CN114394832A - 一种介电温度稳定的锆钛酸钡基瓷料及其制备方法 - Google Patents
一种介电温度稳定的锆钛酸钡基瓷料及其制备方法 Download PDFInfo
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- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 title claims abstract description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910021523 barium zirconate Inorganic materials 0.000 title claims abstract description 39
- 229910052573 porcelain Inorganic materials 0.000 title claims description 44
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 18
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 229910052788 barium Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 238000000748 compression moulding Methods 0.000 claims 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(III) nitrate Inorganic materials [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 32
- 229910052726 zirconium Inorganic materials 0.000 abstract description 18
- 230000008859 change Effects 0.000 abstract description 9
- 230000006698 induction Effects 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract description 2
- 239000011858 nanopowder Substances 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 35
- 239000000243 solution Substances 0.000 description 33
- 239000000463 material Substances 0.000 description 25
- 239000000919 ceramic Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 11
- 230000009466 transformation Effects 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 238000009837 dry grinding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- -1 barium zirconium titanate Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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Abstract
本发明公开了一种介电温度稳定的锆钛酸钡基瓷料及其制备方法,其组分包括(Ba1‑xGdx)(Ti0.9Zr0.1)O3+x/2、MgO及ZnO;制法为首先按摩尔比称量(CH3COO)2Ba、Gd(NO3)3、C16H36O4Ti和Zr(NO3)4·5H2O,通过溶胶凝胶法制得主晶相纳米粉体,随后将主晶相粉体与MgO及ZnO经研磨、模压成型制得片状坯体,最后经烧结制得锆钛酸钡基瓷料。本发明通过复合钙钛矿结构纳米主晶相与改性剂的协同作用使瓷料不仅具有高介电常数、低介电损耗的特点,且由于弥散相变的诱发使介电常数温度变化率小于±15%。
Description
技术领域
本发明涉及一种电子陶瓷及其制备方法,尤其涉及一种介电温度稳定的锆钛酸钡基瓷料及其制备方法。
背景技术
钛酸钡(BaTiO3)是一种优良的介电、压电和铁电材料,可广泛应用于电容器、PTC元件、压电换能器等电子元器件的制造。但其居里点(约120℃)偏高,室温下的介电常数仅为居里温度处介电常数的1/6,从而大大影响了其作为电容器介质的应用范围。
锆钛酸钡[Ba(ZrxTi1-x)O3]作为钛酸钡(BaTiO3)与锆酸钡(BaZrO3)形成的固溶体,兼顾了高介电性与居里温度可调等特点,且因其弛豫特性的出现逐渐成为陶瓷电介质材料的研究热点之一。然而,锆钛酸钡基陶瓷高介、低损且介电温度稳定的多参数协同仍是该材料作为X7R、Y5V型电容器介质材料的技术难点之一。期刊《电子元件与材料》2016年第35卷第3期在“Gd2O3掺杂对BZT基陶瓷结构和介电性能的影响”一文中公开了一种通过传统固相法制备的BaZr0.1Ti0.9O3+xGd2O3(x=0~0.70)陶瓷,其介电常数高达4355时,介电损耗为0.031且介电常数温度稳定性欠佳。期刊《电子元件与材料》2004年第23卷第10期在“二氧化铈掺杂锆钛酸钡陶瓷性能和结构的研究”一文中公开了一种通过固相法制备的CeO2掺杂Ba(Zr,Ti)O3陶瓷,其室温介电常数高达7193,介电常数温度变化率为-80.1%~+19.1%,其室温介电损耗为0.0351。期刊《Journal of Applied Physics》2007年第102卷第8期在“Dielectric properties and relaxor behavior of rare-earth(La,Sm,Eu,Dy,Y)substituted barium zirconium titanate ceramics”一文中公开了一种通过固相法制备的(Ba1-xLnx)Zr0.2Ti0.8-x/4O3(x=0-0.04,Ln=La,Sm,Eu,Dy,Y)系列陶瓷材料,其中x=0.04,Ln=La时损耗角正切可低至0.00005,但室温介电常数仅为650。
因此,现亟需一种不仅具备高介电常数,且同时拥有低介电损耗和高介电温度稳定性的锆钛酸钡基瓷料。
发明内容
发明目的:本发明的第一目的是提供一种高介电常数、低介电损耗且介电温度稳定性佳的锆钛酸钡基瓷料;
本发明的第二目的是提供该锆钛酸钡基瓷料的制备方法。
技术方案:本发明的介电温度稳定的锆钛酸钡基瓷料,按质量百分比包括如下组分:
(Ba1-xGdx)(Ti0.9Zr0.1)O3+x/2 99.7-99.5wt%
MgO 0.15-0.25wt%
ZnO 0.15-0.25wt%;
其中x=0.04-0.05。
上述介电温度稳定的锆钛酸钡基瓷料的制备方法,包括如下步骤:
(1)按摩尔比(1-x):x:0.9:0.1称量(CH3COO)2Ba、Gd(NO3)3、C16H36O4Ti和Zr(NO3)4·5H2O;将C16H36O4Ti、C2H5OH或(CH2OH)2、CH3COOH混合搅拌,得到A液;将Gd(NO3)3、(CH3COO)2Ba与Zr(NO3)4·5H2O溶解于水中,得到B液;
(2)将B液缓慢滴加至A液中,搅拌后调节溶液pH值,继续搅拌后得到溶胶;将溶胶置于恒温环境中使其发生溶胶-凝胶转化,并陈化;将陈化后的凝胶经过干燥和煅烧后,得到主晶相粉体;
(3)按质量百分比向主晶相粉体中加入MgO和ZnO,经过研磨后模压成型制得坯体,将所述坯体烧结制得所述锆钛酸钡基瓷料。
其中,步骤(1)中,所述C16H36O4Ti、C2H5OH或(CH2OH)2、CH3COOH按体积比1:1:4~6混合。
