CN114874004A - 一种高熵六角铁氧体陶瓷及其制备方法 - Google Patents

一种高熵六角铁氧体陶瓷及其制备方法 Download PDF

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CN114874004A
CN114874004A CN202210471214.1A CN202210471214A CN114874004A CN 114874004 A CN114874004 A CN 114874004A CN 202210471214 A CN202210471214 A CN 202210471214A CN 114874004 A CN114874004 A CN 114874004A
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段东平
干科
张晓冬
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Abstract

本发明公开一种高熵六角铁氧体陶瓷及其制备方法，属于无机非金属功能陶瓷技术领域，六角铁氧体经高熵化后的力学性能可获得明显提升。本发明采用SrCO3、BaCO3、MgO、Al2O3、TiO2、Cr2O3、MnO2、Fe2O3、CoO、Ni2O3、CuO、ZnO粉体作为原料，依据磁铅石AB12O19的晶体结构制备高熵六角铁氧体陶瓷。其中，Sr和Ba元素位于晶体结构中的A位，Mg、Al、Ti、Cr、Mn、Fe、Co、Ni、Cu、Zn元素位于晶体结构中的B位。所述高熵六角铁氧体陶瓷具有单相磁铅石结构，陶瓷内部各元素分布均匀，无明显团聚现象。采用高熵组分设计的六角铁氧体陶瓷，其抗弯强度最高可达285.2±0.4MPa，明显优于传统铁氧体陶瓷，使其更适合规模化工业生产，更适用于大尺寸、复杂形状磁性材料领域，可以减少生产和使用过程中因磕碰、跌落等因素导致的产品破损和毁坏。

