CN114644523A - 一种钙钛矿结构高熵介电陶瓷及其制备方法 - Google Patents
一种钙钛矿结构高熵介电陶瓷及其制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 10
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- 238000000034 method Methods 0.000 claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 14
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
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- 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 8
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 8
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 8
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims abstract description 8
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- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 229910002113 barium titanate Inorganic materials 0.000 description 9
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Abstract
本发明公开了一种钙钛矿结构高熵介电陶瓷及其制备方法，属于无机电介质陶瓷领域。本发明所述的钙钛矿结构高熵介电陶瓷，其化学式为(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Me0.5)O3(Me＝Sn,Zr,Hf)。其制备过程为：先按照化学计量比称取原料BaCO3、TiO2、La2O3、SrCO3、Na2CO3、SnO2、ZrO2、HfO2；然后采用湿法球磨混合均匀，经过干燥、煅烧后，再二次球磨、干燥、研磨得到所需的混合粉末；在混合粉末中加入适量的聚乙烯醇混合均匀后，放置模具中压制成片；采用埋烧的方式将压制片放置在密闭的双层氧化铝坩埚内，置于高温箱式电阻炉在空气气氛下烧结；该陶瓷具有击穿场强大、剩余极化强度小、储能效率高和温度稳定性好等优点，在无机介质电容器领域有着广阔的应用前景。
Description
技术领域
本发明涉及一种钙钛矿结构高熵介电陶瓷及其制备方法，属于无机电介质陶瓷领域。
背景技术
钛酸钡陶瓷因为其成本低、绿色无污染、介电性能优异等特点，是目前工程上广泛应用的电介质材料。但是，钛酸钡也存在剩余极化强度高、击穿场强低、介电性能不稳定等缺点，根据储能密度方程
(Wrec、Pmax、Pr、和E分别为放电储能密度、最大极化强度、剩余极化强度和电场强度)，这就造成了钛酸钡的储能密度小且储能效率低。近些年，随着电子技术的飞速发展，人们对介电陶瓷的储能性能要求越来越高。所以，解决目前钛酸钡存在的不足之处，是提高钛酸钡基陶瓷储能性能所亟待解决的问题。
最近几年，由高熵合金演变而来的高熵陶瓷，因为具有多种优异的物理性能而成为材料研究领域的热点。高熵陶瓷是指由五种及以上主元，且各主元的含量相等(或几乎相等)所形成的单相固溶体。根据以往人们的研究发现，高熵陶瓷的核心效应之一就是扩散缓慢，由于固溶体引起的晶格畸变和多元素的协同扩散，原子运动和原子的有效扩散受到阻碍。所以，可以得到具有细小晶粒和晶粒生长缓慢的单相固溶体。依据公式
(其中BDS为击穿场强，G为晶粒尺寸)可知，减小晶粒尺寸能显著增加陶瓷的击穿场强。综上所述，设计、制备得到高熵钙钛矿陶瓷，对解决目前钛酸钡基介电材料存在的问题是十分可行而有意义的。
发明内容
本发明目的在于，为了解决目前钛酸钡介电陶瓷存在的不足，提供一种新型的钙钛矿结构高熵介电陶瓷，所述钙钛矿结构高熵介电陶瓷具有不含铅、高击穿场强、高储能效率、温度稳定性好的优点。所述钙钛矿结构高熵介电陶瓷的化学式为(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Me0.5)O3，其中，Me＝Sn,Zr,Hf。
