CN117567145A - 一种具有尖晶石结构的磁性高熵陶瓷及其制备方法 - Google Patents

一种具有尖晶石结构的磁性高熵陶瓷及其制备方法 Download PDF

Info

Publication number
CN117567145A
CN117567145A CN202311562938.8A CN202311562938A CN117567145A CN 117567145 A CN117567145 A CN 117567145A CN 202311562938 A CN202311562938 A CN 202311562938A CN 117567145 A CN117567145 A CN 117567145A
Authority
CN
China
Prior art keywords
entropy ceramic
magnetic high
spinel structure
entropy
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202311562938.8A
Other languages
English (en)
Inventor
杨玉杰
陈丛亮
张英明
陈冬阳
李�浩
张振宇
孟雨亭
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui University
Original Assignee
Anhui University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anhui University filed Critical Anhui University
Priority to CN202311562938.8A priority Critical patent/CN117567145A/zh
Publication of CN117567145A publication Critical patent/CN117567145A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/2608—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead
    • C04B35/2625—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead containing magnesium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/265—Compositions containing one or more ferrites of the group comprising manganese or zinc and one or more ferrites of the group comprising nickel, copper or cobalt
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3241—Chromium oxides, chromates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Magnetic Ceramics (AREA)

Abstract

本发明提供一种具有尖晶石结构的磁性高熵陶瓷及其制备方法，涉及磁性材料技术领域。所述具有尖晶石结构的磁性高熵陶瓷的化学式为CoFe(Ti0.2Cr0.2Mn0.2Al0.2Me0.2)O4，Me表示+2价的金属元素，且制备方法为将称量过的药品球磨后经过两次无压烧结，制备出目标的磁性高熵陶瓷。本发明克服了现有技术的不足，在常见的高熵尖晶石材料成分设计思路上做出了创新，且整体制备具有周期短、安全、高效、经济操作简单、等特点，且根据本发明获得的高熵尖晶石材料在磁学领域有良好的应用前景，并且为设计高熵材料提供了新思路。

