CN106699169B - 一种高电阻率多铁性复合陶瓷及其制备方法 - Google Patents
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- 239000000919 ceramic Substances 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000009768 microwave sintering Methods 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 24
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- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 19
- 229910001626 barium chloride Inorganic materials 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 19
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- 229910052709 silver Inorganic materials 0.000 claims description 17
- 239000004332 silver Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 16
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 13
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 239000011565 manganese chloride Substances 0.000 claims description 13
- 239000012670 alkaline solution Substances 0.000 claims description 12
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 7
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- 239000000463 material Substances 0.000 abstract description 17
- 229910002771 BaFe12O19 Inorganic materials 0.000 abstract description 9
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Abstract
本发明公开了一种高电阻率多铁性复合陶瓷及其制备方法，属于材料制备技术领域。该复合陶瓷的化学组成表达为：BaTiO3‑BaFe12‑ xMnxO19，0≤x≤1.0。本发明以BaTiO3‑BaFe12O19为基体，通过掺杂Mn2+极大的提高了其电阻率，进而提高介电性能。为多铁性复合陶瓷的实际应用提供了一种切实可行的方法。并且微波烧结法不同于一般的传统烧结，烧结时间很短，烧结过程中不存在温度梯度，此方法结合微波水热法制备的纳米粉体烧结的陶瓷具有晶粒尺寸小，致密度高等诸多优点。
Description
技术领域
本发明属于材料制备技术领域，涉及多铁性材料的制备方法，具体涉及一种高电阻率多铁性复合陶瓷及其制备方法。
背景技术
多铁性材料又称磁电材料，它是指同时具有两种或两种以上基本铁性(铁电性、铁磁性和铁弹性)的材料，多铁性材料的研究与磁电耦合效应的研究是密不可分的，同一材料中磁性和铁电性共存使得多铁性材料不仅仅可以作为单一的磁性材料和铁电性材料来使用，同时，多铁性材料中磁与电的耦合效应，即外加电场导致物质磁化或外加的磁场导致物质内部出现电极化，使得该材料在应用中具有更高的自由度，为器件的小型化和多功能化提供了可能。