本发明的另一目的在于提供所述钙钛矿结构高熵介电陶瓷的制备方法，具体包括以下步骤：
(1)按照化学计量比称取BaCO3、TiO2、La2O3、SrCO3、Na2CO3，其中在SnO2、ZrO2和HfO2三种原料中任意称量一种。
(2)将步骤(1)称取的原料采用湿法球磨，经过干燥、研磨、煅烧后得到混合粉末。
(3)将得到的混合粉末二次球磨、干燥、研磨。
(4)将二次球磨得到的混合粉末加入聚乙烯醇(PVA)，混合均匀后，放置于模具内，压制成陶瓷坯体。
(5)将陶瓷坯体放置在双层氧化铝坩埚内，采用埋烧的方式，置于高温箱式电阻炉在空气气氛下烧结，得到钙钛矿结构高熵介电陶瓷。
优选的，本发明步骤(1)中所涉及的BaCO3、TiO2、La2O3、SrCO3、Na2CO3、SnO2、ZrO2和HfO2的纯度≥99％。
优选的，本发明步骤(2)中球磨的条件为：球磨转速300rpm，球磨时间为12-18h；球磨介质为无水乙醇、ZrO2球，球:料:无水乙醇的质量比为3:1:3，干燥的温度为70-100℃，干燥时间为12-24h。
优选的，本发明步骤(2)中煅烧过程为以10℃/min的升温速率将温度从室温升温到700℃，保温2h。
优选的，本发明步骤(3)中二次球磨的条件为：球磨转速300rpm，球磨时间为6h；球磨介质为无水乙醇、ZrO2球，球:料:无水乙醇的质量比为3:1:3，干燥的温度为70-100℃，干燥时间为12-24h。
优选的，本发明步骤(4)中聚乙烯醇的质量百分比浓度为8wt.％，加入量为每1g混合粉末中加入1滴，将混合均匀后的粉体在280MPa的单轴压力下保压5-8min，压制成直径为18mm的圆片。
优选的，本发明步骤(5)中将压制好的圆片放入氧化铝小坩埚中，在圆片下方垫一层与样品成分相同的混合粉末，并在圆片上方覆盖一层同样的粉末，稍稍压实粉末，然后将小坩埚放置于大坩埚内,置于高温箱式电阻炉进行烧结；烧结过程为以10℃/min的升温速率将温度从室温升温至500℃，保温2h，然后以10℃/min的升温速率将温度升至1000℃，再以5℃/min的升温速率将温度升至1400℃，最后以3℃/min的升温速率升温至1500℃，保温10h后，随炉冷却至室温。
本发明的有益效果：
(1)本发明制备的钙钛矿结构高熵介电陶瓷都能形成单相固溶体，XRD图中并没有发现其他杂相所有的样品均为单一的钙钛矿结构。
(2)本发明将钙钛矿结构高熵介电陶瓷在1450℃下退火30min后，其SEM图可以看出该陶瓷的晶粒尺寸小，说明陶瓷在高温下晶粒的生长速率缓慢，有利于细化晶粒，提高陶瓷的击穿场强。
(3)本发明制备的钙钛矿结构高熵介电陶瓷具有大的击穿场强，(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Me0.5)O3(Me＝Sn,Zr,Hf)击穿场强依次为230kV/cm、200kV/cm、120kV/cm，储能效率高，均大于80％，温度稳定性好。
附图说明
图1为该钙钛矿结构高熵介电陶瓷烧结后的XRD图谱；
图2为该钙钛矿结构高熵介电陶瓷烧结后的元素分布图；
图3为该钙钛矿结构高熵介电陶瓷的介电温谱图；
图4为该钙钛矿结构高熵介电陶瓷的电滞回线图。
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。
实施例1
一种钙钛矿结构高熵介电陶瓷(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Sn0.5)O3制备方法，具体步骤如下：
(1)将BaCO3、TiO2、La2O3、SrCO3、Na2CO3、SnO2按照摩尔比为2：4：1：2：1：4进行称料。
(2)把称好的原料粉末使用行星式球磨机进行球磨，转速为300rpm，球磨时间为18h；球磨介质为无水乙醇、ZrO2球，其中球:料:无水乙醇的质量比为3:1:3；干燥的温度为70℃，干燥时间为24h。然后将干燥后的混合粉末进行煅烧，煅烧过程为以10℃/min的升温速率将温度从室温升温至700℃，保温2h。
(3)将得到的混合粉末二次球磨、干燥、研磨，二次球磨、干燥的具体方法与步骤(2)相同，只是球磨时间为6h。
(4)在二次球磨得到的混合粉末加入适量(1g/滴)的8wt.％的聚乙烯醇(PVA)作粘结剂，混合均匀，然后取2g粉末置于模具内，在280MPa的单轴压力下保压5-8min，压制成直径为18mm的圆片坯体。