Description

一种具有尖晶石结构的磁性高熵陶瓷及其制备方法
技术领域
本发明涉及陶瓷材料技术领域，具体涉及一种具有尖晶石结构的磁性高熵陶瓷及其制备方法。
背景技术
近年来，熵稳定氧化物领域发展迅速。在熵稳定材料中，构型熵(S构型)对吉布斯自由能的贡献驱动熵稳定的氧化物成为单相固态溶液。这种高构型熵主要来自于元素的无序排序。一般来说，当5个具有等摩尔比的金属阳离子同时占据一个或多个威考夫位点(Sconfiguration＝1.61R)时，这种氧化物被称为高熵氧化物(HEOs)。熵对材料的稳定性有很大的影响，因此HEOs可以包含更多的元素。由于其灵活的组成，这些材料可以提供一些惊人的性能。综上所述，HEOs的性质可以通过选择不同阳离子的组合来调整不同的结构。Rost等人于2015年首次报道了通过固态反应合成的单相HEOs。与传统的氧化物相比，HEOs具有复杂的元素组成和有趣的物理和化学性质。因此，HEOs在光学、磁性、催化、储能和电学等领域引起了人们的关注。然而在HEOs领域中缺乏关于新高熵混乱机制的设计和磁性能的研究。
基于上述研究基础，本单位对具有尖晶石结构的磁性高熵陶瓷进行进一步的研究，并且在前授权了CN115594497A公开的“一种具有尖晶石结构的高熵陶瓷及其制备方法和应用”，该项专利主要是基于四种金属元素与Zn组合，通过调节Zn的含量能够有效调整材料的磁学性能，而随着进一步的研究，这种调节方式具有局限性，在高熵陶瓷这领域需要不同的材料来获得不同的性能，即针对这一研究方向需要不同的离子设计来丰富材料选择，为理解和应用多组分功能陶瓷和HEOs提供更多可能。
发明内容
针对现有技术不足，本发明提供一种具有尖晶石结构的磁性高熵陶瓷及其制备方法，通过采用新的离子组成设计思路，合成新型的高熵材料，使得设计的磁性高熵陶瓷材料能够有效应用在磁学领域，并且保证材料的合成便捷性并降低成本。
为实现以上目的，本发明的技术方案通过以下技术方案予以实现：
一种具有尖晶石结构的磁性高熵陶瓷，所述具有尖晶石结构的磁性高熵陶瓷的化学通式为：CoFe(M)0.2O4；其中M为替换CoFe2O4中Fe的五种金属离子，且M具体为Ti、Cr、Mn、Al、Me五种原子比例为1：1：1：1的金属离子，且Me为化合价为+2的金属离子。
优选的，所述M的含量占化学式中总金属离子比例的百分之33.3333％。
具有尖晶石结构的磁性高熵陶瓷的制备方法包括以下步骤：
(1)原料处理：按照化学式中的金属离子比例取金属氧化物粉末，球磨混合成浆料，烘干后得到均匀的混合粉末；
(2)煅烧：将混合粉末放入马弗炉中进行煅烧，得到一次煅烧粉末；
(3)研磨破碎：将一次煅烧粉末置于研钵中充分破碎研磨得到预制粉料；
(4)二次煅烧：将预制粉料放入马弗炉中进行第二次煅烧，得到具有尖晶石结构的磁性高熵陶瓷粉末。
优选的，所述步骤(1)中球磨的方式具体为将金属氧化物粉末置入盛有蒸馏水的金属球磨罐中球磨，以130-330r/min的转速充分混合2-10小时。
优选的，所述步骤(2)中煅烧的方式为加热至790℃-1470℃后进行保温煅烧2-6h。
优选的，所述步骤(3)中破碎研磨国80目筛。
优选的，所述步骤(4)中煅烧的温度为800℃-1570℃，且煅烧的时间为5-20h。
优选的，所述步骤(2)和步骤(4)中煅烧的气氛均为空气气氛。
本发明提供一种具有尖晶石结构的磁性高熵陶瓷及其制备方法，与现有技术相比优点在于：
本发明采用新的离子组成设计思路，合成新型的高熵材料，且本发明提供了一种兼具经济性、高效性和便捷性的合成磁性高熵陶瓷的方法，使得本发明设计的磁性高熵陶瓷材料能够有效应用在磁学、微波吸收领域。
附图说明：
图1为本发明实施例中磁性高熵陶瓷的XRD图，其中(a)为本发明实施例1中磁性高熵陶瓷的XRD图；(b)为本发明实施例2磁性高熵陶瓷的XRD图；(c)为本发明实施例3磁性高熵陶瓷的XRD图；(d)为本发明实施例4磁性高熵陶瓷的XRD图；(e)为本发明实施例5磁性高熵陶瓷的XRD图；
图2为本发明实施例1的高熵陶瓷的SEM图；
图3为本发明实施例1的高熵陶瓷的M-H图；
图4为本发明实施例2的高熵陶瓷的SEM图；
图5为本发明实施例2的高熵陶瓷的M-H图；
图6为本发明实施例3的高熵陶瓷的SEM图；
图7为本发明实施例3的高熵陶瓷的M-H图；
图8为本发明实施例4的高熵陶瓷的SEM图；
图9为本发明实施例4的高熵陶瓷的M-H图；
图10为本发明实施例5的高熵陶瓷的SEM图；
图11为本发明实施例5的高熵陶瓷的M-H图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面结合本发明实施例对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1：
制备化学式为CoFe(Ti0.2Cr0.2Mn0.2Al0.2Mg0.2)O4的磁性高熵陶瓷：
(1)选取Co3O4、Fe2O3、TiO2、Cr2O3、Mn3O4、Al2O3、MgO为原始粉末，将上述原始粉末按化学式中的比例称量，以球磨罐为容器，将其分散于100ml蒸馏水中。
