CN113354410B - 一种陶瓷材料及其制备方法与应用 - Google Patents
一种陶瓷材料及其制备方法与应用 Download PDFInfo
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- CN113354410B CN113354410B CN202110611337.6A CN202110611337A CN113354410B CN 113354410 B CN113354410 B CN 113354410B CN 202110611337 A CN202110611337 A CN 202110611337A CN 113354410 B CN113354410 B CN 113354410B
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- barium titanate
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 65
- 239000000919 ceramic Substances 0.000 claims abstract description 56
- 238000005245 sintering Methods 0.000 claims abstract description 47
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 43
- 239000003985 ceramic capacitor Substances 0.000 claims abstract description 38
- -1 barium titanate compound Chemical class 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 31
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 29
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 29
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 29
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 29
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001238 wet grinding Methods 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 239000003989 dielectric material Substances 0.000 abstract description 7
- 238000005452 bending Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 19
- 239000013078 crystal Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 10
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- 239000002994 raw material Substances 0.000 description 7
- 238000009413 insulation Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000002159 abnormal effect Effects 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
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- 230000007547 defect Effects 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000003990 capacitor Substances 0.000 description 1
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- 238000010344 co-firing Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
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- Ceramic Capacitors (AREA)
Abstract
本发明公开了一种陶瓷材料及其制备方法与应用。本发明陶瓷材料包括钛酸钡系化合物、稀土元素和烧结助剂，其中，稀土元素和烧结助剂的含量都不为0，烧结助剂包括MgO、MnO2和SiO2；以钛酸钡系化合物的摩尔量为基准计算，稀土元素占0～10％，烧结助剂占0～25％，MgO占0～10％，MnO2占0～10％，SiO2占0～5％，MnO2和SiO2的摩尔比为1.1～3，MgO和MnO2的摩尔比为0.3～4。本发明通过优化烧结助剂，从根本上改善了钛酸钡系陶瓷介电材料本身强度弱的缺点，在保证多层陶瓷电容器具有良好电学性能的基础上，提高其抗折强度至≥7.5kgf和抗弯曲强度至≥6.5mm。
Description
技术领域
本发明涉及一种陶瓷材料及其制备方法与应用，具体涉及一种通过优化烧结助剂以提高材料强度的陶瓷材料及其制备方法与应用。
背景技术
多层陶瓷电容器(MLCC)是常见的被动元件之一，广泛应用在家电、手机、计算机及其他智能控制电路中。MLCC的制作过程主要包括成型、烧成及封端三个过程。成型工艺是将陶瓷粉、有机溶剂及添加剂充分混合后流延成陶瓷介质层，在陶瓷介质层上印刷内电极后再进行堆叠，压合和切割形成陶瓷芯片，将上述陶瓷芯片进行烧结和封端就制成陶瓷电容器。多层陶瓷电容器主要可分为I类高频陶瓷电容器和II类高介电陶瓷电容器。
II类多层陶瓷电容器主要应用于消费电子、通信和车载等领域。现有的II类多层陶瓷电容器多采用以钛酸钡系化合物为主成分的陶瓷材料，这类材料本身强度较低，在使用过程中易受到环境温度变化和周围震动的影响而出现开裂，断裂甚至失效等问题。
目前，一些厂家会采用通过优化结构等手段来改善产品使用过程的断裂问题，如贵金属软端子设计，通过在产品端头处增加缓冲层，一般由一种柔性贵金属加导电树脂材料制成，这种结构设计的电容器在接受外力作用时，软端子发生轻微塑性变形，吸收应力而保护产品，但该方案的成本高且软端子共烧技术难度大，而且并没有提高产品本身强度；如通过在有效电极层的上表面、内部和下表面的至少一处中设计一种由更高强度材料组成的加强体，以提高产品整体强度，但该方案中陶瓷介质材料本身强度缺陷仍旧存在。
因此，亟待开发一种成本低、处理难度低，并能从根本上提高陶瓷介质材料强度的技术方案。
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及其制备方法与应用，通过优化烧结助剂以从根本上改善钛酸钡系陶瓷介电材料本身强度弱的缺点，使其强度得到提高，进而提高其制成的多层陶瓷电容器的机械强度，同时，也使获得机械强度高的多层陶瓷电容器的成本和处理难度得到大幅度降低。
为实现上述目的，第一方面，本发明提供了一种陶瓷材料，其包括钛酸钡系化合物、稀土元素和烧结助剂，其中，稀土元素和烧结助剂的含量都不为0，烧结助剂包括MgO、MnO2和SiO2；以所述钛酸钡系化合物的摩尔量为基准计算，所述稀土元素占0～10％，所述烧结助剂占0～25％，所述MgO占0～10％，所述MnO2占0～10％，所述SiO2占0～5％，所述MnO2和所述SiO2的摩尔比为1.1～3，所述MgO和所述MnO2的摩尔比为0.3～4。
优选地，以所述钛酸钡系化合物的摩尔量为基准计算，所述MgO占0.3～3％，所述MnO2占0.33～3％，所述SiO2占0.3～2％，所述MnO2和所述SiO2的摩尔比为1.1～1.5，所述MgO和所述MnO2的摩尔比为0.6～1.5。
