CN115385688A - 一种锆钛酸锶钡基介电陶瓷材料及其制备方法 - Google Patents
一种锆钛酸锶钡基介电陶瓷材料及其制备方法 Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 29
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 37
- 238000000498 ball milling Methods 0.000 claims abstract description 29
- 239000000919 ceramic Substances 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000005303 weighing Methods 0.000 claims abstract description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 7
- 238000007873 sieving Methods 0.000 claims abstract description 7
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000012700 ceramic precursor Substances 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 238000000748 compression moulding Methods 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 2
- JYPVGDJNZGAXBB-UHFFFAOYSA-N bismuth lithium Chemical compound [Li].[Bi] JYPVGDJNZGAXBB-UHFFFAOYSA-N 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 8
- 229910002113 barium titanate Inorganic materials 0.000 description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000003985 ceramic capacitor Substances 0.000 description 3
- 238000009770 conventional sintering Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910002112 ferroelectric ceramic material Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
本发明公开一种锆钛酸锶钡基介电陶瓷材料及其制备方法，属于介电陶瓷制备技术领域。本发明所述方法为了降低BSTZ的烧结温度，拓宽BSTZ介电陶瓷的工作温度范围，在BSTZ中加入Bi(Li0.5Ta0.5)O3(BLT)；制备方法为：按照设计的化学计量比分别称量BaCO3、SrCO3、TiO2、ZrO2、Bi2O3、Li2CO3、Ta2O5；采用湿法球磨混合均匀，经过干燥、预烧、二次球磨、研磨、过筛得到均匀的粉体；将粉末压制成型，然后进行烧结得到介电陶瓷材料；本发明所述方法在该锆钛酸锶钡基体内加入锂钽酸铋(BLT)，可以降低样品的烧结温度，节约了烧结成本；随着BLT的加入，样品在宽温域内体现出稳定的介电常数，拓宽了该无铅介电陶瓷的使用温度范围。
Description
技术领域
本发明涉及一种锆钛酸锶钡基介电陶瓷材料及其制备方法，属于陶瓷材料制备技术领域。
背景技术
电容器是电子电路的重要器件，近年来电子工业的快速发展对电容器材料提出了更高的要求。目前，电介质电容器材料主要可以分为陶瓷和聚合物两大类，聚合物材料的储能密度较高，但其熔点低，在高温下介电性能迅速下降。陶瓷电容器具有较好的介电性能与温度稳定性，更适用于高温高压等极端坏境。
