以贱金属内电极为主的还原烧结方面的研究。
以高介电常数陶瓷介质的多层陶瓷电容器在加载直流偏置电压时，其容量会随偏置电压的增大而下降，这种特性成为直流(DC)偏压特性，或简称偏压特性，这种现象是钛酸钡基铁电体的高介电常数类MLCC特有的现象。当没有外加直流电压时，自发极化为随机取向状态，陶瓷内部的偶极子可以自由翻转，介电常数较大；但当从外部施加直流电压时，由于电介质中的自发极化受到电场方向的束缚，因此不易发生自发极化时的自由相转变，介质的介电常数下降，从而电容器的容量减少。对于高诱电率系列的电容器(B/X5R、R/X7R特性)需要特别注意是否具备低电容电压系数，在电路应用中若不能提供足够的有效容量，就会导致储能能力下降或者阻抗增大去去耦效果变差等不良现象。
电子元器件小型化、高性能的发展趋势要求BME-MLCC朝着大容量、超薄层的方向发展。介质单层厚度不断降低，从5μm降至1μm甚至更薄，这就对陶瓷介质瓷料提出更高的要求。为保证器件的可靠性，介质层的陶瓷晶粒要降到纳米级，并且晶粒大小均匀，这导致对瓷料要求在纳米级且具备良好的改性性能。但是，介质厚度剧减，会引起介电常数的降低，单位厚度的介质上承受的直流电压剧增，产生容量下降的问题。在美国US-62709906B1中晶粒尺寸降至100～200nm，其介电常数为1600～1800；在中国专利CN107739204B中以(Ba1- xSrx)TiO3及其改性添加物为电介质瓷料可实现900～1500的介电常数且电容电压系数变化在40％左右。但以上介电常数均低于2000，DC偏压特性较差，缺乏兼具高介电常数和低偏压特性的瓷料。因此，如何获得细晶且均匀、有较高介电常数且较低DC偏压变化率的X7R稳定型电介质瓷料，瓷料可满足大容量化、贱金属化、薄层化BME-MLCC的要求是本发明所要解决的技术问题。
发明内容
针对上述问题，本发明提供了一种低电压系数的X7R瓷粉及其制备方法和应用。
一方面，本发明提供了一种低电压系数的X7R瓷粉，由纳米钛酸钡为主晶相，以及包覆在纳米钛酸钡表面的复合改性氧化物组成，其厚度优选为3～12nm；所述复合改性氧化物的组成为Dy2O3、Ho2O3、MgO、MnO、SiO2、CaO和BaO。
较佳的，所述纳米钛酸钡的摩尔含量为92～97mol％，所述复合改性氧化物的摩尔分数为8～3mol％。
较佳的，所述复合改性氧化物中Dy：Ho：Mg：Mn：Si：Ca：Ba＝(0～2)：(2～0)：(3～7)：(0.5～3)：(3～4)：(2～5)：(2.5～3.5)；优选地，所述Dy和Ho的摩尔比为3：(1～9)，优选为1：(0.5～1.5)，更优选为1：1。其中，Dy和Ho的掺杂对晶粒生长具有抑制的作用。当Dy3+和Ho3+离子溶解到Ti位点并达到溶解度极限，Ti4+离子被提取到晶界并形成共晶相。而且，细晶粒陶瓷的晶界比例比粗晶粒陶瓷的高，降低了电子载流子引起漏电流。以上两方面共同造成电阻率更高，介电损耗更小。
较佳的，其中Dy：Ho：Mg：Mn：Si：Ca：Ba＝1：1：6：1：3：3.6：2。
较佳的，所述纳米钛酸钡的粒径为150～500nm，优选为150～200nm。本发明人发现：大于0.5μm的细晶粒BaTiO3中90°畴壁出现的几率越小，越不能靠其反复孪生来消除应力，此时陶瓷而导致的内应力导致介电常数提高，所以介电常数增加。但晶粒小于0.5μm时，不能继续减小90°畴，反而使陶瓷晶界增多，晶界处晶胞的自发极化能力丧失，这相当于在陶瓷中引入大量的非铁电相，从而使陶瓷介电常数下降。
另一方面，本发明提供了一种低电压系数的X7R瓷粉的制备方法，包括：
(1)通过超声雾化技术分散获得分散均匀且良好的浆料，浆料制备方法为以水、无水乙醇或异丙醇作为分散剂与钛酸钡粉体按照一定的质量比例进行超声雾化分散，得到钛酸钡粉体悬浮液；
(2)将可溶性的Dy2O3、Ho2O3、MgO、MnO、CaO和BaO所对应的金属硝酸盐或醋酸盐按摩尔比称重，溶解在去离子水中，得到澄清的混合无机盐溶液；