Description

一种高熵六角铁氧体陶瓷及其制备方法
技术领域
本发明涉及无机非金属功能陶瓷技术领域，特别涉及一种力学性能增强的 高熵六角铁氧体陶瓷及其制备方法。
背景技术
高熵工程是近年来出现的新材料设计理念，其概念由高熵合金发展而来。 2004年,Cantor和叶均蔚教授同时报道了单相面心立方结构CrMnFeCoNi等体系 多主元合金，并正式把这种将多种合金元素以近等原子比固溶到一起，形成单 相的材料设计概念定义为高熵合金。随后，高熵的概念逐渐拓展到其它材料中。
高熵陶瓷最早由2015年Rost等人合作报道，将5种氧化物混合均匀加热即 可形成单相(MgNiCoCuZn)O岩盐结构熵稳定氧化物，并得出了高构型熵有利于 单相形成的结论。随后，迅速扩展至萤石结构、钙钛矿结构、尖晶石结构等氧 化物，以及硼化物、碳化物、氮化物、硅化物等非氧化物。
高熵铁氧体陶瓷由2018年Dabrowa等人首先报道，为尖晶石结构 (CrMnFeCoNi)3O4体系，他们证明了较高的混合熵(≥1.61R)会使经过多元素混 合后的铁氧体稳定存在。之后，Dabrowa等人又对(DyGdHoY,X)3Fe5O12为基础 体系的石榴石型高熵铁氧体展开研究，发现该体系不仅具有良好的稳定性，低 温下还具有比钇铁石榴石更高的电导活化能。国内针对高熵铁氧体的研究，有 冒爱琴等人研究的(AlCrMnFeCoNi)3O4六元高熵体系；以及李明亚等人研究的 (CoZnFeMnNi)3O4五元高熵体系。这两种体系均为凝胶法制备的高熵尖晶石粉体，并且都以报道高熵组分和磁学性能为主要内容。
由于研究时间较短，目前针对高熵铁氧体的研究还不够深入，仍处于高熵 组分探索阶段。尤其是高熵六角铁氧体，仅有Vinnik等人采用高温固相反应烧 结得到了磁铅石结构Ba(Fe6Ti1.2Co1.2In1.2Ga1.2Cr1.2)O19等组分的高熵单相产物；他 们的研究证明了高熵磁铅石结构是能够获得的，并具有一定的磁学性能。除此 之外，还未见其他相关研究报道。
目前，针对高熵磁铅石型六角铁氧体研究的报道还很少，关于高熵六角铁 氧体陶瓷也还未见到相关专利。
此外，当前市场应用的六角铁氧体主要以钡铁氧体和锶铁氧体为基础；六 角铁氧体作为永磁体，因其原材料来源丰富、电阻率高、矫顽力大、制备工艺 简单且成本低，可用来制造磁分离器、磁推轴承、扬声器、微波器件等，被广 泛用于轨道交通、新能源、电动汽车等领域。然而，作为研究最深入、应用最 广泛的磁性材料之一，对铁氧体陶瓷电磁学性能的研究不胜枚举；针对其力学 性能的关注比较少见。相比Al2O3、ZrO2等结构陶瓷，铁氧体陶瓷质地更脆、易 碎，不耐冲击震动，稳定性不高。随着时代飞速发展，市场对铁氧体陶瓷的综合性能也提出了更高的要求，使用环境也愈发苛刻。在保证良好电磁学性能的 前提下，还需具有良好的力学性能。优异的力学性能可以提高产品的成品率， 提升极端条件下使用的可靠性，避免跌落和碰撞造成的损坏；同时，铁氧体元 件在制造过程中圆磨、切片、打孔等精密加工过程，也需要良好的机械性能进 行保障；尤其是在特殊领域(如离子加速器中的大型装置等)的大尺寸、复杂 形状铁氧体部件制造，更是需要铁氧体具有较高的力学性能。优异的力学性能 不仅能够拓宽铁氧体的应用范围，还可以提升其可靠性和使用寿命。但是，由 于铁氧体本征强度低，通过外部工艺条件提升力学性能的效果并不显著，当前 尚未见到抗弯强度高于200MPa的六角铁氧体陶瓷的研究报道。如何提升铁氧体 的本征力学性能，是需要重点关注的研究方向之一。
因此，本发明通过熵工程，构建了含Mg、Al等非磁性元素的高熵组分，大 幅提升铁氧体陶瓷的本征力学性能，获得抗弯强度远高于当前市场六角铁氧体 陶瓷的高熵六角铁氧体。
发明内容
因此，为了扩大高熵工程在陶瓷领域的研究和应用范围，克服现有铁氧体 陶瓷力学性能低的不足，本发明提出一种高熵六角铁氧体陶瓷及其制备方法。 本发明提出的高熵磁铅石型六角铁氧体陶瓷的化学组成为： (SrxBa1-x)(Mg(0～1/5)Al(1/7～1/5)Ti(0～1/5)Cr(0～1/5)Mn(0～1/5)Co(0～1/5)Ni(0～1/5)Cu(0～1/5)Zn(0～1/5)Fe(1/7～1/5))12O19，其中x的取值范围为0≤x≤1。
所述一种高熵六角铁氧体陶瓷及其制备方法，高熵六角铁氧体的化学式可 以写作： (SrxBa1-x)(Mg(0～1/5)Al(1/7～1/5)Ti(0～1/5)Cr(0～1/5)Mn(0～1/5)Co(0～1/5)Ni(0～1/5)Cu(0～1/5)Zn(0～1/5)Fe(1/7～1/5))12O19，其中x的取值范围为0≤x≤1。
所述高熵六角铁氧体陶瓷的制备原料为SrCO3、BaCO3、MgO、Al2O3、TiO2、 Cr2O3、MnO2、Fe2O3、CoO、Ni2O3、CuO、ZnO粉体，纯度＞95％，粒径0.05μm ～5μm。
所述一种高熵六角铁氧体陶瓷及其制备方法，具体步骤如下：
步骤1，依据高熵组分设计称量粉体，以适量酒精作为溶剂，以氧化锆研磨 球作为球磨介质，与粉体混合置于聚四氟乙烯球磨罐中球磨，球磨后的浆料经 干燥获得混合粉体。
步骤2，将干燥后的混合粉体过筛、造粒，取一定粒径范围的粉体，放入模 具中压制成片，获得铁氧体陶瓷坯体。
步骤3，将铁氧体陶瓷坯体在空气气氛下高温烧结，获得高熵铁氧体陶瓷。
所述一种高熵六角铁氧体陶瓷及其制备方法，高熵组分设计按照化学式中 的原子比例进行设定。
所述一种高熵六角铁氧体陶瓷及其制备方法，酒精与粉体的质量比为：2≤ 酒精/粉体≤10。
所述一种高熵六角铁氧体陶瓷及其制备方法，氧化锆研磨球直径为 3mm～15mm，研磨球与粉体的质量比为：1≤研磨球/粉体≤3。
所述一种高熵六角铁氧体陶瓷及其制备方法，球磨为行星式球磨或滚筒球 磨，球磨转速为300rpm～600rpm，球磨时间为6小时～24小时；干燥温度为 60℃～100℃，干燥时间为12小时～72小时。
所述一种高熵六角铁氧体陶瓷及其制备方法，混合粉体造粒后取 50μm～500μm的微粉。
所述一种高熵六角铁氧体陶瓷及其制备方法，压片机制片的压力范围为30 MPa～80MPa。
所述一种高熵六角铁氧体陶瓷及其制备方法，烧成温度为1250℃～1550℃， 升温速率为3℃/min～10℃/min，保温时间为1小时～6小时。
附图说明