一般由铁电相和铁磁相两相构成的磁电多铁性复合陶瓷具有可设计性，可调控性，在室温下比单相多铁性材料具有更强磁电效应等优点。然而，多铁性复合陶瓷的性能取决于材料合适的组成相，两相的连通性，体积分数，晶粒尺寸和形状等等因素。因为BaTiO3是典型的铁电相，BaFe12O19是典型的铁磁相，所以BaTiO3-BaFe12O19是最重要的多铁性复合陶瓷的研究体系之一([1]Zijing Dong,et al.Fabrication,structure and propertiesof BaTiO3–BaFe12O19composites with core–shell heterostructure[J].Journal of theEuropean Ceramic Society,2015,35:3513-3520)。一般具有高的电阻率是磁电复合材料获得优异磁电性能的前提条件。BaTiO3-BaFe12O19复合陶瓷体系中BaFe12O19的电阻率比BaTiO3低几个数量级，复合后在两相界面必然会存在电荷的移动。导致材料的漏导增加，损耗增大，介电性能恶化。因此，本研究通过掺杂Mn2+离子，通过Verwey hopping mechanism改善BaFe12O19的性能，从而在不影响材料铁磁性能的前提下，提高BaTiO3-BaFe12O19复合陶瓷的铁电性能，使其多铁性能近一步满足实际应用。
发明内容
本发明的目的在于提供一种高电阻率多铁性复合陶瓷及其制备方法，该方法操作简单，重复性好，经该方法制得的复合陶瓷介电常数高，损耗小，电阻率较高。
本发明是通过以下技术方案来实现：
本发明公开了一种高电阻率多铁性复合陶瓷，该复合陶瓷的化学组成表达为：BaTiO3-BaFe12-xMnxO19，0.2≤x≤0.8。
本发明还公开了一种高电阻率多铁性复合陶瓷的制备方法，包括以下步骤：
1)取TiCl4和BaCl2·2H2O，先后溶解于30ml-50ml蒸馏水中；
2)称取KOH，并溶解于步骤1)所得溶液中；
3)将步骤2)制得的前驱液在180～220℃下，微波水热反应25～35min，制得反应产物，将反应产物水洗至中性；
4)按BaFe12-xMnxO19中Ba2+，Mn2+，Fe3+的摩尔比，称取Ba(NO3)2，MnCl2·4H2O和Fe(NO3)3·9H2O，溶解于蒸馏水中，调节溶液pH值至≥13，制得碱性溶液，将该碱性溶液在170～190℃下，微波水热25～30min，制得反应物，将反应物水洗至中性；
5)将步骤3)和步骤4)制得的产物混合后烘干，得到混合粉体，再加入体积浓度为5％的PVA粘结剂，然后进行造粒、压制成型，制得坯体；
6)将坯体在600℃排胶1.5h-2.5h，得到陶瓷生坯，然后将陶瓷生坯在1000℃～1100℃下微波烧结3min-6min，制得复合陶瓷。
步骤1)和步骤2)中所用的原料摩尔比TiCl4：BaCl2·2H2O：KOH＝1：2：10。
步骤6)制得复合陶瓷后，再对其进行表面抛光，被银电极，在600℃保温10min，烧渗银电极，制得得到复合陶瓷样品。
烧渗银电极的升温制度为：以2℃/min的升温速率从室温升温到200℃，然后以3℃/min的升温速率从200℃升温到500℃，最后以5℃/min的升温速度从500℃升温到600℃，降温时，随炉冷却。
步骤6)所述排胶的升温制度为：以2℃/min的升温速率从室温升温到200℃，然后以3℃/min的升温速率从200℃升温到500℃，最后以5℃/min的升温速度从500℃升温到600℃，降温时，随炉冷却。
步骤6)所述微波烧结的输出功率为1500W，升温速率为25℃/min，且在30min内从室温升温到1000℃～1100℃，降温时，随炉冷却。
步骤3)和步骤4)水洗用水为蒸馏水，水洗5～6次。
原料TiCl4、BaCl2·2H2O、MnCl2·4H2O、Fe(NO3)3·9H2O、KOH和Ba(NO3)2的纯度均为99.0％以上。
与现有技术相比，本发明具有以下有益的技术效果：
本发明提供的一种高电阻率多铁性复合陶瓷及其制备方法，采用Mn2+掺杂BaTiO3-BaFe12O19多铁性复合陶瓷的方法，具有以下优点：
1)采用微波水热法制备粉体，具有晶粒小，尺寸均匀，结晶度高，反应时间短等优点；
2)采用微波烧结法烧结陶瓷，不同于一般的传统烧结，烧结时间短，烧结过程中不存在温度梯度，此方法结合微波水热法制备的纳米粉体烧结的陶瓷具有晶粒尺寸小，致密度高等诸多优点；
3)以TiCl4、BaCl2·2H2O、MnCl2·4H2O、Fe(NO3)3·9H2O、KOH和Ba(NO3)2为原料，原料简单，价格低廉。