其中,步骤(1)中,将Gd(NO3)3、(CH3COO)2Ba与Zr(NO3)4·5H2O按溶质与溶剂物质的量之比为1:40~70溶解于水中。
其中,步骤(2)中,所述pH值为3.0~4.5。
其中,步骤(1)中,将C16H36O4Ti、C2H5OH或(CH2OH)2、CH3COOH混合搅拌0.5~1h,得到A液;将B液缓慢滴加至A液中,搅拌1.5~2.5h后调节溶液pH值;继续搅拌0.5~1h后得到溶胶。
其中,步骤(2)中,将溶胶置于恒温水浴中使其发生溶胶-凝胶转化;所述恒温水浴温度为50~80℃,溶胶-凝胶转化时间为20~50min。
其中,步骤(2)中,所述陈化的温度为20~25℃,时间为8~12h。
其中,步骤(2)中,所述干燥的方式为烘干,所述烘干的温度为80~100℃。
其中,步骤(2)中,所述煅烧的温度为750~1000℃,保温2~3h,升温速率为4~5℃/min。
其中,步骤(3)中的烧结工艺为:在1290~1370℃下保温1~4h,升温速率为4~5℃/min。
有益效果:本发明与现有技术相比,取得如下显著效果:1、该瓷料通过溶胶凝胶法获得(Ba1-xGdx)(Ti0.9Zr0.1)O3+x/2主晶相纳米粉体,在改性剂ZnO及MgO作用下烧结获得微米多晶陶瓷,不仅具有高介电常数、低介电损耗的特点,且由于弥散相变的诱发使该瓷料介电常数温度稳定性显著提高;2、其能够满足隔直及旁路电路对电容器介质材料的使用要求,在汽车、电子电器、医疗等领域中具有广泛的应用前景。
附图说明
图1为本发明实施例1制备的锆钛酸钡基主晶相粉体的透射电镜图;
图2为本发明实施例1制备的锆钛酸钡基瓷料的表面微观形貌图;
图3为本发明实施例1制备的锆钛酸钡基瓷料的X射线衍射图谱。
具体实施方式
下面对本发明作进一步详细描述。
实施例1
该瓷料的主晶相粉体化学式为:(Ba0.96Gd0.04)(Ti0.9Zr0.1)O3.02,x=0.04。
该瓷料组分如下表1所示:
表1实施例1的组分及其含量
组分 | 主晶相粉体 | MgO | ZnO |
含量/wt% | 99.6 | 0.2 | 0.2 |
该瓷料的制备方法包括如下步骤:
(1)按摩尔比0.96:0.04:0.9:0.1称量(CH3COO)2Ba、Gd(NO3)3、C16H36O4Ti和Zr(NO3)4·5H2O;将C16H36O4Ti与C2H5OH和CH3COOH按体积比1:1:4混合并磁力搅拌0.5h,得到A液;将Gd(NO3)3、(CH3COO)2Ba与Zr(NO3)4·5H2O按溶质与溶剂物质的量之比为1:50以去离子水溶解,得到B液;将B液缓慢滴加至A液中,磁力搅拌2h后滴加CH3COOH调节溶液pH值至4.0,继续搅拌0.5h后得到溶胶;将溶胶置于60℃水浴锅中恒温30min使其发生溶胶-凝胶转化,在25℃陈化12h;将陈化后的凝胶在100℃烘干,以5℃/min升温速率于1000℃下煅烧2h,得到主晶相粉体。由图1可以看出该主晶相粉体的一次粒子为纳米级。
(2)按表1的质量分数向主晶相粉体中加入MgO和ZnO,在玛瑙研钵内干法研磨1h,随后模压成型制得坯体,将该坯体置于分散有二氧化锆垫料的陶瓷垫板上,控制升温速率5℃/min升至1320℃烧结保温2h成瓷,最后随炉冷却至室温,制得锆钛酸钡基瓷料。由图2可以看出该瓷料致密且粒度分布均匀,其平均晶粒尺寸为微米级。由图3可知该瓷料为钙钛矿结构单相固溶体。
将制备的瓷料进行性能检测可知,该实施例制备的锆钛酸钡基瓷料的室温介电常数为3732,介电损耗为0.0211,-30℃~85℃范围内介电常数温度变化率为+7.2~-13.4%。
实施例2
该瓷料的主晶相粉体化学式为:(Ba0.95Gd0.05)(Ti0.9Zr0.1)O3.025,x=0.05。
该瓷料组分如下表2所示:
表2实施例2的组分及其含量
组分 | 主晶相粉体 | MgO | ZnO |
含量/wt% | 99.6 | 0.2 | 0.2 |
该瓷料的制备方法包括如下步骤:
(1)按摩尔比0.95:0.05:0.9:0.1称量(CH3COO)2Ba、Gd(NO3)3、C16H36O4Ti和Zr(NO3)4·5H2O。将C16H36O4Ti与C2H5OH和CH3COOH按体积比1:1:4混合并磁力搅拌0.5h,得到A液。将Gd(NO3)3、(CH3COO)2Ba与Zr(NO3)4·5H2O按溶质与溶剂物质的量之比为1:60以去离子水溶解,得到B液。将B液缓慢滴加至A液中,磁力搅拌2h后滴加CH3COOH调节溶液pH值至4.0,继续搅拌0.5h后得到溶胶。将溶胶置于60℃水浴锅中恒温30min使其发生溶胶-凝胶转化,在25℃陈化8h。将陈化后的凝胶在100℃烘干,以5℃/min升温速率于1000℃下煅烧2h,得到主晶相粉体。
(2)按表2的质量分数向主晶相粉体中加入MgO和ZnO,在玛瑙研钵内干法研磨1h,随后模压成型制得坯体,将该坯体置于分散有二氧化锆垫料的陶瓷垫板上,控制升温速率5℃/min升至1320℃烧结保温2h成瓷,最后随炉冷却至室温,制得锆钛酸钡基瓷料。
将制备的瓷料进行性能检测可知,该实施例制备的锆钛酸钡基瓷料的室温介电常数为3194,介电损耗为0.0179,-30℃~85℃范围内介电常数温度变化率为+10.0~-7.6%。
实施例3
该瓷料的主晶相粉体化学式为:(Ba0.954Gd0.046)(Ti0.9Zr0.1)O3.023,x=0.046。
该瓷料组分如下表3所示:
表3实施例3的组分及其含量
组分 | 主晶相粉体 | MgO | ZnO |
含量/wt% | 99.7 | 0.15 | 0.15 |
该瓷料的制备方法包括如下步骤:
(1)按摩尔比0.954:0.046:0.9:0.1称量(CH3COO)2Ba、Gd(NO3)3、C16H36O4Ti和Zr(NO3)4·5H2O。将C16H36O4Ti与C2H5OH和CH3COOH按体积比1:1:5混合并磁力搅拌1h,得到A液。将Gd(NO3)3、(CH3COO)2Ba与Zr(NO3)4·5H2O按溶质与溶剂物质的量之比为1:50以去离子水溶解,得到B液。将B液缓慢滴加至A液中,磁力搅拌2h后滴加CH3COOH调节溶液pH值至3.0,继续搅拌0.5h后得到溶胶。将溶胶置于60℃水浴锅中恒温30min使其发生溶胶-凝胶转化,在25℃陈化10h。将陈化后的凝胶在100℃烘干,以4℃/min升温速率于1000℃下煅烧2h,得到主晶相粉体。
(2)按表3的质量分数向主晶相粉体中加入MgO和ZnO,在玛瑙研钵内干法研磨1h,随后模压成型制得坯体,将该坯体置于分散有二氧化锆垫料的陶瓷垫板上,控制升温速率4℃/min升至1320℃烧结保温2h成瓷,最后随炉冷却至室温,制得锆钛酸钡基瓷料。
将制备的瓷料进行性能检测可知,该实施例制备的锆钛酸钡基瓷料的室温介电常数为3476,介电损耗为0.0192,-30℃~85℃范围内介电常数温度变化率为+8.9~-10.6%。
实施例4
该瓷料的主晶相粉体化学式为:(Ba0.96Gd0.04)(Ti0.9Zr0.1)O3.02,x=0.04。
该瓷料组分如下表4所示:
表4实施例4的组分及其含量
组分 | 主晶相粉体 | MgO | ZnO |
含量/wt% | 99.7 | 0.15 | 0.15 |
该瓷料的制备方法包括如下步骤:
(1)按摩尔比0.96:0.04:0.9:0.1称量(CH3COO)2Ba、Gd(NO3)3、C16H36O4Ti和Zr(NO3)4·5H2O。将C16H36O4Ti与C2H5OH和CH3COOH按体积比1:1:4混合并磁力搅拌0.5h,得到A液。将Gd(NO3)3、(CH3COO)2Ba与Zr(NO3)4·5H2O按溶质与溶剂物质的量之比为1:40以去离子水溶解,得到B液。将B液缓慢滴加至A液中,磁力搅拌1.5h后滴加CH3COOH调节溶液pH值至3.0,继续搅拌0.5h后得到溶胶。将溶胶置于50℃水浴锅中恒温20min使其发生溶胶-凝胶转化,在20℃陈化8h。将陈化后的凝胶在80℃烘干,以4℃/min升温速率于750℃下煅烧2h,得到主晶相粉体。