钛酸钡是一种优异的无铅介电、铁电陶瓷材料，但由于其在不同的温度范围存在着相变，介电常数因相变波动较大。目前通常采用元素掺杂来改变钛酸钡的相变温度，减小其介电常数的波动。通过在钛酸钡中加入Sr2+，调节Sr2+和Ba2+之间的比例可以改变钛酸钡的居里温度点，从而调节钛酸钡介电陶瓷的使用温度。但是钛酸锶钡(BST)在烧结过程中Ti4+易变价，不利于介电性能的提升，通过在BST中加入Zr4+能够有效抑制Ti4+的变价。
发明内容
本发明的目的在于提供一种锆钛酸锶钡（Ba0.6Sr0.4(Ti0.7Zr0.3)O3）基陶瓷材料，所述的锆钛酸锶钡基介电陶瓷材料化学组成为：(1-x)Ba0.6Sr0.4(Ti0.7Zr0.3)O3-xBi(Li0.5Ta0.5)O3，其中，x=0~0.20，且x≠0，所述介电陶瓷在宽温域内介电常数稳定。
本发明的另一目的在于提供所述锆钛酸锶钡（Ba0.6Sr0.4(Ti0.7Zr0.3)O3）基介电陶瓷材料的制备方法，具体包括以下步骤：
（1）按照Ba0.6Sr0.4(Ti0.7Zr0.3)O3的化学计量比称取BaCO3、SrCO3、TiO2、ZrO2，然后进行球磨，烘干后于1300~1350℃煅烧3~4小时合成得到BSTZ粉体；按照Bi(Li0.5Ta0.5)O3的化学计量比称量Bi2O3、Li2CO3、Ta2O5，然后进行球磨，烘干后于750~850℃煅烧3~4小时，合成得到BLT粉体。
（2）将步骤（1）得到的粉体分别研磨、过筛；按照(1-x)Ba0.6Sr0.4(Ti0.7Zr0.3)O3-xBi(Li0.5Ta0.5)O3的化学计量比分别称量BSTZ粉体和BLT粉体，再进行二次球磨；球磨参数与一次球磨参数相同。
（3）将混合的粉末烘干后在模具中进行压制，烧结得到Ba0.6Sr0.4(Ti0.7Zr0.3)O3基介电陶瓷材料材料。
优选的，本发明步骤（1）中混合球磨中以无水乙醇和氧化锆小球作为球磨介质，无水乙醇、氧化锆小球和原料的质量比为(4~4.5):(4~4.5):1，其中，球磨转速为300~400转/分钟，球磨时间为16~18小时。
优选的，本发明所述球磨完成后烘干条件为：将湿料取出在80~100℃烘干10~12小时。
优选的，本发明步骤（2）中所述的过筛是过60~120目筛。
优选的，本发明步骤（3）中压制成型的条件为：114~151MPa单轴压力下保压6~10min。
优选的，本发明步骤（3）中烧结条件为：在试样周围敷设一层与样品相同成分的陶瓷前驱体粉末，采用埋烧的方式，以5~6℃/min的升温速率加热至烧结温度1100~1500℃保温8~10小时，冷却降温后得到该Ba0.6Sr0.4(Ti0.7Zr0.3)O3基陶瓷材料。
本发明的原理：锆钛酸锶钡(BSTZ)的烧结温度达到1500℃，烧结难度大；因此，在Ba0.6Sr0.4(Ti0.7Zr0.3)O3中加入Bi(Li0.5Ta0.5)O3(BLT)，可以使Ba0.6Sr0.4(Ti0.7Zr0.3)O3的烧结温度降低到1200℃左右，同时使Ba0.6Sr0.4(Ti0.7Zr0.3)O3介电常数在宽温域内表现出温度稳定性，满足容温变化率（∣∆C/C25°C∣≤15%）在±15%以内；本发明通过掺入BLT来改善Ba0.6Sr0.4(Ti0.7Zr0.3)O3的烧结性能与介电性能。
本发明的有益效果：
（1）本发明制备的Ba0.6Sr0.4(Ti0.7Zr0.3)O3介电陶瓷，通过Bi(Li0.5Ta0.5)O3的掺入，使得Ba0.6Sr0.4(Ti0.7Zr0.3)O3的烧结温度从1500℃下降到1150℃，节约了烧结成本。
（2）本发明制备的Ba0.6Sr0.4(Ti0.7Zr0.3)O3介电陶瓷，通过掺入Bi(Li0.5Ta0.5)O3，Ba0.6Sr0.4(Ti0.7Zr0.3)O3的介电常数在宽温度（-100~350℃）范围内保持稳定，满足容温变化率±15%（∣∆C/C25°C∣≤15%）；拓宽了该锆钛酸锶钡介电陶瓷的使用温度范围，有望作为介电陶瓷材料应用于高温陶瓷电容器。
附图说明
图1为该锆钛酸锶钡基介电陶瓷材料烧结后的XRD图谱。
图2为该锆钛酸锶钡基介电陶瓷材料烧结后表面形貌图，其中，a、b、c、d分别对应对比实施例1、实施例1、实施例2和实施例3。
图3为该锆钛酸锶钡基介电陶瓷材料晶粒尺寸统计图，其中，a、b、c、d分别对应对比实施例1、实施例1、实施例2和实施例3。
图4为该锆钛酸锶钡基介电陶瓷材料的介电温谱，其中，a、b、c、d分别对应对比实施例1、实施例1、实施例2和实施例3。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明，但本发明的保护范围并不限于所述内容。
对比实施例1
一种在宽温域内介电常数稳定的锆钛酸锶钡介电陶瓷材料Ba0.6Sr0.4(Ti0.7Zr0.3)O3(BSTZ)的制备方法，具体步骤如下：
（1）将纯度在99%以上BaCO3、SrCO3、TiO2、ZrO2按Ba0.6Sr0.4(Ti0.7Zr0.3)O3化学计量比称量，加入无水乙醇和氧化锆小球；无水乙醇、氧化锆小球和混料的质量比为4:4:1，在行星式球磨机中球磨16小时得到混合均匀的湿料，将湿料取出后在80℃干燥箱烘干12小时，得到干粉。
（2）将得到的干粉于1300℃煅烧4小时；再经过16小时的二次球磨，球磨参数与一次球磨相同，球磨完成后取出湿料在80℃干燥12小时。
（3）将混合均匀的干粉研磨后，过120目筛，接着在151MPa单轴压力下将粉末压成直径10mm、厚度1~1.3mm的陶瓷圆片。
（4）将陶瓷圆片置于刚玉坩埚后，四周敷设一层成分相同的干粉，在空气气氛下，以5˚/分钟升温到1500℃保温8小时，后随炉冷却，得到BSTZ陶瓷。
实施例1
一种在宽温域内介电常数稳定的锆钛酸锶钡基介电陶瓷材料材料0.90Ba0.6Sr0.4(Ti0.7Zr0.3)O3-0.10Bi(Li0.5Ta0.5)O3（简写0.90BSTZ-0.10BLT）的制备方法，具体步骤如下：
（1）将纯度在99%以上BaCO3、SrCO3、TiO2、ZrO2、Bi2O3、Li2CO3、Ta2O5分别按Ba0.6Sr0.4(Ti0.7Zr0.3)O3和Bi(Li0.5Ta0.5)O3化学计量比称量，加入无水乙醇和氧化锆小球。无水乙醇、氧化锆小球和混料的质量比为4:4:1，在行星式球磨机中球磨16小时得到混合均匀的湿料，将湿料取出后在80℃干燥箱烘干12小时，得到干粉；Ba0.6Sr0.4(Ti0.7Zr0.3)O3干粉于1300℃煅烧4小时，Bi(Li0.5Ta0.5)O3干粉于800℃煅烧4小时，煅烧完成后。
（2）按0.90Ba0.6Sr0.4(Ti0.7Zr0.3)O3-0.10Bi(Li0.5Ta0.5)O3化学计量比分别称量BSTZ、BLT，加入无水乙醇和氧化锆小球进行二次球磨；无水乙醇、氧化锆小球和混料的质量比为4:4:1，在行星式球磨机中球磨16小时得到混合均匀的湿料，将湿料取出后在80℃干燥箱烘干12小时。
（3）将混合均匀的干粉研磨后，过120目筛，接着在151MPa单轴压力下将粉末压成直径10mm、厚度1.3mm的陶瓷圆片。
（4）将陶瓷圆片置于刚玉坩埚后，四周敷设一层成分相同的干粉，在空气气氛下，以5˚/分钟升温到1300℃保温8小时，后随炉冷却，得到0.90BSTZ-0.10BLT陶瓷。
实施例2
一种在宽温域内介电常数稳定的锆钛酸锶钡基介电陶瓷材料材料0.85Ba0.6Sr0.4(Ti0.7Zr0.3)O3-0.15Bi(li0.5Ta0.5)O3(0.85BSTZ-0.15BLT)的制备方法，具体步骤如下：
（1）将纯度在99%以上BaCO3、SrCO3、TiO2、ZrO2、Bi2O3、Li2CO3、Ta2O5分别按Ba0.6Sr0.4(Ti0.7Zr0.3)O3、Bi(Li0.5Ta0.5)O3化学计量比称量，加入无水乙醇和氧化锆小球。无水乙醇、氧化锆小球和混料的质量比为4:4:1，在行星式球磨机中球磨16小时得到混合均匀的湿料，将湿料取出后在100℃干燥箱烘干10小时，得到干粉；Ba0.6Sr0.4(Ti0.7Zr0.3)O3干粉于1350℃煅烧3小时，Bi(Li0.5Ta0.5)O3干粉于850℃煅烧3小时，煅烧完成后。
（2）按0.85Ba0.6Sr0.4(Ti0.7Zr0.3)O3-0.15Bi(Li0.5Ta0.5)O3化学式计量比分别称量BSTZ、BLT，加入无水乙醇和氧化锆小球进行二次球磨；无水乙醇、氧化锆小球和混料的质量比为4:4:1，在行星式球磨机中球磨16小时得到混合均匀的湿料；将湿料取出后在80℃干燥箱烘干12小时。
（3）将混合均匀的干粉研磨后，过120目筛，接着在114MPa单轴压力下将粉末压成直径10mm、厚度1mm的陶瓷圆片。
（4）将陶瓷圆片置于刚玉坩埚后，四周敷设一层成分相同的干粉，在空气气氛下，以5˚/分钟升温到1200℃保温8小时，后随炉冷却，得到0.85BSTZ-0.15BLT陶瓷。
实施例3
一种在宽温域内介电常数稳定的锆钛酸锶钡基介电陶瓷材料材料0.80Ba0.6Sr0.4(Ti0.7Zr0.3)O3-0.20Bi(Li0.5Ta0.5)O3(0.80BSTZ-0.20BLT)的制备方法，具体步骤如下：
（1）将纯度在99%以上BaCO3、SrCO3、TiO2、ZrO2、Bi2O3、Li2CO3、Ta2O5分别按Ba0.6Sr0.4(Ti0.7Zr0.3)O3、Bi(Li0.5Ta0.5)O3化学计量比称量，加入无水乙醇和氧化锆小球。无水乙醇、氧化锆小球和混料的质量比为4:4:1，在行星式球磨机中球磨16小时得到混合均匀的湿料，将湿料取出后在80℃干燥箱烘干12小时，得到干粉；Ba0.6Sr0.4(Ti0.7Zr0.3)O3干粉于1300℃煅烧4小时，Bi(Li0.5Ta0.5)O3干粉于800℃煅烧4小时，煅烧完成后。
（2）按0.80Ba0.6Sr0.4(Ti0.7Zr0.3)O3-0.20Bi(Li0.5Ta0.5)O3化学式计量比分别称量BSTZ、BLT，加入无水乙醇和氧化锆小球进行二次球磨；无水乙醇、氧化锆小球和混料的质量比为4:4:1，在行星式球磨机中球磨16小时得到混合均匀的湿料。湿料取出后在80℃干燥箱烘干12小时。
（3）将混合均匀的干粉研磨后，过120目筛，接着在114MPa单轴压力下将粉末压成直径10mm，厚度1.2mm的陶瓷圆片。
（4）将陶瓷圆片置于刚玉坩埚后，四周敷设一层成分相同的干粉，在空气气氛下，以5˚/分钟升温到1150℃保温8小时，后随炉冷却，得到0.80BSTZ-0.20BLT陶瓷。
结果分析：
图1为实施例1~4四组样品常规烧结后的XRD图谱；由图1可以看出，所有实施例均为纯的立方相钙钛矿结构。
图2(a~d)分别为实施例1~4四组样品常规烧结后的表面形貌图；由图2可以看出，四组样品的晶粒晶界界限明显，表面存在少量的气孔。
图3(a~d)分别为实施例1~4四组样品常规烧结后的晶粒尺寸分布统计图；由图3可以看出，BSTZ的平均晶粒尺寸为2.67μm，0.90BSTZ-0.10BLT的平均晶粒尺寸为1.74μm；由此可以看出，掺入BLT使得样品平均晶粒尺寸减小的同时烧结温度也下降。
图4(a~d)分别为实施例1~4四组样品在打磨光滑表面，涂敷银浆烧制成银电极后测试的介电温谱图；由图4可以看出BSTZ的介电常数在测试温度范围内（-100~350℃）从3600变化到270，0.80BSTZ-0.20BLT样品在500kHz条件下，在测试温度范围（-100~350℃）内介电常数在158~160之间变化，表现出温度稳定性。
表1为四组样品在100kHz下以25℃为基准温度的容温变化率
由表1可以看出随着BLT的掺入，陶瓷样品的工作温度范围不断增加，0.85BSTZ-0.15BLT和0.80BSTZ-0.20BLT样品的工作温度达到350℃，满足国际电子工业协会(EIA)标准中X9R(-55~200℃)型陶瓷电容器的使用温度要求。
Claims (7)
1.一种锆钛酸锶钡基介电陶瓷材料，其特征在于：所述的锆钛酸锶钡基介电陶瓷材料化学组成为：(1-x)Ba0.6Sr0.4(Ti0.7Zr0.3)O3-xBi(Li0.5Ta0.5)O3，其中，x=0~0.20，且x≠0，所述介电陶瓷在宽温域内介电常数稳定。
2.权利要求1所述锆钛酸锶钡基介电陶瓷材料的制备方法，其特征在于：具体包括以下步骤：
（1）按照Ba0.6Sr0.4(Ti0.7Zr0.3)O3的化学计量比称取BaCO3、SrCO3、TiO2、ZrO2，然后进行球磨，烘干后于1300~1350℃煅烧3~4小时合成得到BSTZ粉体；按照Bi(Li0.5Ta0.5)O3的化学计量比称量Bi2O3、Li2CO3、Ta2O5，然后进行球磨，烘干后于750~850℃煅烧3~4小时，合成得到BLT粉体；
（2）将步骤（1）得到的粉体分别研磨、过筛；按照(1-x)Ba0.6Sr0.4(Ti0.7Zr0.3)O3-xBi(Li0.5Ta0.5)O3的化学计量比分别称量BSTZ粉体和BLT粉体，再进行二次球磨；球磨参数与第一次球磨相同；
（3）将混合的粉末烘干后在模具中进行压制，烧结得到Ba0.6Sr0.4(Ti0.7Zr0.3)O3基介电陶瓷材料材料。
3.根据权利要求2所述锆钛酸锶钡基介电陶瓷材料的制备方法，其特征在于：步骤（1）或（2）中混合球磨中以无水乙醇和氧化锆小球作为球磨介质，无水乙醇、氧化锆小球和原料的质量比为(4~4.5):(4~4.5):1，其中，球磨转速为300~400转/分钟，球磨时间为16~18小时。
4.根据权利要求3所述锆钛酸锶钡基介电陶瓷材料的制备方法，其特征在于：球磨完成后烘干条件为：将湿料取出在80~100℃烘干10~12小时。
5.根据权利要求1或4所述锆钛酸锶钡基介电陶瓷材料的制备方法，其特征在于：步骤（2）中所述的过筛是过60~120目筛。
6.根据权利要求5所述锆钛酸锶钡基介电陶瓷材料的制备方法，其特征在于：步骤（3）中压制成型的条件为：114~151MPa单轴压力下保压6~10min。
7.根据权利要求6所述锆钛酸锶钡基介电陶瓷材料的制备方法，其特征在于：步骤（3）中烧结条件为：在试样周围敷设一层与样品成分相同的陶瓷前驱体粉末，采用埋烧的方式，以5~6℃/min的升温速率加热至烧结温度1100~1500℃保温8~10小时，冷却降温后得到该Ba0.6Sr0.4(Ti0.7Zr0.3)O3基陶瓷材料。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH038760A (ja) * | 1989-06-06 | 1991-01-16 | Matsushita Electric Ind Co Ltd | 電圧依存性非直線抵抗体磁器組成物およびバリスタの製造方法 |
| CN101024574A (zh) * | 2007-01-30 | 2007-08-29 | 合肥工业大学 | 铋基钙钛矿替代的铌酸钾钠系无铅压电陶瓷及其制备方法 |
| CN107778004A (zh) * | 2017-11-15 | 2018-03-09 | 广东工业大学 | 一种锆钛酸锶钡陶瓷及其制备方法和应用 |
| CN111763084A (zh) * | 2020-07-10 | 2020-10-13 | 广东工业大学 | 一种高电卡效应的掺锰钛酸锶钡陶瓷及其制备方法和应用 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH038760A (ja) * | 1989-06-06 | 1991-01-16 | Matsushita Electric Ind Co Ltd | 電圧依存性非直線抵抗体磁器組成物およびバリスタの製造方法 |
| CN101024574A (zh) * | 2007-01-30 | 2007-08-29 | 合肥工业大学 | 铋基钙钛矿替代的铌酸钾钠系无铅压电陶瓷及其制备方法 |
| CN107778004A (zh) * | 2017-11-15 | 2018-03-09 | 广东工业大学 | 一种锆钛酸锶钡陶瓷及其制备方法和应用 |
| CN111763084A (zh) * | 2020-07-10 | 2020-10-13 | 广东工业大学 | 一种高电卡效应的掺锰钛酸锶钡陶瓷及其制备方法和应用 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116444266A (zh) * | 2023-04-03 | 2023-07-18 | 昆明理工大学 | 一种Ba0.6Sr0.4(Ti0.7Zr0.3)O3基介电陶瓷的制备方法 |
| CN116444266B (zh) * | 2023-04-03 | 2023-11-21 | 昆明理工大学 | 一种Ba0.6Sr0.4(Ti0.7Zr0.3)O3基介电陶瓷的制备方法 |
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