(3)将正硅酸四乙酯按摩尔比溶解在乙醇和去离子水混合溶液中，得到澄清稳定的混合有机盐溶液；
(4)将混合无机盐溶液和混合有机盐溶液分别滴加到钛酸钡粉体悬浮液中，同时按0.1～0.2滴/s加入稀释氨水溶液，调节混合溶液pH值至8.5～10.5并陈化一定时间，得到混合粉体；
(5)将混合粉体在空气中300～500℃下在预烧2～4小时，得到低电压系数的X7R瓷粉。
较佳的，所述混合无机盐溶液：混合有机盐溶液的体积比＝(5：4)～(2：1)。
再一方面，本发明提供了一种兼具高介电常数和低电容电压系数的介质陶瓷块体材料，选用上述低电压系数的X7R瓷粉作为原料进行造粒，再经压制成型、脱粘、烧结和退火得到。
较佳的，所述脱粘的温度为750～800℃，时间为1～3小时。
较佳的，所述烧结的气氛为还原性气氛，温度为1300～1360℃，时间为2～4小时，优选所述还原气氛为N2/H2混合气氛，更优选N2和H2的体积比为98：2～95：5。
较佳的，所述退火的气氛为氧分压为1～50Pa的弱氧化条件，温度为800～950℃，时间为4～6小时。
较佳的，当纳米钛酸钡的粒径为150～200nm时，所述介质陶瓷块体材料室温下介电常数大于2200，且DC偏压变化率小于20％。其中，DC偏压导致介电常数下降与BaTiO3晶粒的90°畴和畴壁运动有关。在施加电场前，BaTiO3中存在畴壁，畴壁主要被Dy/Ho等离子和带正电的氧空位所产生的缺陷偶极子夹持。当首次施加直流偏置时，少量未夹持的畴壁移动。随着时间的推移，直流场的连续施加移动了各离子位点。Dy/Ho等离子引入和化学包覆法，很好的改性了纳米BaTiO3粉体表面，使各个元素等量均匀的分布在颗粒表面，烧结后陶瓷可以形成具有核壳结构的陶瓷。这些增强了畴壁运动限制，进而削弱了施加电场导致的介电常数下降。
有益效果：
本发明中，制成性能优异的温度稳定型(X7R/X5R型)MLCC材料。其室温介电常数(圆片样品)可以控制在2000～2700之间，满足X7R/X5R性能要求，容温变化率小，介电损耗小，并且绝缘电阻率高，在室温附近的绝缘电阻率为(8.278～9.347)×1012Ω·cm、40kV/cm电场下DC偏压介电常数为(1940～1990)且其DC偏压变化率小于20％，性能稳定。晶粒尺寸小于300nm，粒度均匀，可靠性强，适用于生产大容量、超薄介电层的多层陶瓷电容器。
附图说明
图1和图2分别为实施例1中制备的介质陶瓷块体材料的介电温谱和TCC变化；图3和图4为实施例1中制备的介质陶瓷块体材料的偏压特性图；
图5为实施例1中制备的介质陶瓷块体材料烧结并抛光热腐蚀后表面形貌的扫描电镜照片，(a)-(d)分别是BT1-BT4；
图6为实施例1中包覆改性的粉体的透射电镜照片，(a)-(d)分别是BT1-BT4。
具体实施方式
以下通过下述实施方式进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。
在本公开中，采用化学包覆制备用于BME-MLCC的低电容电压系数的X7R瓷粉，具体来说通过化学沉淀包覆法将改性元素均匀包覆在纳米钛酸钡颗粒表面。进一步，再在还原气氛下烧结制备得到具有较高介电常数且满足X7R温度稳定性的电介质陶瓷块体材料，其电容电压系数低，偏压特性优良。本发明中，瓷料可以实现还原气氛烧结介质陶瓷，该陶瓷在性能上具有良好的偏压稳定性，其在最大电场40kV/cm下变化率在20％以下；在介电温度稳定性方面复合X7R温度稳定性；此外该改性瓷料实现了晶粒尺寸大小的控制和均匀，晶粒尺寸基本维持在原始粉体大小。以上瓷料性能结果为实现实用性更小型化的BME-MLCC提供了依据。
在本发明优选实施方式中，X7R瓷粉由纳米钛酸钡为主晶相和纳米包覆复合改性氧化物组成，所述钛酸钡BaTiO3主晶相在配方中所占摩尔分数为～92mol％，纳米包覆层复合氧化物在配方中占摩尔分数为～8mol％。主要通过化学沉淀法将改性元素均匀包覆在主晶相纳米钛酸钡表面。