按照实施例1～6获得的高熵六角铁氧体陶瓷，其磁学性能和力学性能列于 表1。图1是按照实施例1～4获得的高熵六角铁氧体陶瓷的物相组成以及实施例 1粉体烧结前的X射线衍射图谱，可以看到烧结前粉体物相组成混乱，而烧结 后的样品均为磁铅石相。图2是按照实施例1获得的高熵六角铁氧体 Sr(Mg1/5Al1/5Ti1/5Cr1/5Fe1/5)12O19陶瓷内部微观组织形貌，可以看到各元素分布均 匀，无明显分相；图3是高熵六角铁氧体Sr(Mg1/5Al1/5Ti1/ 5Cr1/5Fe1/5)12O19的坯体右)与陶瓷(左)样品宏观照片，可以看到烧结样品发生了明显的收缩；图4 是高熵六角铁氧体Sr(Mg1/5Al1/5Ti1/5Cr1/5Fe1/5)12O19陶瓷的磁学性能，具体参数在表1中体现。
具体实施方式
提供下述实施例是为了更好地进一步理解本发明，并不局限于所述最佳实 施方式，不对本发明的内容和保护范围构成限制，任何人在本发明的启示下或 是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近 似的产品，均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者，按照本领域内的文献所描述的常规 实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者，均为可 以通过市购获得的常规试剂产品。
实施实例1.
高熵六角铁氧体陶瓷Sr(Mg1/5Al1/5Ti1/5Cr1/5Fe1/5)12O19的制备。
将15.83克SrCO3、10.37克MgO、13.12克Al2O3、20.55克TiO2、19.56克 Cr2O3、20.55克Fe2O3与400克酒精混合，以300rpm转速球磨12小时，球磨后 的粉体在80℃干燥24小时。将干燥后的混合粉体造粒、过筛，取50μm～200μm 的微粉，放入压片机中，以30MPa的压力制成坯体。将铁氧体坯体在空气下以 8℃/min的升温速率升温至1300℃，保温2个小时后随炉降温，即可得到高熵 六角铁氧体Sr(Mg1/5Al1/5Ti1/5Cr1/5Fe1/5)12O19陶瓷。
实施实例2.
高熵六角铁氧体陶瓷Ba(Mg1/5Al1/5Ti1/5Cr1/5Fe1/5)12O19的制备。
将21.16克BaCO3、10.37克MgO、13.12克Al2O3、20.55克TiO2、19.56 克Cr2O3、20.55克Fe2O3与400克酒精混合，以450rpm转速球磨12小时，球 磨后的粉体在80℃干燥24小时。将干燥后的混合粉体造粒、过筛，取 100μm～250μm的微粉，放入压片机中，以40MPa的压力制成坯体。将铁氧体 坯体在空气下以8℃/min的升温速率升温至1350℃，保温2个小时后随炉降温， 即可得到高熵六角铁氧体Ba(Mg1/5Al1/5Ti1/5Cr1/5Fe1/5)12O19陶瓷。
实施实例3.
高熵六角铁氧体陶瓷Sr0.5Ba0.5(Mg1/5Al1/5Ti1/5Cr1/5Fe1/5)12O19的制备。
将7.92克SrCO3、10.58克BaCO3、10.37克MgO、13.12克Al2O3、20.55 克TiO2、19.56克Cr2O3、20.55克Fe2O3与500克酒精混合，以400rpm转速球 磨18小时，球磨后的粉体在80℃干燥24小时。将干燥后的混合粉体造粒、过 筛，取50μm～250μm的微粉，放入压片机中，以50MPa的压力制成坯体。将铁 氧体坯体在空气下以5℃/min的升温速率升温至1400℃，保温2个小时后随炉 降温,即可得到高熵六角铁氧体Sr0.5Ba0.5(Mg1/5Al1/5Ti1/5Cr1/5Fe1/5)12O19陶瓷。
实施实例4.
高熵六角铁氧体陶瓷Sr(Mg1/6Al1/6Cr1/6Mn1/6Fe1/6Zn1/6)12O19的制备。
将15.83克SrCO3、8.062克MgO、10.20克Al2O3、15.2克Cr2O3、17.392 克MnO2、15.97克Fe2O3、16.282克ZnO与500克酒精混合，以500rpm转速球 磨18小时，球磨后的粉体在100℃干燥6小时。将干燥后的混合粉体造粒、过 筛，取150μm～300μm的微粉，放入压片机中，以50MPa的压力制成坯体。将 铁氧体坯体在空气下以5℃/min的升温速率升温至1500℃，保温4个小时后随 炉降温，即可得到高熵六角铁氧体Sr(Mg1/6Al1/6Cr1/6Mn1/6Fe1/6Zn1/6)12O19陶瓷。
实施实例5.
高熵六角铁氧体陶瓷Sr(Al1/7Ti1/7Cr1/7Mn1/7Co1/7Ni1/7Fe1/7)12O19的制备。
将15.83克SrCO3、8.74克Al2O3、13.69克TiO2、13.03克Cr2O3、14.91克 MnO2、12.85克CoO、14.18克Ni2O3、13.69克Fe2O3与600克酒精混合，以550rpm 转速球磨24小时，球磨后的粉体在70℃干燥24小时。将干燥后的混合粉体造 粒、过筛，取50μm～100μm的微粉，放入压片机中，以60MPa的压力制成坯体。 将铁氧体坯体在空气下以3℃/min的升温速率升温至1250℃，保温2个小时后 随炉降温，即可得到高熵六角铁氧体Sr(Al1/7Ti1/7Cr1/7Mn1/7Fe1/ 7Ni1/7Fe1/7)12O19陶 瓷。
实施实例6.
高熵六角铁氧体陶瓷Ba(Mg1/5Al1/5Cr1/5Fe1/5Cu1/5)12O19的制备。
将21.16克BaCO3、10.37克MgO、13.12克Al2O3、19.09克CuO、19.56 克Cr2O3、20.55克Fe2O3与600克酒精混合，以600rpm转速球磨6小时，球磨 后的粉体在90℃干燥12小时。将干燥后的混合粉体造粒、过筛，取300μm～500μm 的微粉，放入压片机中，以55MPa的压力制成坯体。将铁氧体坯体在空气下以 10℃/min的升温速率升温至1380℃，保温3个小时后随炉降温，即可得到高熵 六角铁氧体Ba(Mg1/5Al1/5Cr1/5Fe1/5Cu1/5)12O19陶瓷。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的 限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其 它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举，而由 此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
表1实施例1～6获得的高熵六角铁氧体陶瓷的综合性能
Figure BDA0003622487110000081