优选地，以所述钛酸钡系化合物的摩尔量为基准计算，所述稀土元素占0.2～3％。
优选地，所述钛酸钡系化合物为(Ba1-x-yCaxSry)m(Ti1-p-qZrpHfq)O3，其中，x＝0-0.18，y＝0-0.02，p＝0-0.02，q＝0-0.02，m＝0.990-1.06。
优选地，所述稀土元素为La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y中至少一种。
优选地，所述钛酸钡系化合物为BaTiO3，所述稀土元素为Ho。更有选地，以所述钛酸钡系化合物的摩尔量为基准计算，所述稀土元素占0.5％，所述MgO占0.62％，所述MnO2占0.78％，所述SiO2占0.6％，所述MnO2和所述SiO2的摩尔比为1.3，所述MgO和所述MnO2的摩尔比为0.8。
第二方面，本发明还提供了一种上述陶瓷材料的制备方法，其包括以下步骤：
将Mg、Mn、Si以及稀土元素的化合物和钛酸钡系化合物混合，粉碎，煅烧，即得所述陶瓷材料。
优选地，所述Mg、Mn、Si以及稀土元素的化合物为Mg、Mn、Si以及稀土元素的氧化物、盐类物质中的至少一种；煅烧温度为800～1200℃，煅烧时间为1～4h。更优选地，煅烧温度为800～1100℃，煅烧时间为1～3h。
优选地，在混合和煅烧之间进行湿法粉碎，在湿法粉碎和煅烧之间进行干燥处理。
第三方面，本发明提供了一种陶瓷浆料，其包含溶剂、粘合剂和上述陶瓷材料。
优选地，所述陶瓷浆料为多层陶瓷电容器用陶瓷浆料。
第四方面，本发明提供了使用上述陶瓷浆料制成的陶瓷介质层、陶瓷芯片或多层陶瓷电容器。
第五方面，本发明提供了上述陶瓷材料在制备多层陶瓷电容器中的应用。
与现有技术相比，本发明的有益效果为：本发明对钛酸钡系陶瓷介电材料中的烧结助剂进行了优化，通过对烧结助剂中的MnO2和SiO2的摩尔比以及MgO和MnO2的摩尔比的合理调控，使MnO2、SiO2等烧结助剂成分在相对较低的温度下形成液相，更充分地扩散到BaTiO3晶粒表面，这促进了材料的烧结，改善了材料的烧结状态，提高了材料致密性，同时位于晶界上的玻璃相对微裂纹的扩展起到延缓或阻止作用，能进一步提高材料的强度；另外，Mg含量的合理调整，可抑制晶粒的异常长大，在保证多层陶瓷电容器具有良好电学性能的基础上，提高其抗折强度(≥7.5kgf)和抗弯曲强度(≥6.5mm)。
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，“以钛酸钡系化合物的摩尔量为基准计算，稀土元素占0～10％，烧结助剂占0～25％，MgO占0～10％，MnO2占0～10％，SiO2占0～5％”是指稀土元素摩尔量为钛酸钡系化合物摩尔量的0～10％，烧结助剂摩尔量为钛酸钡系化合物摩尔量的0～25％，MgO摩尔量为钛酸钡系化合物摩尔量的0～10％，MnO2摩尔量为钛酸钡系化合物摩尔量的0～10％，SiO2摩尔量为钛酸钡系化合物摩尔量的0～5％，其他类似描述同理。
本文中，“MnO2和SiO2的摩尔比为1.1～3，MgO和MnO2的摩尔比为0.3～4”是指MnO2摩尔量/SiO2摩尔量＝1.1～3，MgO摩尔量/MnO2摩尔量＝0.3～4，其他类似描述同理。
本文中，“Mg、Mn、Si以及稀土元素的化合物”是指Mg的化合物、Mn的化合物、Si的化合物以及稀土元素的化合物。“Mg、Mn、Si以及稀土元素的氧化物、盐类物质中的至少一种”是指Mg的氧化物、盐类物质中的至少一种，Mn的氧化物、盐类物质中的至少一种，Si的氧化物、盐类物质中的至少一种，以及稀土元素的氧化物、盐类物质中的至少一种。