其中，纳米钛酸钡BaTiO3在配方中占摩尔分数为～92mol％，粒径优选为150nm、200nm、300nm和500nm。
其中，纳米包覆层复合氧化物油Dy2O3、Ho2O3、MgO、MnO、SiO2、CaO和BaO组成，所占摩尔分数优选为～8％。
以下示例性地说明化学沉淀包覆法制备纳米包覆钛酸钡陶瓷瓷料方法。
将钛酸钡粉体和溶剂(水、无水乙醇或异丙醇等)混合，在1000-1500W下超声雾化分散20～30min，功率比为40％～60％，超声波频率范围为20～50kHZ，其中将超声探头深入液面10～30mm，超声开关间隔在2～5s：3～10s得到分散良好的钛酸钡粉体悬浮液。本发明中，超声雾化分散不同于普通超声分散，区别1：结构不同。由超声探头、换能器、信号发生器和封闭橱构成；区别2：接触不同。超声探头与溶液接触，换能器的机械振动传给液体，使液体发生隆起，并在隆起的周围发生空化作用，空化产生的冲击波在液面上引起有限振幅的表面张力波，进行分散。区别3：分散效果不同。超声雾化分散是波动分散，是液体雾化，分散性要优于经过水相的超声分散。
将可溶性的Dy2O3、Ho2O3、MgO、MnO、CaO和BaO类氧化物所对应的金属硝酸盐或醋酸盐按摩尔比称重，溶解在去离子水中，得到澄清的混合无机盐溶液。
将正硅酸四乙酯按摩尔比溶解在乙醇和去离子水混合溶液中，混合溶液按体积无水乙醇：去离子水＝3:1，混合均匀后得到澄清稳定的混合有机盐溶液。
将混合无机盐溶液与混合有机盐溶液分别滴加到钛酸钡悬浮液中，强烈搅拌，使混合均匀。按0.1～0.2滴/s加入稀释氨水溶液，调节混合溶液pH值至8.5～10.5并陈化数小时，通过共沉淀反应，使掺杂改性元素均匀包覆在钛酸钡颗粒表面，得到悬浮液2。其中，混合无机盐溶液：混合有机盐溶液＝5:4～2:1(体积比)。
将悬浮液2在75～80℃烘干，得到混合粉体。将混合粉体于450℃在空气中预烧2h，得到X7R瓷粉。
以下示例性地说明抗还原介电陶瓷块体材料的制备方法。
将X7R瓷粉加入粘结剂造粒陈化，随后压制成型，然后升温排塑，得到陶瓷坯体。所述的粘结剂为聚乙烯醇(PVA)，粘结剂的加入量为陶瓷粉料重量的6～8wt％；所述排塑条件为：1～2℃/min的升温速率升温至750～800℃，保温1～3小时，全程通入氮气保护。
在还原气氛下烧结：烧结过程中通入按流量比98：2～95：5的N2/H2，同时加湿，将氧分压控制在10-8～10-12atm的范围内，1～2℃/min的升温速率升温至1300～1360℃，保温2h完成致密化。
在弱氧化条件下退火：炉温在800～950℃，保温4小时，氧分压控制在1～50Pa内，冷却到室温。
将烧结好的陶瓷片加工成所需尺寸，超声清洁，溅射Au电极，得到所述的热释电陶瓷材料。
本发明中，所得介电陶瓷块体材料在室温附近具有较高的相对介电常数(～2220)、较高的绝缘电阻率(～9×1012Ω·cm)、较低的介电损耗(～0.7％)，具有优良的介电温度稳定性满足EIA-X7R标准(-55～125℃，ΔC/C25℃≤±15％)，且满足了电容量随电压的变化量小的要求，偏压特性优良。可与贱金属在还原气氛下烧结，用于生产大容量、超薄介电层的BME-MLCC产品。
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。
实施例1
利用化学沉淀包覆的方法制备具有较高介电常数且偏压特性优良满足X7R的超细晶温度稳定型BME-MLCC用的电介质瓷料。该瓷料由纳米钛酸钡主晶相和纳米包覆层复合氧化物组成，所述钛酸钡BaTiO3主晶相在配方中所占摩尔分数为92mol％；所述纳米包覆层复合氧化物的用量占材料总量的2mol％。