经本发明方法制备的高电阻率多铁性复合陶瓷提高了多铁性BaTiO3-BaFe12O19的铁电性能，具有晶粒小，尺寸均匀，结晶度高，介电常数高，损耗小，磁滞回线磁化强度高等优点，为多铁性BaTiO3-BaFe12O19复合陶瓷的实际应用提供了一种切实可行的方法。
附图说明
图1是一种高电阻率多铁性复合陶瓷材料的XRD图谱；
图2(a)、图2(b)、图2(c)、图2(d)、图2(e)、图2(f)分别为x＝0、0.2、0.4、0.6、0.8、1.0的高电阻率多铁性复合陶瓷的SEM照片；
图3是一种高电阻率多铁性复合陶瓷的电阻率的变化图谱；
图4是一种高电阻率多铁性复合陶瓷的介电常数和损耗随频率的变化图谱；
图5是一种高电阻率多铁性复合陶瓷材料的电滞回线；
图6是一种高电阻率多铁性复合陶瓷材料的磁滞回线。
具体实施方式
下面结合具体的实施例对本发明做进一步的详细说明，所述是对本发明的解释而不是限定。
实施例1
本实施例中复合陶瓷BaTiO3-BaFe12-xMnxO19中x＝0.2，制备方法包括以下步骤：
1)取TiCl4和BaCl2·2H2O，先后溶解于40ml蒸馏水中；
2)称取KOH，并溶解于步骤1)所得溶液中；
3)将步骤2)制得的前驱液在180～220℃下，微波水热反应25～35min，制得反应产物，将反应产物水洗至中性；
4)按BaFe12-xMnxO19中Ba2+，Mn2+，Fe3+的摩尔比，称取Ba(NO3)2，MnCl2·4H2O和Fe(NO3)3·9H2O，溶解于蒸馏水中，调节溶液pH值至≥13，制得碱性溶液，将该碱性溶液在170～190℃下，微波水热25～30min，制得反应物，将反应物水洗至中性；
5)将步骤3)和步骤4)制得的产物混合后烘干，得到混合粉体，再加入体积浓度为5％的PVA粘结剂，然后进行造粒、压制成型，制得坯体；
6)将坯体在600℃排胶2h，得到陶瓷生坯，然后将陶瓷生坯在1000℃～1100℃下微波烧结5min，制得复合陶瓷。
步骤1)和步骤2)中所用的原料摩尔比TiCl4：BaCl2·2H2O：KOH＝1：2：10。
步骤6)制得复合陶瓷后，再对其进行表面抛光，被银电极，在600℃保温10min，烧渗银电极，制得得到复合陶瓷样品。
烧渗银电极的升温制度为：以2℃/min的升温速率从室温升温到200℃，然后以3℃/min的升温速率从200℃升温到500℃，最后以5℃/min的升温速度从500℃升温到600℃，降温时，随炉冷却。
步骤6)所述排胶的升温制度为：以2℃/min的升温速率从室温升温到200℃，然后以3℃/min的升温速率从200℃升温到500℃，最后以5℃/min的升温速度从500℃升温到600℃，降温时，随炉冷却。
步骤6)所述微波烧结的输出功率为1500W，升温速率为25℃/min，且在30min内从室温升温到1000℃～1100℃，降温时，随炉冷却。
步骤3)和步骤4)水洗用水为蒸馏水，水洗5～6次。
原料TiCl4、BaCl2·2H2O、MnCl2·4H2O、Fe(NO3)3·9H2O、KOH和Ba(NO3)2的纯度均为99.0％以上。
实施例2
本实施例中复合陶瓷BaTiO3-BaFe12-xMnxO19中x＝0.4，制备方法包括以下步骤：
1)取TiCl4和BaCl2·2H2O，先后溶解于40ml蒸馏水中；
2)称取KOH，并溶解于步骤1)所得溶液中；
3)将步骤2)制得的前驱液在180～220℃下，微波水热反应25～35min，制得反应产物，将反应产物水洗至中性；
4)按BaFe12-xMnxO19中Ba2+，Mn2+，Fe3+的摩尔比，称取Ba(NO3)2，MnCl2·4H2O和Fe(NO3)3·9H2O，溶解于蒸馏水中，调节溶液pH值至≥13，制得碱性溶液，将该碱性溶液在170～190℃下，微波水热25～30min，制得反应物，将反应物水洗至中性；
5)将步骤3)和步骤4)制得的产物混合后烘干，得到混合粉体，再加入体积浓度为5％的PVA粘结剂，然后进行造粒、压制成型，制得坯体；
6)将坯体在600℃排胶2h，得到陶瓷生坯，然后将陶瓷生坯在1000℃～1100℃下微波烧结5min，制得复合陶瓷。
步骤1)和步骤2)中所用的原料摩尔比TiCl4：BaCl2·2H2O：KOH＝1：2：10。
步骤6)制得复合陶瓷后，再对其进行表面抛光，被银电极，在600℃保温10min，烧渗银电极，制得得到复合陶瓷样品。
烧渗银电极的升温制度为：以2℃/min的升温速率从室温升温到200℃，然后以3℃/min的升温速率从200℃升温到500℃，最后以5℃/min的升温速度从500℃升温到600℃，降温时，随炉冷却。