(2)按表4的质量分数向主晶相粉体中加入MgO和ZnO,在玛瑙研钵内干法研磨1h,随后模压成型制得坯体,将该坯体置于分散有二氧化锆垫料的陶瓷垫板上,控制升温速率4℃/min升至1290℃烧结保温1h成瓷,最后随炉冷却至室温,制得锆钛酸钡基瓷料。
将制备的瓷料进行性能检测可知,该实施例制备的锆钛酸钡基瓷料的室温介电常数为3520,介电损耗为0.0232,-30℃~85℃范围内介电常数温度变化率为+7.9~-13.7%。
实施例5
该瓷料的主晶相粉体化学式为:(Ba0.95Gd0.05)(Ti0.9Zr0.1)O3.025,x=0.05。
该瓷料组分如下表5所示:
表5实施例5的组分及其含量
组分 | 主晶相粉体 | MgO | ZnO |
含量/wt% | 99.5 | 0.25 | 0.25 |
该瓷料的制备方法包括如下步骤:
(1)按摩尔比0.95:0.05:0.9:0.1称量(CH3COO)2Ba、Gd(NO3)3、C16H36O4Ti和Zr(NO3)4·5H2O。将C16H36O4Ti与C2H5OH和CH3COOH按体积比1:1:6混合并磁力搅拌1h,得到A液。将Gd(NO3)3、(CH3COO)2Ba与Zr(NO3)4·5H2O按溶质与溶剂物质的量之比为1:70以去离子水溶解,得到B液。将B液缓慢滴加至A液中,磁力搅拌2.5h后滴加CH3COOH调节溶液pH值至4.5,继续搅拌1h后得到溶胶。将溶胶置于80℃水浴锅中恒温50min使其发生溶胶-凝胶转化,在25℃陈化12h。将陈化后的凝胶在100℃烘干,以5℃/min升温速率于1000℃下煅烧3h,得到主晶相粉体。
(2)按表5的质量分数向主晶相粉体中加入MgO和ZnO,在玛瑙研钵内干法研磨1.5h,随后模压成型制得坯体,将该坯体置于分散有二氧化锆垫料的陶瓷垫板上,控制升温速率5℃/min升至1370℃烧结保温4h成瓷,最后随炉冷却至室温,制得锆钛酸钡基瓷料。
将制备的瓷料进行性能检测可知,该实施例制备的锆钛酸钡基瓷料的室温介电常数为3274,介电损耗为0.0189,-30℃~85℃范围内介电常数温度变化率为+11.5~-8.3%。
实施例6
该瓷料的主晶相粉体化学式为:(Ba0.96Gd0.04)(Ti0.9Zr0.1)O3.02,x=0.04。
该瓷料组分如下表6所示:
表6实施例6的组分及其含量
组分 | 主晶相粉体 | MgO | ZnO |
含量/wt% | 99.65 | 0.2 | 0.15 |
该瓷料的制备方法包括如下步骤:
(1)按摩尔比0.96:0.04:0.9:0.1称量(CH3COO)2Ba、Gd(NO3)3、C16H36O4Ti和Zr(NO3)4·5H2O。将C16H36O4Ti与(CH2OH)2和CH3COOH按体积比1:1:4混合并磁力搅拌0.5h,得到A液。将Gd(NO3)3、(CH3COO)2Ba与Zr(NO3)4·5H2O按溶质与溶剂物质的量之比为1:40以去离子水溶解,得到B液。将B液缓慢滴加至A液中,磁力搅拌1.5h后滴加CH3COOH调节溶液pH值至3.0,继续搅拌0.5h后得到溶胶。将溶胶置于50℃水浴锅中恒温20min使其发生溶胶-凝胶转化,在20℃陈化8h。将陈化后的凝胶在80℃烘干,以4℃/min升温速率于750℃下煅烧2h,得到主晶相粉体。
(2)按表6的质量分数向主晶相粉体中加入MgO和ZnO,在玛瑙研钵内干法研磨1h,随后模压成型制得坯体,将该坯体置于分散有二氧化锆垫料的陶瓷垫板上,控制升温速率4℃/min升至1290℃烧结保温1h成瓷,最后随炉冷却至室温,制得锆钛酸钡基瓷料。
将制备的瓷料进行性能检测可知,该实施例制备的锆钛酸钡基瓷料的室温介电常数为3190,介电损耗为0.0176,-30℃~85℃范围内介电常数温度变化率为+10.9~-14.1%。
实施例7
该瓷料的主晶相粉体化学式为:(Ba0.95Gd0.05)(Ti0.9Zr0.1)O3.025,x=0.05。
该瓷料组分如下表7所示:
表7实施例7的组分及其含量
组分 | 主晶相粉体 | MgO | ZnO |
含量/wt% | 99.55 | 0.2 | 0.25 |
该瓷料的制备方法包括如下步骤:
(1)按摩尔比0.95:0.05:0.9:0.1称量(CH3COO)2Ba、Gd(NO3)3、C16H36O4Ti和Zr(NO3)4·5H2O。将C16H36O4Ti与(CH2OH)2和CH3COOH按体积比1:1:6混合并磁力搅拌1h,得到A液。将Gd(NO3)3、(CH3COO)2Ba与Zr(NO3)4·5H2O按溶质与溶剂物质的量之比为1:50以去离子水溶解,得到B液。将B液缓慢滴加至A液中,磁力搅拌1.5h后滴加CH3COOH调节溶液pH值至4.0,继续搅拌0.5h后得到溶胶。将溶胶置于50℃水浴锅中恒温20min使其发生溶胶-凝胶转化,在20℃陈化10h。将陈化后的凝胶在80℃烘干,以4℃/min升温速率于1000℃下煅烧2h,得到主晶相粉体。
(2)按表7的质量分数向主晶相粉体中加入MgO和ZnO,在玛瑙研钵内干法研磨1h,随后模压成型制得坯体,将该坯体置于分散有二氧化锆垫料的陶瓷垫板上,控制升温速率4℃/min升至1290℃烧结保温2h成瓷,最后随炉冷却至室温,制得锆钛酸钡基瓷料。
将制备的瓷料进行性能检测可知,该实施例制备的锆钛酸钡基瓷料的室温介电常数为3234,介电损耗为0.0188,-30℃~85℃范围内介电常数温度变化率为+9.1~-11.3%。
Claims (10)
1.一种介电温度稳定的锆钛酸钡基瓷料,其特征在于,按质量百分比包括如下组分:
(Ba1-xGdx)(Ti0.9Zr0.1)O3+x/2 99.7-99.5wt%
MgO 0.15-0.25wt%
ZnO 0.15-0.25wt%;
其中x=0.04-0.05。
2.一种权利要求1所述介电温度稳定的锆钛酸钡基瓷料的制备方法,其特征在于,包括如下步骤:
(1)按摩尔比(1-x):x:0.9:0.1称量(CH3COO)2Ba、Gd(NO3)3、C16H36O4Ti和Zr(NO3)4·5H2O;将C16H36O4Ti、C2H5OH或(CH2OH)2、CH3COOH混合搅拌,得到A液;将Gd(NO3)3、(CH3COO)2Ba与Zr(NO3)4·5H2O溶解于水中,得到B液;
(2)将B液缓慢滴加至A液中,搅拌后调节溶液pH值,继续搅拌后得到溶胶;将溶胶置于恒温环境中使其发生溶胶-凝胶转化,并陈化;将陈化后的凝胶经过干燥和煅烧后,得到主晶相粉体;
(3)按质量百分比向主晶相粉体中加入MgO和ZnO,经过研磨后模压成型制得坯体,将所述坯体烧结制得所述锆钛酸钡基瓷料。
3.根据权利要求2所述介电温度稳定的锆钛酸钡基瓷料的制备方法,其特征在于,步骤(1)中,所述C16H36O4Ti、C2H5OH或(CH2OH)2、CH3COOH按体积比1:1:4~6混合。
4.根据权利要求2所述介电温度稳定的锆钛酸钡基瓷料的制备方法,其特征在于,步骤(1)中,将Gd(NO3)3、(CH3COO)2Ba与Zr(NO3)4·5H2O按溶质与溶剂物质的量之比为1:40~70溶解于水中。
5.根据权利要求2所述介电温度稳定的锆钛酸钡基瓷料的制备方法,其特征在于,步骤(2)中,所述pH值为3.0~4.5。
6.根据权利要求2所述介电温度稳定的锆钛酸钡基瓷料的制备方法,其特征在于,步骤(2)中,将溶胶置于恒温水浴中使其发生溶胶-凝胶转化;所述恒温水浴温度为50~80℃,溶胶-凝胶转化时间为20~50min。
7.根据权利要求2所述介电温度稳定的锆钛酸钡基瓷料的制备方法,其特征在于,步骤(2)中,所述陈化的温度为20~25℃,时间为8~12h。
8.根据权利要求2所述介电温度稳定的锆钛酸钡基瓷料的制备方法,其特征在于,步骤(2)中,所述干燥的方式为烘干,所述烘干的温度为80~100℃。
9.根据权利要求2所述介电温度稳定的锆钛酸钡基瓷料的制备方法,其特征在于,步骤(2)中,所述煅烧的温度为750~1000℃,保温2~3h,升温速率为4~5℃/min。
10.根据权利要求2所述介电温度稳定的锆钛酸钡基瓷料的制备方法,其特征在于,步骤(3)中的烧结工艺为:在1290~1370℃下保温1~4h,升温速率为4~5℃/min。
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