为解决以钛酸钡系化合物为主要成分的陶瓷材料强度较低，导致其制成的多层陶瓷电容器在使用过程中易出现开裂，断裂甚至失效的问题，本发明对陶瓷材料中的烧结助剂进行优化，通过对烧结助剂中Mn和Si比例的合理调控，使得MnO2、SiO2等烧结助剂成分在较低的温度下形成液相，可更充分地扩散到BaTiO3晶粒表面，促进材料的烧结，改善材料的烧结状态，提高材料致密性，同时晶界处玻璃相的存在可阻止或延缓微裂纹的扩展，进一步提高材料的强度；另外，通过对Mg含量的合理调控，可抑制晶粒的异常长大，防止材料的Df(即介电损耗)、IR(即绝缘电阻)等电学性能恶化，在保证多层陶瓷电容器具有良好电学性能的基础上，提高其抗折强度至≥7.5kgf和抗弯曲强度至≥6.5mm。具体而言，本发明陶瓷材料包括钛酸钡系化合物、稀土元素和烧结助剂，其中，稀土元素和烧结助剂的含量都不为0，烧结助剂包括MgO、MnO2和SiO2；以钛酸钡系化合物的摩尔量为基准计算，稀土元素占0～10％，烧结助剂占0～25％，MgO占0～10％，MnO2占0～10％，SiO2占0～5％，MnO2和SiO2的摩尔比为1.1～3，MgO和MnO2的摩尔比为0.3～4。
当MgO与钛酸钡系化合物的摩尔比超过10％时，制备多层陶瓷电容器时所需烧成温度上升，烧结性恶化，从而抑制物质移动，导致多层陶瓷电容器寿命加速恶化，因此，选择MgO与钛酸钡系化合物的摩尔比在10％以下。优选MgO与钛酸钡系化合物的摩尔比为0.3～3％，这样不仅制备多层陶瓷电容器时所需烧成温度更低，烧结性更好，而且相较MgO与钛酸钡系化合物的摩尔比小于0.3％时，能更好地抑制晶粒的异常长大，获得更高的电阻率，更好的TCC(电容的温度变化率)。
当MnO2与钛酸钡系化合物的摩尔比超过10％时，容易发生半导化，老化率高，DC-bias(即直流偏置)特性低下，因此，选择MnO2与钛酸钡系化合物的摩尔比在10％以下。优选MnO2与钛酸钡系化合物的摩尔比为0.33～3％，这样不仅制得的多层陶瓷电容器不易发生半导化，老化率更低，DC-bias特性更好，而且相较MnO2与钛酸钡系化合物的摩尔比低于0.33％时，能够使耐还原性低的多层陶瓷电容器获得更高的绝缘电阻。
当SiO2与钛酸钡系化合物的摩尔比超过5％时，晶粒容易长大，导致TCC特性恶化，因此，选择SiO2与钛酸钡系化合物的摩尔比在5％以下。优选SiO2与钛酸钡系化合物的摩尔比为0.3～2％，这样不仅能有效避免晶粒长大，具有更好的TCC特性，而且相较SiO2与钛酸钡系化合物的摩尔比低于0.3％时，所需烧成温度低，烧结性更好，所得多层陶瓷电容器的寿命更长。
当MnO2和SiO2的摩尔比超过3以及低于1.1时，烧结助剂形成液相的温度较高，玻璃相等扩散效果较差，导致材料强度改善效果不达预期，因此，选择MnO2和SiO2的摩尔比为1.1～3。优选MnO2和SiO2的摩尔比为1.1～1.5。
当MgO和MnO2的摩尔比超过4时，虽然制备多层陶瓷电容器的烧结过程中，晶粒长大受到抑制，但是所需烧结温度较高，烧结性较差，同时抑制了稀土等元素的扩散，导致寿命恶化；当MgO和MnO2的摩尔比低于0.3时，制备多层陶瓷电容器的烧结过程中，抑制晶粒长大的效果较低，导致晶粒异常长大，电阻率、TCC等性能恶化，因此，选择MgO和MnO2的摩尔比为0.3～4。优选MgO和MnO2的摩尔比为0.6～1.5。
当稀土元素与钛酸钡系化合物的摩尔比超过10％时，静电容量温度系数更趋于稳定，材料介电常数低，烧结性低下，绝缘电阻劣化，因此，选择稀土元素与钛酸钡系化合物的摩尔比在10％以下。优选稀土元素与钛酸钡系化合物的摩尔比为0.2～3％，这样不仅耗用稀土元素更少，材料介电常数更好，烧结性更好，绝缘电阻更高，而且能够避免稀土元素与钛酸钡系化合物的摩尔比较低而导致的高温绝缘电阻较低，高温寿命时间较短的问题。
在一些实施方式中，钛酸钡系化合物为(Ba1-x-yCaxSry)m(Ti1-p-qZrpHfq)O3，其中，x＝0-0.18，y＝0-0.02，p＝0-0.02，q＝0-0.02，m＝0.990-1.06。当m＜0.990时，容易晶粒异常长大，绝缘电阻减小；当m＞1.06时，烧结性下降，因此选择m＝0.990-1.06。
稀土元素可以选择La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y、Sc中至少一种。优选稀土元素为La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y中至少一种。
钛酸钡系化合物可选择通过固相法制成的粉末，也可选择通过共沉淀法、水热法、草酸盐法等方法制备而成。但钛酸钡系化合物的制备方法并不局限于此。