(2)在球磨罐中加入钢球进行球磨；以230r/min的转速充分混合3小时，将其烘干后获得球磨料。
(3)将上述球磨料在空气气氛中加热至950℃进行一次煅烧，热处理时间为2小时。
(4)将上述煅烧后的粉末取出后用研钵破碎，将破碎后的粉末过80目筛网后获得预制料。
(5)将上述预制料重新置入马弗炉，在空气气氛中升温至1180℃，保温时间为10小时，取出破碎后得到所述磁性高熵陶瓷。
实施例2：
制备化学式为CoFe(Ti0.2Cr0.2Mn0.2Al0.2Fe0.2)O4的磁性高熵陶瓷：
(1)选取Co3O4、Fe2O3、TiO2、Cr2O3、Mn3O4、Al2O3、Fe2O3为原始粉末，将上述原始粉末按化学式中的比例称量，以球磨罐为容器，将其分散于100ml蒸馏水中。
(2)在球磨罐中加入钢球进行球磨；以230r/min的转速充分混合3小时，将其烘干后获得球磨料。
(3)将上述球磨料在空气气氛中加热至950℃进行一次煅烧，热处理时间为2小时。
(4)将上述煅烧后的粉末取出后用研钵破碎，将破碎后的粉末过80目筛网后获得预制料。
(5)将上述预制料重新置入马弗炉，在空气气氛中升温至1180℃，保温时间为10小时，取出破碎后得到所述磁性高熵陶瓷。
实施例3：
制备化学式为CoFe(Ti0.2Cr0.2Mn0.2Al0.2Ni0.2)O4的磁性高熵陶瓷：
(1)选取Co3O4、Fe2O3、TiO2、Cr2O3、Mn3O4、Al2O3、NiO为原始粉末，将上述原始粉末按化学式中的比例称量，以球磨罐为容器，将其分散于100ml蒸馏水中。
(2)在球磨罐中加入钢球进行球磨；以230r/min的转速充分混合3小时，将其烘干后获得球磨料。
(3)将上述球磨料在空气气氛中加热至950℃进行一次煅烧，热处理时间为2小时。
(4)将上述煅烧后的粉末取出后用研钵破碎，将破碎后的粉末过80目筛网后获得预制料。
(5)将上述预制料重新置入马弗炉，在空气气氛中升温至1180℃，保温时间为10小时，取出破碎后得到所述磁性高熵陶瓷。
实施例4：
制备化学式为CoFe(Ti0.2Cr0.2Mn0.2Al0.2Cu0.2)O4的磁性高熵陶瓷：
(1)选取Co3O4、Fe2O3、TiO2、Cr2O3、Mn3O4、Al2O3、CuO为原始粉末，将上述原始粉末按化学式中的比例称量，以球磨罐为容器，将其分散于100ml蒸馏水中。
(2)在球磨罐中加入钢球进行球磨；以230r/min的转速充分混合3小时，将其烘干后获得球磨料。
(3)将上述球磨料在空气气氛中加热至950℃进行一次煅烧，热处理时间为2小时。
(4)将上述煅烧后的粉末取出后用研钵破碎，将破碎后的粉末过80目筛网后获得预制料。
(5)将上述预制料重新置入马弗炉，在空气气氛中升温至1180℃，保温时间为10小时，取出破碎后得到所述磁性高熵陶瓷。
实施例5：
制备化学式为CoFe(Ti0.2Cr0.2Mn0.2Al0.2Zn0.2)O4的磁性高熵陶瓷：
(1)选取Co3O4、Fe2O3、TiO2、Cr2O3、Mn3O4、Al2O3、ZnO为原始粉末，将上述原始粉末按化学式中的比例称量，以球磨罐为容器，将其分散于100ml蒸馏水中。
(2)在球磨罐中加入钢球进行球磨；以230r/min的转速充分混合3小时，将其烘干后获得球磨料。
(3)将上述球磨料在空气气氛中加热至790℃-1470℃进行一次煅烧，热处理时间为2小时。
(4)将上述煅烧后的粉末取出后用研钵破碎，将破碎后的粉末过80目筛网后获得预制料。
(5)将上述预制料重新置入马弗炉，在空气气氛中升温至1180℃，保温时间为10小时，取出破碎后得到所述磁性高熵陶瓷。
检测：
1、物相检测：
通过X射线衍射(XRD)分析上述实施例1-5制备的磁性高熵陶瓷的物相，结果如图1所示：图1中(a)为实施例1的磁性高熵陶瓷样品的XRD谱图，(b)为实施例2的磁性高熵陶瓷样品的XRD谱图，(c)为实施例3的磁性高熵陶瓷样品的XRD谱图，(d)为实施例4的磁性高熵陶瓷样品的XRD谱图，(e)为实施例5的磁性高熵陶瓷样品的XRD谱图。由图1中的XRD测试结果可知上述实施例1-5均具有尖晶石结构(Fd3_m)。
2、形貌检测：
使用扫描电子显微镜观察上述实施例1-5所制得的磁性高熵陶瓷样品的形貌，具体实施例1的磁性高熵陶瓷样品的形貌如图2所示，实施例2的磁性高熵陶瓷样品的形貌如图4所示，实施例3的磁性高熵陶瓷样品的形貌如图6所示，实施例4的磁性高熵陶瓷样品的形貌如图8所示，实施例5的磁性高熵陶瓷样品的形貌如图10所示。
其中大多数烧结粉末是紧密连接的多面体粒子。平均粒径随Me阳离子的取代而波动。
3、磁性能检测：
使用振动样品磁强计测量上述实施例1-5所制得的磁性高熵陶瓷样品的磁性能：其中图3、图5、图7、图9、图11分别为实施例1、实施例2、实施例3、实施例4、实施例5磁性高熵陶瓷样品的M-H图，具体磁学性能测量性能如下表所示：
以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。