Claims (10)

1.一种高熵六角铁氧体陶瓷及其制备方法，其特征在于，高熵六角铁氧体的化学式可以写作：
(SrxBa1-x)(Mg(0～1/5)Al(1/7～1/5)Ti(0～1/5)Cr(0～1/5)Mn(0～1/5)Co(0～1/5)Ni(0～1/5)Cu(0～1/5)Zn(0～1/5)Fe(1/7～1/5))12O19，其中x的取值范围为0≤x≤1。
2.根据权利要求1所述，一种高熵六角铁氧体陶瓷及其制备方法，其特征在于：制备高熵六角铁氧体的原料为SrCO3、BaCO3、MgO、Al2O3、TiO2、Cr2O3、MnO2、Fe2O3、CoO、Ni2O3、CuO、ZnO粉体，纯度＞95％，粒径0.05μm～5μm。
3.根据权利要求2所述，一种高熵六角铁氧体陶瓷及其制备方法，其特征在于：
具体步骤如下
步骤1，依据高熵组分设计称量粉体，以适量酒精作为溶剂，以氧化锆研磨球作为球磨介质，与粉体混合置于聚四氟乙烯球磨罐中球磨，球磨后的浆料经干燥获得混合粉体。
步骤2，将干燥后的混合粉体过筛、造粒，取一定粒径范围的粉体，放入模具中压制成片，获得铁氧体陶瓷坯体。
步骤3，将铁氧体陶瓷坯体在空气气氛下高温烧结，获得高熵铁氧体陶瓷。
4.根据权利要求2所述的方法，其特征在于：所述高熵组分设计按照化学式中的原子比例进行设定。
5.根据权利要求2所述的方法，其特征在于：所述适量酒精与粉体的质量比为：2≤酒精/粉体≤10。
6.根据权利要求2所述的方法，其特征在于：所述氧化锆研磨球直径为3mm～15mm，研磨球与粉体的质量比为：1≤研磨球/粉体≤3。
7.根据权利要求2所述的方法，其特征在于：球磨为行星式球磨或滚筒球磨，球磨转速为300rpm～600rpm，球磨时间为6小时～24小时；干燥温度为60℃～100℃，干燥时间为12小时～72小时。
8.根据权利要求2所述的方法，其特征在于：混合粉体造粒后取50μm～500μm微粉。
9.根据权利要求2所述的方法，其特征在于：压片机制片的压力范围为30MPa～80MPa。
10.根据权利要求2所述的方法，其特征在于：烧成温度为1250℃～1550℃，升温速率为3℃/min～10℃/min，保温时间为1小时～6小时。
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CN118495937A (zh) * 2024-05-09 2024-08-16 太原理工大学 一种高熵磁铅石型钡铁氧体陶瓷及其制备方法

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