所用纳米钛酸钡粉体粒径有150nm、200nm、300nm和500nm分别实施，试样编号做粒径150nm试样为BT1、粒径200nm试样为BT2、粒径300nm试样为BT3、粒径500nm试样为BT4。
所述纳米包覆层由下列成分的氧化物复合组成：xA+yB+zC；
其中A表示为MgO、MnO、CaO和BaO；B表示为Dy2O3和Ho2O3；C表示为SiO2；x、y、z分别是A、B和C各类氧化物相对于BaTiO3的摩尔分数，其中x:6.3mol％，y:1mol％(0.5mol％Dy2O3+0.5mol％Ho2O3)，z:1.5mol％。A类复合氧化物包覆层中各元素摩尔比为Mg：Ca：Mn：Ba＝6:3.6:1:2。其中，Dy：Ho：Mg：Mn：Si：Ca：Ba＝1：1：6：1：3：3.6：2。
由本发明的化学包覆法工艺制备包覆的钛酸钡瓷料制备抗还原介电陶瓷，包括超声雾化技术分散纳米粒度的BaTiO3粉体。钛酸钡粉体和溶剂(水、无水乙醇或异丙醇等)按质量比的5:4～2称量、混合，在1000-1500W(功率比为40％～60％)下超声雾化分散20～30min，超声波频率范围为20-50kHZ，其中将超声探头深入液面约10～30mm，超声开关间隔在2～5s：3～10s得到分散良好的钛酸钡粉体悬浮液。所述的超声雾化装置是由超声探头、换能器、信号发生器和封闭橱构成，不同于其他水相超声分散，其超声分散是通过超声探头与溶液接触，换能器的机械振动传给液体，使液体发生隆起，并在隆起的周围发生空化作用，空化产生的冲击波在液面上引起有限振幅的表面张力波。这种波动分散，是液体雾化，进行分散；包括化学包覆法改性纳米BaTiO3粉体。将分散后的浆料与配置的有机和无机离子溶液进行混合，磁力搅拌4～6小时，随后按0.1～0.2滴/s加入稀释5倍的氨水溶液，调节混合溶液pH值至8.5～10.5并陈化8～24h，通过共沉淀反应，使掺杂改性元素均匀包覆在钛酸钡颗粒表面。得到的溶液在75～80℃烘干，得到混合粉体，并将混合粉体于450℃在空气中预烧2h，目标X7R瓷粉。
该瓷料经由8wt％的PVA粘结剂，造粒，压块陈化24小时，过120目筛，在1.4～1.6MPa压力下压制成型，然后800℃下全程氮气气氛中排塑2h，得到陶瓷素坯。
在体积比98:2的N2/H2还原气氛下1300-1350℃烧结2h。然后在弱氧化条件下于900℃退火4h。
将烧结好的陶瓷片磨薄至0.5mm，清洗，烘干样品表面溅射银电极，进行电学性能测试，性能参数见表1。图1(横坐标为温度T、纵坐标为介电常数Dielectric constant和介电损耗Dielectric loss)和图2的曲线给出的是本实施例样品1-4的介电常数随温度变化的特性曲线，从图1和图2中可知随着晶粒尺寸的减小，介电常数具有明显的变化趋势。细晶粒样品(BT1和BT2)的介电曲线比粗晶粒样品(BT3和BT4)的介电曲线更平坦，细晶粒陶瓷BT1的介电常数较低，粗晶粒陶瓷BT4的介电常数较高。在整个温度范围内，介电常数与晶粒尺寸呈正相关。所有样品BT1～BT4具有良好的温度稳定性，符合EIA-X7R标准(-55～125℃，ΔC/C25℃≤±15％)。图3和图4的曲线给出的是本实施例样品1-4的偏压特性曲线，从图3和图4中可知当施加的最大偏置电场(Electric Field)为40kV/cm直流电场，所有样品的介电常数(Dielectric constant)都随着电场的升高而逐渐减小，变化率α表现出很大的晶粒尺寸依赖性。晶粒尺寸越小，α的绝对值越小，这意味着晶粒尺寸越细的陶瓷表现出更好的偏置场稳定性，BT1的α绝对值小于20％表现出优异的偏压稳定性。从图5可知所有陶瓷均烧结致密，晶粒分布均匀，大小一致，根据统计结果，所有陶瓷样品的平均晶粒尺寸基本保持在原始BaTiO3粒径左右，比如粉体粒径是200nm的BaTiO3经过烧结后可以得到晶粒尺寸为260nm的陶瓷。图6可知化学包覆并经预烧处理后的不同粒度尺寸BaTiO3粉体的微观形貌。所有样品都具有均匀的包覆层(其中(a)为10.5nm，(b)为7.3nm、(c)为5.3nm、(d)为4.6nm)，并且包覆层的厚度随着粒径的增加而逐渐减小(10.5nm～4.6nm)。