Claims (8)

1.一种具有尖晶石结构的磁性高熵陶瓷，其特征在于，所述具有尖晶石结构的磁性高熵陶瓷的化学通式为：CoFe(M)0.2O4；其中M为替换CoFe2O4中Fe的五种金属离子，且M具体为Ti、Cr、Mn、Al、Me五种原子比例为1：1：1：1的金属离子，且Me为化合价为+2的金属离子。
2.根据权利要求1所述的一种具有尖晶石结构的磁性高熵陶瓷，其特征在于：所述M的含量占化学式中总金属离子比例的百分之33.3333％。
3.一种如权利1或2任一所述具有尖晶石结构的磁性高熵陶瓷的制备方法，其特征在于，制备方法包括以下步骤：
(1)原料处理：按照化学式中的金属离子比例取金属氧化物粉末，球磨混合成浆料，烘干后得到均匀的混合粉末；
(2)煅烧：将混合粉末放入马弗炉中进行煅烧，得到一次煅烧粉末；
(3)研磨破碎：将一次煅烧粉末置于研钵中充分破碎研磨得到预制粉料；
(4)二次煅烧：将预制粉料放入马弗炉中进行第二次煅烧，得到具有尖晶石结构的磁性高熵陶瓷粉末。
4.根据权利要求3所述的一种具有尖晶石结构的磁性高熵陶瓷的制备方法，其特征在于：所述步骤(1)中球磨的方式具体为将金属氧化物粉末置入盛有蒸馏水的金属球磨罐中球磨，以130-330r/min的转速充分混合2-10小时。
5.根据权利要求3所述的一种具有尖晶石结构的磁性高熵陶瓷的制备方法，其特征在于：所述步骤(2)中煅烧的方式为加热至790℃-1470℃后进行保温煅烧2-6h。
6.根据权利要求3所述的一种具有尖晶石结构的磁性高熵陶瓷的制备方法，其特征在于：所述步骤(3)中破碎研磨国80目筛。
7.根据权利要求3所述的一种具有尖晶石结构的磁性高熵陶瓷的制备方法，其特征在于：所述步骤(4)中煅烧的温度为800℃-1570℃，且煅烧的时间为5-20h。
8.根据权利要求3所述的一种具有尖晶石结构的磁性高熵陶瓷的制备方法，其特征在于：所述步骤(2)和步骤(4)中煅烧的气氛均为空气气氛。
CN202311562938.8A 2023-11-22 2023-11-22 一种具有尖晶石结构的磁性高熵陶瓷及其制备方法 Pending CN117567145A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311562938.8A CN117567145A (zh) 2023-11-22 2023-11-22 一种具有尖晶石结构的磁性高熵陶瓷及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311562938.8A CN117567145A (zh) 2023-11-22 2023-11-22 一种具有尖晶石结构的磁性高熵陶瓷及其制备方法