(5)将压制好的坯体放入氧化铝小坩埚中，在坯体下方垫一层与其成分相同的混合粉末，并在坯体上方覆盖一层同样的粉末，稍稍压实粉末，然后将小坩埚放置于大坩埚内，一起置于高温箱式电阻炉内进行烧结；烧结过程为以10℃/min的升温速率将温度从室温升温至500℃，保温2h，然后以10℃/min的升温速率将温度升至1000℃，再以5℃/min的升温速率将温度升至1400℃，最后以3℃/min的升温速率升温至1500℃，保温10h后，随炉冷却至室温，得到(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Sn0.5)O3高熵陶瓷。
实施例2
一种钙钛矿结构高熵介电陶瓷(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Zr0.5)O3制备方法，具体步骤如下：
(1)将BaCO3、TiO2、La2O3、SrCO3、Na2CO3、ZrO2按照摩尔比为2：4：1：2：1：4进行称料。
(2)把称好的原料粉末使用行星式球磨机进行球磨，转速为300rpm，球磨时间为15h；球磨介质为无水乙醇、ZrO2球，其中球:料:无水乙醇的质量比为3:1:3；干燥的温度为80℃，干燥时间为18h；然后将干燥后的混合粉末进行煅烧，煅烧过程为以10℃/min的升温速率将温度从室温升温至700℃，保温2h。
(3)将得到的混合粉末二次球磨、干燥、研磨，二次球磨、干燥的具体方法与步骤(2)相同，只是球磨时间为6h。
(4)在二次球磨得到的混合粉末加入适量(1g/滴)的8wt.％的聚乙烯醇(PVA)作粘结剂，混合均匀，然后取2g粉末置于模具内，在280MPa的单轴压力下保压5-8min，压制成直径为18mm的圆片坯体。
(5)将压制好的坯体放入氧化铝小坩埚中，在坯体下方垫一层与其成分相同的混合粉末，并在坯体上方覆盖一层同样的粉末，稍稍压实粉末，然后将小坩埚放置于大坩埚内，一起置于高温箱式电阻炉内进行烧结。烧结过程为以10℃/min的升温速率将温度从室温升温至500℃，保温2h，然后以10℃/min的升温速率将温度升至1000℃，再以5℃/min的升温速率将温度升至1400℃，最后以3℃/min的升温速率升温至1500℃，保温10h后，随炉冷却至室温，得到(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Zr0.5)O3高熵陶瓷。
实施例3
一种钙钛矿结构高熵介电陶瓷(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Hf0.5)O3制备方法，具体步骤如下：
(1)将BaCO3、TiO2、La2O3、SrCO3、Na2CO3、HfO2按照摩尔比为2：4：1：2：1：4进行称料。
(2)把称好的原料粉末使用行星式球磨机进行球磨，转速为300rpm，球磨时间为12h；球磨介质为无水乙醇、ZrO2球，其中球:料:无水乙醇的质量比为3:1:3；干燥的温度为100℃，干燥时间为12h。然后将干燥后的混合粉末进行煅烧，煅烧过程为以10℃/min的升温速率将温度从室温升温至700℃，保温2h。
(3)将得到的混合粉末二次球磨、干燥、研磨，二次球磨、干燥的具体方法与步骤(2)相同，只是球磨时间为6h。
(4)在二次球磨得到的混合粉末加入适量(1g/滴)的8wt.％的聚乙烯醇(PVA)作粘结剂，混合均匀，然后取2g粉末置于模具内，在280MPa的单轴压力下保压5-8min，压制成直径为18mm的圆片坯体。
(5)将压制好的坯体放入氧化铝小坩埚中，在坯体下方垫一层与其成分相同的混合粉末，并在坯体上方覆盖一层同样的粉末，稍稍压实粉末，然后将小坩埚放置于大坩埚内，一起置于高温箱式电阻炉内进行烧结。烧结过程为以10℃/min的升温速率将温度从室温升温至500℃，保温2h，然后以10℃/min的升温速率将温度升至1000℃，再以5℃/min的升温速率将温度升至1400℃，最后以3℃/min的升温速率升温至1500℃，保温10h后，随炉冷却至室温，得到(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Hf0.5)O3高熵陶瓷。
图1本发明实施例1～3制备的(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Me0.5)O3(Me＝Sn,Zr,Hf)高熵陶瓷烧结后的XRD图谱，由图谱中可以清楚看出，实施例1～3制备的高熵陶瓷都能形成单相固溶体，没有检测到其他杂相，均为单一的钙钛矿结构。
图2为实施实例1～3制备的(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Me0.5)O3(Me＝Sn,Zr,Hf)高熵陶瓷烧结后的EDS图谱，从图中可以知道，实施例1～3制备的陶瓷的所有元素都均匀地分布在样品中，无元素偏析现象。
图3为实施实例1～3制备的(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Me0.5)O3(Me＝Sn,Zr,Hf)高熵陶瓷烧结后的介电温谱图，由图3可知，(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Me0.5)O3高熵陶瓷表现出频率色散现象，存在一定的弛豫行为，并且温度稳定性很好。
图4为实施实例1～3制备的(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Me0.5)O3(Me＝Sn,Zr,Hf)高熵陶瓷烧结后的电滞回线图，由图4中陶瓷的电滞回线可知，(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Me0.5)O3(Me＝Sn,Zr,Hf)的击穿场强大，都大于BaTiO3的击穿场强；并且储能效率高，均大于80％。
Claims (8)
1.一种钙钛矿结构高熵介电陶瓷，其特征在于，所述钙钛矿结构高熵介电陶瓷为：(La0.25Sr0.25Ba0.25Na0.25)(Ti0.5Me0.5)O3，其中Me＝Sn,Zr,Hf。
2.权利要求1所述钙钛矿结构高熵介电陶瓷的制备方法，其特征在于，具体包括以下步骤：
(1)按照化学计量比称取BaCO3、TiO2、La2O3、SrCO3、Na2CO3，并且在SnO2、ZrO2和HfO2三种原料中任意称量一种；
(2)将步骤(1)称取的原料采用湿法球磨，经过干燥、研磨、煅烧后得到混合粉末；
(3)将得到的混合粉末二次球磨、干燥、研磨；
(4)将步骤(3)二次球磨得到的混合粉末加入聚乙烯醇混合均匀，然后放置于模具内，压制成陶瓷坯体；
(5)采用埋烧的方式将陶瓷坯体放置在双层氧化铝坩埚内，置于高温箱式电阻炉内，在空气气氛下烧结，得到钙钛矿结构高熵介电陶瓷。
3.根据权利要求2所述钙钛矿结构高熵介电陶瓷的制备方法，其特征在于：BaCO3、TiO2、La2O3、SrCO3、Na2CO3、SnO2、ZrO2和HfO2的纯度≥99％。
4.根据权利要求2所述钙钛矿结构高熵介电陶瓷的制备方法，其特征在于：步骤(2)中球磨的条件为：球磨转速300rpm，球磨时间为12-18h；球磨介质为无水乙醇、ZrO2球，球:料:无水乙醇的质量比为3:1:3，干燥的温度为70-100℃，干燥时间为12-24h。
5.根据权利要求2所述钙钛矿结构高熵介电陶瓷的制备方法，其特征在于：步骤(2)中煅烧的条件为：在马弗炉中以10℃/min的升温速率将温度从室温升温到700℃下保温2h。
6.根据权利要求2所述钙钛矿结构高熵介电陶瓷的制备方法，其特征在于：步骤(3)中二次球磨的条件为：球磨转速300rpm，球磨时间为6h；球磨介质为无水乙醇、ZrO2球，球:料:乙醇的质量比为3:1:3，干燥的温度为70-100℃，干燥时间为12-24h。
7.根据权利要求2所述钙钛矿结构高熵介电陶瓷的制备方法，其特征在于：步骤(4)中聚乙烯醇的质量百分比浓度为8wt.％，加入量为每1g混合粉末中加入1滴；压制成形条件为：采用粉末单轴压片机进行压片，其中单轴压力为280MPa，保压时间为5-8min。
8.根据权利要求2所述钙钛矿结构高熵介电陶瓷的制备方法，其特征在于：步骤(5)中烧结的条件为：在小坩埚底部垫一层与陶瓷坯体成分相同的混合粉末，将陶瓷坯体放置在粉末上方，再在坯体上覆盖一层同样的混合粉末，压实，盖上小坩埚盖，再将小坩埚放置在带盖密封的大坩埚内，置于高温箱式电阻炉进行烧结，以10℃/min的升温速率将温度从室温升温至500℃，保温2h，然后以10℃/min的升温速率将温度升至1000℃，再以5℃/min的升温速率将温度升至1400℃，最后以3℃/min的升温速率升温至1500℃，保温10h后，随炉冷却至室温后得到该钙钛矿结构高熵介电陶瓷。
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| CN116003106B (zh) * | 2023-01-09 | 2024-02-23 | 东北大学秦皇岛分校 | 一种高介电纯相高熵氧化物材料及其制备方法 |
| CN116924796A (zh) * | 2023-08-14 | 2023-10-24 | 昆明理工大学 | 一种abo3型低介电损耗陶瓷及其制备方法 |
| CN116924796B (zh) * | 2023-08-14 | 2024-05-14 | 昆明理工大学 | 一种abo3型低介电损耗陶瓷及其制备方法 |
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