本发明陶瓷材料可选择通过包括以下步骤的制备方法制备而成：将Mg、Mn、Si以及稀土元素的化合物和钛酸钡系化合物混合，煅烧，即得所述陶瓷材料。在一些实施方式中，在该混合和煅烧之间，还进行湿法粉碎；湿法粉碎后煅烧前进行干燥处理。湿法粉碎所用溶剂选择为水、乙醇中的至少一种，但并不局限于此。湿法粉碎所用粉碎介质可采用氧化锆球，但并不局限于此。在一些实施方式中，该煅烧温度为800～1200℃，煅烧时间为1～4h。在一些优选实施方式中，该煅烧温度为800～1100℃，煅烧时间为1～3h。
本发明陶瓷材料能应用于制备多层陶瓷电容器中的应用。在一些实施方式中，该制备方法包括以下步骤：
(1)将陶瓷浆料的原料混合球磨得到陶瓷浆料，其中陶瓷浆料的原料包括本发明陶瓷材料、粘合剂和溶剂；
(2)将上述陶瓷浆料流延形成一层薄膜，烘干，得到陶瓷介质层；
(3)通过印刷工艺在步骤(2)所得陶瓷介质层的表面形成内电极层；
(4)将上述印有内电极的陶瓷介质层经叠层、压合、排胶和烧结处理，即得陶瓷芯片；
(5)在陶瓷芯片的两端面涂敷外部电极用导电性膏，以600～900℃的温度进行烘烤处理，形成外部电极；
(6)实施电解镀覆而在外部电极的表面形成由Ni、Cu、Ni-Cu合金等构成的第一镀覆膜，然后在该第一镀覆膜的表面形成由焊料、锡等构成的第二镀覆膜，即得多层陶瓷电容器。排胶和烧结可选择在大气气氛下以250～350℃的温度进行热处理，使粘合剂燃烧而除去，然后在由H2-N2-H2O气体构成的强还原性气氛下(例如，氧分压为1011～1013MPa)以1100～1300℃的烧成温度进行大约1～3小时(如1.5小时、2小时、2.5小时等)的烧结处理。外部电极用导电性膏中含有的导电性材料，从低成本化的观点出发，优选使用Ag、Cu、或者以它们的合金为主成分的材料。
在另外一些实施方式中，该制备方法包括以下步骤：
(1)将陶瓷浆料的原料混合球磨得到陶瓷浆料，其中陶瓷浆料的原料包括本发明陶瓷材料、粘合剂和溶剂；
(2)将上述陶瓷浆料流延形成一层薄膜，烘干，得到陶瓷介质层；
(3)通过印刷工艺在步骤(2)所得陶瓷介质层的表面形成内电极层；
(4)将上述印有内电极的陶瓷介质层经叠层和压合，即得层叠成型体，在该层叠成型体的两端面涂敷外部电极用导电性膏，之后经排胶和烧结处理，即得陶瓷芯片；
(5)实施电解镀覆而在外部电极的表面形成由Ni、Cu、Ni-Cu合金等构成的第一镀覆膜，然后在该第一镀覆膜的表面形成由焊料、锡等构成的第二镀覆膜，即得多层陶瓷电容器。排胶和烧结可选择在大气气氛下以250～350℃的温度进行热处理，使粘合剂燃烧而除去，然后在由H2-N2-H2O气体构成的强还原性气氛下(例如，氧分压为1011～1013MPa)以1100～1300℃的烧成温度进行大约1～3小时(如1.5小时、2小时、2.5小时等)的烧结处理。外部电极用导电性膏中含有的导电性材料，从低成本化的观点出发，优选使用Ag、Cu、或者以它们的合金为主成分的材料。
发明人在研究过程中，采用以下测试方法对制得的多层陶瓷电容器进行性能测定：
(1)采用表1中的测试方法；
表1
(2)抗折强度：采用拉力测试仪测试，将产品固定在测试台磨具上，使用拉力测试仪对其施加1mm/S的压力，直至产品断裂。抗折强度达标的标准为≥7.5kgf；
(3)抗弯曲强度：采用拉力测试仪测试，将产品焊接在专用PVB(聚乙烯醇缩丁醛酯)板上，对PVB板反向施加1mm/s的压力，直至产品容量变化率大于10％。抗弯曲强度达标的标准为≥6.5mm。
实施例1～26与对比例1～12
实施例1～26(简记为实1～26)与对比例1～12(简记为对1～12)分别提供了一种陶瓷材料，这些陶瓷材料包括钛酸钡系化合物、稀土元素和烧结助剂，其中钛酸钡系化合物均为(Ba1-x-yCaxSry)m(Ti1-p-qZrpHfq)O3，x均为0，y均为0，p均为0，q均为0，m均为1，这些钛酸钡系化合物都固相法制备而成，并且为同一批次制成的粉末；记稀土元素与钛酸钡系化合物的摩尔比为a％，MgO与钛酸钡系化合物的摩尔比为b％，MnO2与钛酸钡系化合物的摩尔比为c％，SiO2与钛酸钡系化合物的摩尔比为d％，a、b、c、d、b/c以及c/d的取值见表2。
表2