Publications (1)

Publication Number Publication Date
CN117567145A true CN117567145A (zh) 2024-02-20

Family

ID=89885878

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311562938.8A Pending CN117567145A (zh) 2023-11-22 2023-11-22 一种具有尖晶石结构的磁性高熵陶瓷及其制备方法

Country Status (1)

Country Link
CN (1) CN117567145A (zh)

Similar Documents

Publication Publication Date Title
CN111763087B (zh) 一系列立方萤石型高熵铈氧化物纳米粉体及其制备方法
Aczel et al. Frustration by competing interactions in the highly distorted double perovskites La 2 Na B′ O 6 (B′= Ru, Os)
CN113372108B (zh) 一种具有良好光吸收性能的高熵陶瓷材料的制备方法
CN109650876A (zh) 一种a位高熵钙钛矿氧化物及其制备方法
CN102674823A (zh) 六角晶系y型铁氧体电磁材料及其制备方法
CN111470859B (zh) 一种六元尖晶石型铁钴铬锰镁锌系高熵氧化物及其粉体制备方法
Martin de Vidales et al. Thermal behavior in air and reactivity in acid medium of cobalt manganese spinels MnxCo3-xO4 (1. ltoreq. x. ltoreq. 3) synthesized at low temperature
CN102173463A (zh) 铁基复合氧化物Ca2Fe2O5的制备方法
Wahba et al. Flower-like morphology of blue and greenish-gray ZnCoxAl2-xO4 nanopigments
JP6070454B2 (ja) フェライト化合物
Wu et al. Enhanced near-and mid-infrared radiation property of MgCr2O4 by doping with Cu ions
Kumar et al. Cation distribution in mixed Mg-Mn ferrite systems from X-ray diffraction technique and saturation magnetization
Botta et al. Two alternative synthesis routes for MnZn ferrites using mechanochemical treatments
CN117567145A (zh) 一种具有尖晶石结构的磁性高熵陶瓷及其制备方法
CN106747392A (zh) 一种Ho/Co复合掺杂Ni‑Zn铁氧体陶瓷的制备方法
CN115594497B (zh) 一种具有尖晶石结构的高熵陶瓷及其制备方法和应用
US11827569B2 (en) Yttrium aluminum garnet powder and processes for synthesizing same
WO2014084059A1 (ja) フェライト化合物
Chérif et al. Structure, magnetic properties and Mössbauer spectra of La 0.67 Sr 0.33 Fe x Mn 1− x O 3 manganites oxide prepared by mechanical ball milling method
Boudaya et al. Preparation and characterization of the spinel series Co6+ x Ni4-xMn8O24 (0≤ x≤ 4)
Amaran et al. Structural and morphology changes in PrMnO3 manganite induced by Ba (x= 0.33) doping
CN115594496B (zh) 一种具有尖晶石结构的中熵陶瓷及其制备方法
Pani et al. A correlation of lattice distortion with the magnetic properties of calcium doped bismuth ferrite thin films
KR100859418B1 (ko) 초거대 자기 저항을 갖는 망간 산화물 제조방법
Hyung et al. New perovskite related-compounds of Ru (V) in K2NiF4 type structure

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination