CN107500755A - 一种低温烧结的mlcc用陶瓷介质材料及其制备方法 - Google Patents
一种低温烧结的mlcc用陶瓷介质材料及其制备方法 Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 50
- 238000005245 sintering Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000470 constituent Substances 0.000 claims abstract description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 11
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 9
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims abstract description 9
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 9
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 9
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 9
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 9
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003990 capacitor Substances 0.000 claims abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003985 ceramic capacitor Substances 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
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- 229910010252 TiO3 Inorganic materials 0.000 claims description 2
- 239000003989 dielectric material Substances 0.000 claims description 2
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- 239000000843 powder Substances 0.000 abstract description 6
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 229910052759 nickel Inorganic materials 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
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- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
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- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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Abstract
本发明提供一种低温烧结的MLCC用陶瓷介质材料，其包括95～99％的主晶相成分和1～5％的改性添加物，主晶相成分包括Sr、Si掺杂的BaTiO3，改性添加物选自ZrO2、MnCO3、MgO、Y2O3、ZnO、Yb2O3、Er2O3、La2O3、SiO2中的两者种或两种以上。其制备方法为将通过固相合成得到主晶相成分；将主晶相成分和改性添加物进行湿法球磨，干燥得到陶瓷介质粉末材料。该材料具有良好的介电性能，制成的多层陶瓷介质电容器能够在还原气氛中以1240±20℃进行烧结，其介电常数介于3400～3800之间，符合X7R特性要求、及MLCC高性能、贱金属化发展趋势的要求，具有广阔的市场应用前景。
Description
技术领域
本发明涉及陶瓷介质领域，且特别涉及一种低温烧结的MLCC用陶瓷介质材料及其制备方法。
背景技术
片式多层陶瓷电容器(MLCC)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。MLCC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)，形成一个类似独石的结构体。适合在空气气氛中烧结的MLCC，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(MLCC)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MLCC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MLCC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标准X7R温度特性的陶瓷介质材料，通常是以BaTiO3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CN101848879A，CN101333105A，CN104291808A等制作的X7R粉料可在较低的烧结温度下成瓷，但其均是以纯BaTiO3为主晶相，采用后添加的方式进行掺杂，获得符合X7R特性的材料，制备方法复杂，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低温烧结的MLCC用陶瓷介质材料，此陶瓷介质材料以Sr、Si掺杂的BaTiO3为主晶相，辅以一定的改性添加物，具有良好的分散性、均匀性，烧结温度低。