实施例1～26与对比例1～12的陶瓷材料的制备工艺相同，包括以下步骤：按预定的比例称量Ho2O3、MgO、MnO2和SiO2，然后与钛酸钡粉体、纯水及直径3～5mm氧化锆球一起加入球磨设备中，进行湿法粉碎，再对混合物进行干燥处理，然后900℃煅烧，煅烧时长2小时，制备得到陶瓷原料粉末。
将实施例1～26与对比例1～12的陶瓷材料采用相同的工艺制成多层陶瓷电容器，包括以下步骤：
(1)将陶瓷浆料的原料混合球磨得到陶瓷浆料，其中陶瓷浆料的原料包括本发明陶瓷材料、粘合剂和溶剂；
(2)将上述陶瓷浆料流延形成一层薄膜，烘干，得到陶瓷介质层；
(3)通过印刷工艺在步骤(2)所得陶瓷介质层的表面形成内电极层；
(4)将上述印有内电极的陶瓷介质层经叠层和压合处理，再在大气气氛下以260℃的温度进行热处理，使粘合剂燃烧而除去，然后在由H2-N2-H2O气体构成的强还原性气氛下(氧分压为1011～1013MPa)以1200℃的烧成温度进行大约2小时的烧结处理，即得陶瓷芯片；
(5)在陶瓷芯片的两端面涂敷外部电极用导电性膏，以800℃的温度进行烘烤处理，形成外部电极；
(6)实施电解镀覆而在外部电极的表面形成由Ni、Cu、Ni-Cu合金等构成的第一镀覆膜，进而，在该第一镀覆膜的表面形成由焊料、锡等构成的第二镀覆膜，至此完成制造多层陶瓷电容器。除所用陶瓷材料不同外，各实施例和对比例制备多层陶瓷电容器所用其他原料均相同。
对这些多层陶瓷电容器进行性能测试，部分结果见表3。
表3
另外，实施例1～26制成的多层陶瓷电容器的TCC(-55℃)也在±15％以内。
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，所述陶瓷材料包括钛酸钡系化合物、稀土元素和烧结助剂，其中，稀土元素和烧结助剂的含量都不为0，烧结助剂包括MgO、MnO2和SiO2；以所述钛酸钡系化合物的摩尔量为基准计算，所述稀土元素占0～10％，所述烧结助剂占0～25％，所述MgO占0.3～3％，所述MnO2占0.33～3％，所述SiO2占0.3～2％，所述MnO2和所述SiO2的摩尔比为1.1～1.5，所述MgO和所述MnO2的摩尔比为0.6～0.98。
2.根据权利要求1所述的陶瓷材料，其特征在于，以所述钛酸钡系化合物的摩尔量为基准计算，所述稀土元素占0.2～3％。
3.根据权利要求1所述的陶瓷材料，其特征在于，所述钛酸钡系化合物为(Ba1-x- yCaxSry)m(Ti1-p-qZrpHfq)O3，其中，x＝0-0.18，y＝0-0.02，p＝0-0.02，q＝0-0.02，m＝0.990-1.06；所述稀土元素为La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y中至少一种。
4.根据权利要求1所述的陶瓷材料，其特征在于，所述钛酸钡系化合物为BaTiO3，所述稀土元素为Ho。
5.根据权利要求4所述的陶瓷材料，其特征在于，以所述钛酸钡系化合物的摩尔量为基准计算，所述稀土元素占0.5％，所述MgO占0.62％，所述MnO2占0.78％，所述SiO2占0.6％，所述MnO2和所述SiO2的摩尔比为1.3，所述MgO和所述MnO2的摩尔比为0.8。
6.一种如权利要求1～5任一项所述的陶瓷材料的制备方法，其特征在于，所述制备方法包括以下步骤：
将Mg、Mn、Si以及稀土元素的化合物和钛酸钡系化合物混合，煅烧，即得所述陶瓷材料。
7.根据权利要求6所述的制备方法，其特征在于，所述Mg、Mn、Si以及稀土元素的化合物为Mg、Mn、Si以及稀土元素的氧化物、盐类物质中的至少一种；煅烧温度为800～1200℃，煅烧时间为1～4h，在混合和煅烧之间进行湿法粉碎，在湿法粉碎和煅烧之间进行干燥处理。
8.一种陶瓷浆料，其特征在于，所述陶瓷浆料包含溶剂、粘合剂和如权利要求1～5任一项所述的陶瓷材料。
9.根据权利要求8所述的陶瓷浆料，其特征在于，所述陶瓷浆料为多层陶瓷电容器用陶瓷浆料。
10.使用如权利要求8或9所述的陶瓷浆料制成的陶瓷介质层、陶瓷芯片或多层陶瓷电容器。
11.如权利要求1～5任一项所述的陶瓷材料在制备多层陶瓷电容器中的应用。
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