实施例2
本实施例2中介质陶瓷块体材料的制备过程参照实施例1，区别在于：0.75mol％Dy2O3+0.25mol％Ho2O3。
实施例3
本实施例3中介质陶瓷块体材料的制备过程参照实施例1，区别在于：0.75mol％Ho2O3+0.25mol％Dy2O3。
实施例4
本实施例4中介质陶瓷块体材料的制备过程参照实施例1，区别在于：1mol％Ho2O3+0mol％Dy2O3
实施例5
本实施例5中介质陶瓷块体材料的制备过程参照实施例1中，区别在于1mol％Dy2O3+0mol％Ho2O3。
表1：

Claims (10)

1.一种低电压系数的X7R瓷粉，其特征在于，由纳米钛酸钡为主晶相，以及包覆在纳米钛酸钡表面的复合改性氧化物组成；所述复合改性氧化物的组成为Dy2O3、Ho2O3、MgO、MnO、SiO2、CaO和BaO。
2.根据权利要求1所述的低电压系数的X7R瓷粉，其特征在于，所述纳米钛酸钡的摩尔含量为92～97mol%，所述复合改性氧化物的摩尔分数为8～3mol%。
3.根据权利要求1所述的低电压系数的X7R瓷粉，其特征在于，所述复合改性氧化物中Dy：Ho：Mg：Mn：Si：Ca：Ba=（0～2）：（2～0）：（3～7）：（0.5～3）：（3～4）：（2～5）：（2.5～3.5）；优选地，所述Dy和Ho的摩尔比为1：（0.5～1.5），更优选为1：1，更优选为1：1。
4.根据权利要求3所述的低电压系数的X7R瓷粉，其特征在于，其中Dy：Ho：Mg：Mn：Si：Ca：Ba=1：1：6：1：3：3.6：2。
5.根据权利要求1-4中任一项所述的低电压系数的X7R瓷粉，其特征在于，所述纳米钛酸钡的粒径为150～500nm，优选为150～200nm。
6.一种权利要求1-5中任一项所述的低电压系数的X7R瓷粉的制备方法，其特征在于，包括：
（1）以水、无水乙醇或异丙醇为作为溶剂和钛酸钡粉体进行超声雾化分散，得到钛酸钡粉体悬浮液；
（2）将可溶性的Dy2O3、Ho2O3、MgO、MnO、CaO和BaO所对应的金属硝酸盐或醋酸盐按摩尔比称重，溶解在去离子水中，得到澄清的混合无机盐溶液；
（3）将正硅酸四乙酯按摩尔比溶解在乙醇和去离子水混合溶液中，得到澄清稳定的混合有机盐溶液；
（4）将混合无机盐溶液和混合有机盐溶液分别滴加到钛酸钡粉体悬浮液中，同时按0.1～0.2滴/s加入稀释氨水溶液，调节混合溶液pH值至8.5～10.5并陈化一定时间，得到混合粉体；
（5）将混合粉体在空气中400～600℃下在预烧1～4小时，得到低电压系数的X7R瓷粉。
7.根据权利要求6所述的制备方法，其特征在于，所述混合无机盐溶液：混合有机盐溶液的体积比=（5 : 4）～（2 : 1）。
8.一种兼具高介电常数和低电容电压系数的介质陶瓷块体材料，其特征在于，是选用权利要求1-5中任一项所述的低电压系数的X7R瓷粉作为原料进行造粒，再经压制成型、脱粘、烧结和退火得到。
9.根据权利要求8所述的介质陶瓷块体材料，其特征在于，所述脱粘的温度为750～800℃，时间为1～3小时；
所述烧结的气氛为还原性气氛，温度为1300～1360℃，时间为1.5～3小时，优选所述还原气氛为N2/H2混合气氛，更优选N2和H2的体积比为98：2～95：5；
所述退火的气氛为氧分压为1～50Pa的弱氧化条件，温度为800～950℃，时间为4～6小时。
10.根据权利要求8或9所述的介质陶瓷块体材料，其特征在于，当纳米钛酸钡的粒径为150～200nm时，所述介质陶瓷块体材料室温下介电常数大于2200，且DC偏压变化率小于20%。
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