本发明的另一目的在于提供一种低温烧结的MLCC用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。
本发明解决其技术问题是采用以下技术方案来实现的。
本发明提出一种低温烧结的MLCC用陶瓷介质材料，包括质量分数为95～99％的主晶相成分和质量分数为1～5％的改性添加物，主晶相成分包括Sr、Si掺杂的BaTiO3，改性添加物选自ZrO2、MnCO3、MgO、Y2O3、ZnO、Yb2O3、Er2O3、La2O3、SiO2中的两者种或两种以上。
本发明提出上述的一种低温烧结的MLCC用陶瓷介质材料的制备方法，包括以下步骤：
S1，将碳酸钡、硅的氧化物或碳酸盐、锶的氧化物或碳酸盐、二氧化钛进行湿法球磨，然后在空气气氛下煅烧2～4h，煅烧温度为1100℃～1150℃，得到主晶相成分；
S2，将主晶相成分和改性添加物进行湿法球磨，干燥得到陶瓷介质材料。
本发明实施例的一种低温烧结的MLCC用陶瓷介质材料及其制备方法的有益效果为：
以Sr、Si掺杂的BaTiO3作为主晶相材料，利用硅、锶的氧化物或碳酸盐的形式进行预先掺杂，得到掺杂有Sr、Si的BaTiO3，生产工序简单，然后再进行改性掺杂，获得符合X7R温度特性的陶瓷介质材料，其介电常数可达3400-3800，该材料制备过程简单，获得的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1240±20℃进行烧结，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。
下面对本发明实施例的一种低温烧结的MLCC用陶瓷介质材料及其制备方法进行具体说明。
本发明实施例提供的一种低温烧结的MLCC用陶瓷介质材料，包括质量分数为95～99％的主晶相成分和质量分数为1～5％的改性添加物，主晶相成分包括Sr、Si掺杂的BaTiO3，改性添加物选自ZrO2、MnCO3、MgO、Y2O3、ZnO、Yb2O3、Er2O3、La2O3、SiO2中的两者种或两种以上。在该主晶相通过预先掺杂能够对钛酸钡进行有效改性，提高材料的介电常数，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，各组分在陶瓷介质材料中的质量分数如下：ZrO2为0.0～0.5％；MnCO3为0～1.5％；MgO为0～2.0％；Y2O3为0～1.5％；ZnO为0.0～0.5％；Yb2O3为0～0.4％；Er2O3为0～0.2％；La2O3为0～0.2％；SiO2为0.3～0.6％。
进一步地，在本发明较佳实施例中，改性添加物中，各组分在陶瓷介质材料中的质量分数如下：ZrO2为0.2～0.5％；MnCO3为0.5～1.5％；MgO为0.8～2.0％；Y2O3为0.5～1.5％；ZnO为0.2～0.5％；Yb2O3为0～0.4％；Er2O3为0～0.2％；La2O3为0～0.2％；SiO2为0.3～0.6％。
更为优选地，主晶相成分为96％，改性添加物包括以下成分：ZrO2为0.2％；MnCO3为0.6％；MgO为0.8％；Y2O3为1.0％；ZnO为0.2％；Yb2O3为0.2％；Er2O3为0.2％；La2O3为0.2％；SiO2为0.6％。
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，例如进一步提高介电性能。
进一步地，在本发明较佳实施例中，主晶相成分为(Ba1-x-ySrxSiy)TiO3，x＝0.0016～0.002，y＝0.003～0.0034。更为优选的，x＝0.0018，y＝0.0032。在对BaTiO3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。使用上述用量的Sr、Si得到预先掺杂的BaTiO3，改变了主晶相的微观结构、介电性能和烧结特性等，使其能够在较低的温度下烧结，并能获得高介电常数。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，在本发明较佳实施例中，陶瓷介质材料的介电常数介于3400～3800，容温变化率为±15％，室温介电损耗≤2.5％
本发明还提供上述的低温烧结的MLCC用陶瓷介质材料的制备方法，包括以下步骤：
S1，将碳酸钡、硅的氧化物或碳酸盐、锶的氧化物或碳酸盐及二氧化钛进行湿法球磨，然后在空气气氛下煅烧2～4h，煅烧温度为1100℃～1150℃，得到主晶相成分；
S2，将主晶相成分和改性添加物进行湿法球磨，干燥得到陶瓷介质材料。
进一步地，硅的氧化物或碳酸盐选用二氧化硅，锶的氧化物或碳酸盐选用碳酸锶。碳酸钡、碳酸锶、二氧化硅和二氧化钛的质量比为70:0.1:30:0.07。
进一步地，步骤S1中，按重量比1:1～2将物料和水混合进行湿法球磨。
进一步地，步骤S2中，按重量比1:0.6～1将物料和水混合进行湿法球磨。更为优选地，该步骤中，在湿法球磨过程中，加入混合物质量分数2～5％的表面活性剂，例如加入一定量的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，步骤S2中，将物料球磨至平均颗粒尺寸达400～800nm。球磨完毕后用喷雾干燥塔或其他方法进行干燥。
本发明提供一种低温烧结的MLCC用陶瓷介质材料制成的多层陶瓷电容器，烧结条件为：在还原气氛下，在1220～1260℃条件下烧结。能够制得介电常数为3400-3800的多层陶瓷电容器，特性达到X7R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和性能作进一步的详细描述。
实施例
(1)以高纯、超细的碳酸钡、碳酸锶、二氧化硅和二氧化钛按表1的组成比例置于球磨机中进行湿法球磨，混合均匀，用喷雾干燥塔进行干燥，分别在空气炉中于1100℃、1125℃、1150℃条件下煅烧3小时，合成BaTiO3主晶相。
(2)按1的组成比例，把BaTiO3主晶相及各种改性添加物按配方组成的重量比称重，置于球磨机中，按重量比为物料：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400～800nm。砂磨完毕后用喷雾干燥塔进行干燥，最后得到陶瓷介质粉末材料。
(3)制备多层陶瓷电容器试样：取上述方法获得的陶瓷介质粉末材料，按比例计算，于100g粉末中加入40-60g无水乙醇，30-45gPVB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，于温度1240±20℃烧结，保温1.5-6小时。
表1 BaTiO3主晶相的配方表
表2陶瓷介质材料的配方表
表3介电性能测试结果表
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好的X7R陶瓷介质材料，可以在1220℃～1260℃的温度范围内，通过调整不同原料的配比可形成室温介电常数介于3400～3800，容温变化率介于+15％～-15％之间，室温介电损耗≤2.5％的连续可调系统的介质陶瓷材料。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X7R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)
1.一种低温烧结的MLCC用陶瓷介质材料，其特征在于，包括质量分数为95～99％的主晶相成分和质量分数为1～5％的改性添加物，所述主晶相成分包括Sr、Si掺杂的BaTiO3，所述改性添加物选自ZrO2、MnCO3、MgO、Y2O3、ZnO、Yb2O3、Er2O3、La2O3、SiO2中的两者种或两种以上。
2.根据权利要求1所述的低温烧结的MLCC用陶瓷介质材料，其特征在于，所述改性添加物中，各组分在所述陶瓷介质材料中的质量分数如下：ZrO2为0.0～0.5％；MnCO3为0～1.5％；MgO为0～2.0％；Y2O3为0～1.5％；ZnO为0.0～0.5％；Yb2O3为0～0.4％；Er2O3为0～0.2％；La2O3为0～0.2％；SiO2为0.3～0.6％。
3.根据权利要求1所述的低温烧结的MLCC用陶瓷介质材料，其特征在于，所述改性添加物中，各组分在所述陶瓷介质材料中的质量分数如下：ZrO2为0.2～0.5％；MnCO3为0.5～1.5％；MgO为0.8～2.0％；Y2O3为0.5～1.5％；ZnO为0.2～0.5％；Yb2O3为0～0.4％；Er2O3为0～0.2％；La2O3为0～0.2％；SiO2为0.3～0.6％。
4.根据权利要求1所述的低温烧结的MLCC用陶瓷介质材料，其特征在于，所述主晶相成分为(Ba1-x-ySrxSiy)TiO3，x＝0.0016～0.002，y＝0.003～0.0034。
5.根据权利要求1所述的低温烧结的MLCC用陶瓷介质材料，其特征在于，所述陶瓷介质材料的介电常数介于3400～3800，容量变化率为±15％，室温介电损耗≤2.5％。
6.根据权利要求1所述的低温烧结的MLCC用陶瓷介质材料，其特性在于，所述陶瓷介质材料在还原气氛中1220～1260℃条件下烧结制得多层陶瓷电容器。
7.根据权利要求6所述的低温烧结的MLCC用陶瓷介质材料，其特性在于，所述多层陶瓷电容器的介电常数为3400～3800，符合X7R温度特性。
8.一种如权利要求1～7任意一项所述的低温烧结的MLCC用陶瓷介质材料的制备方法，其特征在于，包括以下步骤：
S1，将碳酸钡、硅的氧化物或碳酸盐、锶的氧化物或碳酸盐、二氧化钛进行湿法球磨，然后在空气气氛下煅烧2～4h，煅烧温度为1100℃～1150℃，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进行湿法球磨，干燥得到所述陶瓷介质材料。
9.根据权利要求8所述的制备方法，其特征在于，步骤S1中，按重量比1:1～2将物料和水混合进行湿法球磨。
10.根据权利要求8所述的制备方法，其特征在于，步骤S2中，按重量比1:0.6～1将物料和水混合进行湿法球磨。
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| CN110550948A (zh) * | 2019-09-30 | 2019-12-10 | 厦门松元电子有限公司 | 高耐压陶瓷电容器介质材料、其制备方法及其电容器的制备方法 |
| CN116041058A (zh) * | 2023-01-09 | 2023-05-02 | 山东国瓷功能材料股份有限公司 | 一种电介质材料、其制备方法及多层片式陶瓷电容器 |
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| CN108129145A (zh) * | 2018-02-05 | 2018-06-08 | 厦门三行电子有限公司 | 一种x7r陶瓷电容器介质材料及其制备方法 |
| CN108129145B (zh) * | 2018-02-05 | 2020-03-24 | 厦门三行电子有限公司 | 一种x7r陶瓷电容器介质材料及其制备方法 |
| CN110550948A (zh) * | 2019-09-30 | 2019-12-10 | 厦门松元电子有限公司 | 高耐压陶瓷电容器介质材料、其制备方法及其电容器的制备方法 |
| CN116041058A (zh) * | 2023-01-09 | 2023-05-02 | 山东国瓷功能材料股份有限公司 | 一种电介质材料、其制备方法及多层片式陶瓷电容器 |
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