步骤6)所述排胶的升温制度为：以2℃/min的升温速率从室温升温到200℃，然后以3℃/min的升温速率从200℃升温到500℃，最后以5℃/min的升温速度从500℃升温到600℃，降温时，随炉冷却。
步骤6)所述微波烧结的输出功率为1500W，升温速率为25℃/min，且在30min内从室温升温到1000℃～1100℃，降温时，随炉冷却。
步骤3)和步骤4)水洗用水为蒸馏水，水洗5～6次。
原料TiCl4、BaCl2·2H2O、MnCl2·4H2O、Fe(NO3)3·9H2O、KOH和Ba(NO3)2的纯度均为99.0％以上。
实施例3
本实例中复合陶瓷BaTiO3-BaFe12-xMnxO19中x＝0.6，制备方法包括以下步骤：
1)取TiCl4和BaCl2·2H2O，先后溶解于40ml蒸馏水中；
2)称取KOH，并溶解于步骤1)所得溶液中；
3)将步骤2)制得的前驱液在180～220℃下，微波水热反应25～35min，制得反应产物，将反应产物水洗至中性；
4)按BaFe12-xMnxO19中Ba2+，Mn2+，Fe3+的摩尔比，称取Ba(NO3)2，MnCl2·4H2O和Fe(NO3)3·9H2O，溶解于蒸馏水中，调节溶液pH值至≥13，制得碱性溶液，将该碱性溶液在170～190℃下，微波水热25～30min，制得反应物，将反应物水洗至中性；
5)将步骤3)和步骤4)制得的产物混合后烘干，得到混合粉体，再加入体积浓度为5％的PVA粘结剂，然后进行造粒、压制成型，制得坯体；
6)将坯体在600℃排胶2h，得到陶瓷生坯，然后将陶瓷生坯在1000℃～1100℃下微波烧结5min，制得复合陶瓷。
步骤1)和步骤2)中所用的原料摩尔比TiCl4：BaCl2·2H2O：KOH＝1：2：10。
步骤6)制得复合陶瓷后，再对其进行表面抛光，被银电极，在600℃保温10min，烧渗银电极，制得得到复合陶瓷样品。
烧渗银电极的升温制度为：以2℃/min的升温速率从室温升温到200℃，然后以3℃/min的升温速率从200℃升温到500℃，最后以5℃/min的升温速度从500℃升温到600℃，降温时，随炉冷却。
步骤6)所述排胶的升温制度为：以2℃/min的升温速率从室温升温到200℃，然后以3℃/min的升温速率从200℃升温到500℃，最后以5℃/min的升温速度从500℃升温到600℃，降温时，随炉冷却。
步骤6)所述微波烧结的输出功率为1500W，升温速率为25℃/min，且在30min内从室温升温到1000℃～1100℃，降温时，随炉冷却。
步骤3)和步骤4)水洗用水为蒸馏水，水洗5～6次。
原料TiCl4、BaCl2·2H2O、MnCl2·4H2O、Fe(NO3)3·9H2O、KOH和Ba(NO3)2的纯度均为99.0％以上。
实施例4
本实例中复合陶瓷BaTiO3-BaFe12-xMnxO19中x＝0.8，制备方法包括以下步骤：
1)取TiCl4和BaCl2·2H2O，先后溶解于40ml蒸馏水中；
2)称取KOH，并溶解于步骤1)所得溶液中；
3)将步骤2)制得的前驱液在180～220℃下，微波水热反应25～35min，制得反应产物，将反应产物水洗至中性；
4)按BaFe12-xMnxO19中Ba2+，Mn2+，Fe3+的摩尔比，称取Ba(NO3)2，MnCl2·H2O和Fe(NO3)3·9H2O，溶解于蒸馏水中，调节溶液pH值至≥13，制得碱性溶液，将该碱性溶液在170～190℃下，微波水热25～30min，制得反应物，将反应物水洗至中性；
5)将步骤3)和步骤4)制得的产物混合后烘干，得到混合粉体，再加入体积浓度为5％的PVA粘结剂，然后进行造粒、压制成型，制得坯体；
6)将坯体在600℃排胶2h，得到陶瓷生坯，然后将陶瓷生坯在1000℃～1100℃下微波烧结5min，制得复合陶瓷。
步骤1)和步骤2)中所用的原料摩尔比TiCl4：BaCl2·2H2O：KOH＝1：2：10。
步骤6)制得复合陶瓷后，再对其进行表面抛光，被银电极，在600℃保温10min，烧渗银电极，制得得到复合陶瓷样品。
烧渗银电极的升温制度为：以2℃/min的升温速率从室温升温到200℃，然后以3℃/min的升温速率从200℃升温到500℃，最后以5℃/min的升温速度从500℃升温到600℃，降温时，随炉冷却。
步骤6)所述排胶的升温制度为：以2℃/min的升温速率从室温升温到200℃，然后以3℃/min的升温速率从200℃升温到500℃，最后以5℃/min的升温速度从500℃升温到600℃，降温时，随炉冷却。
步骤6)所述微波烧结的输出功率为1500W，升温速率为25℃/min，且在30min内从室温升温到1000℃～1100℃，降温时，随炉冷却。
步骤3)和步骤4)水洗用水为蒸馏水，水洗5～6次。
原料TiCl4、BaCl2·2H2O、MnCl2·4H2O、Fe(NO3)3·9H2O、KOH和Ba(NO3)2的纯度均为99.0％以上。
请参见图1及图2，实施以上实例所制备的BaTiO3-BaFe12-xMnxO19复合陶瓷材料的XRD图谱和SEM照片中可以看出，以上实施例中已经合成了BaTiO3和BaFe12-xMnxO19相共存的复合陶瓷。同时，可以看出没有其他杂相存在，且这两相结晶度较高，没有互相反应，化学相容性较好。参见图3，可以看出电阻率随着组分的增加，逐渐增大。参见图4，可以看出介电常数达到10000以上，介电性能优良。参见图5，复合陶瓷具有较饱和的电滞回线，在x＝0.6时获得了最优的铁电性。参见图6，可以看出通过掺杂Mn2+，复合陶瓷的饱和磁化强度仍然保持在较高水平。
综上所述，本发明通过微波水热法和微波烧结法制备了BaTiO3-BaFe12-xMnxO19复合陶瓷。以BaTiO3-BaFe12-xMnxO19为基体，通过掺杂Mn2+极大的提高了其电阻率，进而提高介电性能。并且微波烧结法不同于一般的传统烧结，烧结时间很短，烧结过程中不存在温度梯度，此方法结合微波水热法制备的纳米粉体烧结的陶瓷具有晶粒尺寸小，致密度高等诸多优点，为多铁性复合材料的实际应用提供了一种切实可行的方法。
本发明公开的采用BaTiO3-BaFe12-xMnxO19复合陶瓷及其制备方法有可能成为制备多铁性复合材料在技术上和经济上兼优的新配方。
Claims (4)
1.一种高电阻率多铁性复合陶瓷，其特征在于，复合陶瓷的化学组成表达为：BaTiO3-BaFe12-xMnxO19，x＝0.6。
2.一种基于权利要求1所述的高电阻率多铁性复合陶瓷的制备方法，其特征在于，包括以下步骤：
1)取TiCl4和BaCl2·2H2O，先后溶解于蒸馏水中；
2)称取KOH，并溶解于步骤1)所得溶液中，所用TiCl4、BaCl2·2H2O和KOH的摩尔比为1：2：10；
3)将步骤2)制得的前驱液在180℃～220℃下，微波水热反应25～35min，制得反应产物，将反应产物用蒸馏水洗5～6次至中性；
4)按BaFe12-xMnxO19中Ba2+，Fe3+，Mn2+的摩尔比，称取Ba(NO3)2，MnCl2·4H2O和Fe(NO3)3·9H2O，溶解于蒸馏水中，调节溶液pH值至≥13，制得碱性溶液，将碱性溶液在170～190℃下，微波水热25～30min，制得反应物，将反应物用蒸馏水洗5～6次至中性；
5)将步骤3)和步骤4)制得的产物混合后烘干，得到混合粉体，再加入体积浓度为5％的PVA粘结剂，然后进行造粒、压制成型，制得坯体；
6)将坯体在550℃-600℃排胶1.5h-2.5h，排胶的升温制度为：以2℃/min的升温速率从室温升温到200℃，然后以3℃/min的升温速率从200℃升温到500℃，最后以5℃/min的升温速度从500℃升温到600℃，降温时，随炉冷却；得到陶瓷生坯，然后将陶瓷生坯在1000℃～1100℃下微波烧结3min-6min，微波烧结的输出功率为1500W，升温速率为25℃/min，且在30min内从室温升温到1000℃～1100℃，降温时，随炉冷却，制得复合陶瓷；
原料TiCl4、BaCl2·2H2O、MnCl2·4H2O、Fe(NO3)3·9H2O、KOH和Ba(NO3)2的纯度均为99.0％以上。
3.根据权利要求2所述的高电阻率多铁性复合陶瓷的制备方法，其特征在于，步骤6)制得复合陶瓷后，再对其进行表面抛光，被银电极，在600℃保温10min，烧渗银电极，制得复合陶瓷样品。
4.根据权利要求3所述的高电阻率多铁性复合陶瓷的制备方法，其特征在于，烧渗银电极的升温制度为：以2℃/min的升温速率从室温升温到200℃，然后以3℃/min的升温速率从200℃升温到500℃，最后以5℃/min的升温速度从500℃升温到600℃，降温时，随炉冷却。
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