CN115611624B - 一种宽温高Tc高磁导率锰锌铁氧体材料及其制备方法 - Google Patents

一种宽温高Tc高磁导率锰锌铁氧体材料及其制备方法 Download PDF

Info

Publication number
CN115611624B
CN115611624B CN202211326098.0A CN202211326098A CN115611624B CN 115611624 B CN115611624 B CN 115611624B CN 202211326098 A CN202211326098 A CN 202211326098A CN 115611624 B CN115611624 B CN 115611624B
Authority
CN
China
Prior art keywords
ferrite material
temperature
manganese
equal
raw materials
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.)
Active
Application number
CN202211326098.0A
Other languages
English (en)
Other versions
CN115611624A (zh
Inventor
李明治
严迪阳
李永劬
王微达
王士杰
谈海烽
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.)
Haining Lianfeng Magnet Industry Co ltd
Original Assignee
Haining Lianfeng Magnet Industry Co ltd
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 Haining Lianfeng Magnet Industry Co ltd filed Critical Haining Lianfeng Magnet Industry Co ltd
Priority to CN202211326098.0A priority Critical patent/CN115611624B/zh
Publication of CN115611624A publication Critical patent/CN115611624A/zh
Application granted granted Critical
Publication of CN115611624B publication Critical patent/CN115611624B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C04B35/2633—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 barium, strontium or calcium
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/342—Oxides
    • H01F1/344—Ferrites, e.g. having a cubic spinel structure (X2+O)(Y23+O3), e.g. magnetite Fe3O4
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • 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
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C04B2235/3203—Lithium oxide 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
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • 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
    • C04B2235/3239—Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate
    • 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
    • C04B2235/3275—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
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates 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
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate

Landscapes

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

Abstract

本发明公开了一种宽温高Tc高磁导率锰锌铁氧体材料及其制备方法，宽温高Tc高磁导率锰锌铁氧体材料至少包括FeFe2O4、MnFe2O4、ZnFe2O4三种单元铁氧体固溶形成的复合铁氧体材料，三种单元铁氧体的含量以百分比计算，分别为α、β、γ，满足数量关系：5.78％≤α≤7.33％，30.49％≤γ≤34.43％，且α+β+γ＝1。本发明中的设计方法及制造工艺制备出的宽温高Tc高磁导率锰锌铁氧体材料，其起始磁导率μi≥7000(25℃，10kHz)，居里温度Tc＞170℃，同时在20℃～100℃的宽温度范围内，起始磁导率最小值μi_min≥6000，制得的材料克服了现有7K高磁导率锰锌铁氧体材料的不足，是一种宽温高Tc高磁导率锰锌铁氧体材料，适合推广应用。

Description

一种宽温高Tc高磁导率锰锌铁氧体材料及其制备方法
技术领域
本发明涉及锰锌铁氧体材料技术领域，具体涉及宽温高Tc高磁导率锰锌铁氧体材料及其制备方法。特别是在宽温度范围内有高磁导率的锰锌铁氧体材料，属于氧化物制备磁性材料领域。
背景技术
当前全球电子信息产业，新型照明技术、电子产品数字化等方面的飞速发展，向材料工业不断提出更高更新的需求，高磁导率软磁材料也面临同样的挑战。为了满足电子变压器等电子器件的平面化、片式化及轻量化的发展需求，需要提高铁氧体材料的磁导率；同时，为了让电子器件更好的适应其应用于环境温差大的场合，在满足高性能要求的基础上，必然要求铁氧体材料具有高的温度稳定性。因此，开发出具有宽温高Tc高磁导率的锰锌铁氧体材料是十分重要的。
目前，针对高磁导率锰锌铁氧体材料，国内外都开发出了不同牌号的铁氧体材料。Ferroxcube也开发的3E25、3E26、3E27、3E65等，日本TDK公司很早就开发的HP5、DN70等，中国台湾越峰也开发出A05、A07等；以及以横店东磁和天通为代表的内资企业也开发出了R5K、R7K、TSR7、等都是磁导率高于5000低于10000的高磁导率材料。在同时兼顾高磁导率、居里温度的条件下，磁导率为7000左右的高导材料受到广泛的重视和应用。传统的7000高导材料难以适应环境温差较大的场合，因此急需开发出一款居里温度达到170℃以上的材料，它的磁导率的温度特性良好，其起始磁导率在极大的温度范围内稳定在7000左右。这种宽温高Tc高磁导率铁氧体材料将在汽车电子等恶劣工况下具有显著的竞争优势，市场前景广阔。
综上所述，开发出的铁氧体材料在在宽温度范围内有高磁导率的锰锌铁氧体材料，同时又有成本优势，将在市场上具有很大的竞争优势，也是亟需要解决的问题。
发明内容
为了解决上述技术问题，本发明采用了以下技术方案：
采用本发明中的设计方法及制造工艺制备出的宽温高Tc高磁导率锰锌铁氧体材料，其起始磁导率μi≥7000(25℃，10kHz)，居里温度Tc＞170℃，同时在20℃～100℃的宽温度范围内，起始磁导率最小值μi_min≥6000。
一种宽温高Tc高磁导率锰锌铁氧体材料，
宽温高Tc高磁导率锰锌铁氧体材料至少包括FeFe2O4、MnFe2O4、ZnFe2O4三种单元铁氧体固溶形成的复合铁氧体材料，三种单元铁氧体的含量以百分比计算，分别为α、β、γ，满足数量关系：5.78％≤α≤7.33％，30.49％≤γ≤34.43％，且α+β+γ＝1。
作为本方案的进一步改进，铁氧体材料由Fe2O3、MnO、ZnO为原料制备而成，含量以mol％计算，含量分别为a％、b％、c％，a+b+c＝100，且有公式Tc＝9.40a-3.40b-11.93c-15.3，Tc＞170℃。
作为本方案的进一步改进，还包括添加剂组合物，所述添加剂组合物为BiVO4、LiCoO2、TiO2、CaCO3中的任意3种或者3种以上组分。
作为本方案的进一步改进，添加剂组合为BiVO4和LiCoO2和TiO2，
其中，BiVO4含量为200～500ppm，LiCoO2含量为300～800ppm，TiO2含量为200～500ppm。
作为本方案的进一步改进，添加剂组合为BiVO4和LiCoO2，
其中，BiVO4含量为200～500ppm，LiCoO2含量为300～800ppm。
一种宽温高Tc高磁导率锰锌铁氧体材料的制备方法，宽温高Tc高磁导率锰锌铁氧体材料包括下列步骤：
(1)原料混合：根据单元铁氧体含量百分比计算出三种主原料的投料量，称量好后使用振磨机混合，使三种原材料分布均匀；
(2)预烧：混合好的原料进入回转窑预烧，清除原料内的酸根离子和其他杂质，并初步反应生成铁氧体；
(3)砂磨：将预烧后的粉料加入添加剂组合、纯水、PVA、消泡剂后进行砂磨，粉料砂磨粒径控制在0.7～1.2μm；
(4)喷雾造粒：将砂磨后的浆料在喷雾塔中进行喷雾造粒；
(5)将喷雾造粒的粉料使用成型机压制成生坯，在钟罩窑中使用1340℃～1360℃之间的温度烧结7～10小时，降温过程中气氛使用平衡方程进行设定，冷却后即得到所述的软磁铁氧体材料。
作为本方案的进一步改进，所述步骤(5)中的烧结时间为8小时。
作为本方案的进一步改进，所述步骤(5)中的烧结温度为1360℃。
与现有技术相比，本发明具备下述有益效果：
本发明从铁氧体的化学组成出发，通过对组成铁氧体材料的单元铁氧体的数量和比例、添加剂组合、居里温度Tc、工艺条件等方面控制，实现了材料的高Tc、高磁导率特性和温度稳定性；
为了提高磁导率和改善温度特性，添加剂组合中一般都会选用低熔点的助熔剂和形成高阻晶界的CaCO3等等。在本发明专利中，结合传统的添加剂理论上，选用了BiVO4和LiCoO2作为必用的添加剂，上述添加剂的添加显著改善了磁导率和温度特性，BiVO4的熔点只有500℃，在烧结的过程中形成液相，可以促进晶粒均匀长大，提高磁导率；LiCoO2作为添加剂可以和主配方中的Fe2O3反应生成Li0.5Fe0.5Fe2O4和CoFe2O4，Li0.5Fe0.5Fe2O4可以进一步提升居里温度，而CoFe2O4拥有很大的磁晶各向异性常数K1，可以进一步有效补偿铁氧体的磁晶各向异性常数K1，调整磁导率的温度特性和二峰位置，可以大幅改善磁导率的温度特性；
通过选用BiVO4和LiCoO2作为必用的添加剂，本发明制备了一种宽温高Tc高磁导率锰锌铁氧体材料，该铁氧体电磁性能的测试条件如下：起始磁导率μi：B＜0.25mT；饱和磁通密度Bs：1kHz/1194A*m-1，单位为mT。其起始磁导率μi≥7000(25℃，10kHz)，居里温度Tc＞170℃，同时在20℃～100℃的宽温度范围内，起始磁导率最小值μi_min≥6000。综上，制得的材料克服了现有7K高磁导率锰锌铁氧体材料的不足，是一种宽温高Tc高磁导率锰锌铁氧体材料，适合推广应用。
附图说明
附图1为本发明中实施例中制备的宽温高Tc高磁导率锰锌铁氧体材料，典型的磁导率温度曲线。
具体实施方式
为了使本发明的目的、技术方案和优点更加清楚，以下结合实施例对本发明作进一步说明：
实施例1～4：
铁氧体材料内FeFe2O4、MnFe2O4、ZnFe2O4三种单元铁氧体含量α、β、γ,且满足6.30％≤α≤6.82％，31.45％≤γ≤33.44％，添加剂组合为0.04wt％BiVO4、0.06wt％LiCoO2、0.02％ CaCO3，α、β、γ及Tc的具体值见表-1中所示。铁氧体材料的具体制备方法如下：
(1)原料混合：根据三种单元铁氧体含量百分比计算出三种主原料的投料量，称量好后使用振磨机混合，使三种原材料分布均匀；
(2)预烧：混合好的原料进入回转窑预烧，清除原料内的酸根离子和其他杂质，并初步反应生成铁氧体；
(3)砂磨：将预烧后的粉料加入添加剂组合、纯水、PVA、消泡剂后进行砂磨，粉料砂磨粒径控制在0.7～1.1μm；
(4)喷雾造粒：将砂磨后的浆料在喷雾塔中进行喷雾造粒；
(5)将喷雾造粒的粉料使用成型机压制成生坯，在钟罩窑中使1360℃温度烧结8小时，降温过程中气氛使用平衡方程进行设定，冷却后即得到所述的软磁铁氧体材料。
实施例1～4的具体配方见表-1中所示。
实施例1～4样品的主要技术指标见表-2中所示。
对比例1～4：
对比例1～4中均有配方参数超出本发明前述给定的范围。其中，对比例1～2中α值超出本发明前述给定的范围，对比例3～4中γ值超出本发明前述给定的范围，并且对比例1、对比例4的Tc均超出了本发明前述给定的范围。对比例1～4的添加剂组合和制备工艺与实施例1-4完全相同。
对比例1～4样品的主要技术指标见表-2所示。
表-1实施例1～4及对比例1～4组分配方
表-2实施例1～4及对比例1～4样品的主要技术指标
实施例5～8：
实施例5～8的铁氧体材料内FeFe2O4、MnFe2O4、ZnFe2O4三种单元铁氧体含量完全相同，α、γ的值分别为α＝6.56％，γ＝32.46％，添加剂组合见表-3中所示，制备工艺与实施例1～4完全相同。
实施例5～8样品的主要技术指标见表-4中所示。
对比例5～8：
对比例5～8中的三种单元铁氧体含量与实施例5～8完全相同，但是添加剂组合中BiVO4和LiCoO2分别超出本发明前述给定的范围，添加剂组合见表-3所示，制备工艺与实施例5～8也完全相同。
对比例5～8样品的主要技术指标见表-4中所示。
实施例9～10：
实施例9～10的铁氧体材料内FeFe2O4、MnFe2O4、ZnFe2O4三种单元铁氧体含量完全相同，α、γ的值分别为α＝6.56％，γ＝32.46％，添加剂组合中只有TiO2含量不同，如表-3所示,制备工艺与实施例1～4完全相同。
实施例9～10样品的主要技术指标见表-4中所示。
对比例9～10：
对比例9～10中的三种单元铁氧体含量与实施例9～10也完全相同，但是添加剂组合中TiO2超出本发明前述给定的范围，添加剂组合见表-3所示，制备工艺与实施例9～10也完全相同。
对比例9～10样品的主要技术指标见表-4中所示。
表-3实施例5～10及对比例5～10组分配方
表-4实施例5～10及对比例5～10样品的主要技术指标
可以看出，本发明专利制备了一种宽温高Tc高磁导率锰锌铁氧体材料，其起始磁导率μi≥7000(25℃，10kHz)，居里温度Tc＞170℃，同时在20℃～100℃的宽温度范围内，起始磁导率最小值μi_min≥6000。
在本发明专利中，结合传统的添加剂理论上，选用了BiVO4和LiCoO2作为必用的添加剂，上述添加剂的添加显著改善了磁导率和温度特性，BiVO4的熔点只有500℃，在烧结的过程中形成液相，可以促进晶粒均匀长大，提高磁导率；LiCoO2作为添加剂可以和主配方中的Fe2O3反应生成Li0.5Fe0.5Fe2O4和CoFe2O4，Li0.5Fe0.5Fe2O4可以进一步提升居里温度，而CoFe2O4拥有很大的磁晶各向异性常数K1，可以进一步有效补偿铁氧体的磁晶各向异性常数K1，调整磁导率的温度特性和二峰位置，可以大幅改善磁导率的温度特性。
以上所述仅为本发明的优选实施方式，并非因此限制本发明的专利范围，凡是利用本发明所作的等效变换，均在本发明的专利保护范围内。

Claims (5)

1.一种宽温高Tc高磁导率锰锌铁氧体材料，其特征在于：
宽温高Tc高磁导率锰锌铁氧体材料至少包括FeFe2O4、MnFe2O4、ZnFe2O4三种单元铁氧体固溶形成的复合铁氧体材料，三种单元铁氧体的含量以百分比计算，分别为α、β、γ，满足数量关系：5.78％≤α≤7.33％，30.49％≤γ≤34.43％，且α+β+γ＝1；
还包括添加剂组合物，添加剂组合为BiVO4和LiCoO2和TiO2，
其中，BiVO4含量为200～500ppm，LiCoO2含量为300～800ppm，TiO2含量为200～500ppm。
2.根据权利要求1所要求的宽温高Tc高磁导率锰锌铁氧体材料，其特征在于：铁氧体材料由Fe2O3、MnO、ZnO为原料制备而成，含量以mol％计算，含量分别为a％、b％、c％，a+b+c＝100，且有公式Tc＝9.40a-3.40b-11.93c-15.3，Tc＞170℃。
3.一种权利要求1或2任一项所述宽温高Tc高磁导率锰锌铁氧体材料的制备方法，其特
征在于：宽温高Tc高磁导率锰锌铁氧体材料包括下列步骤：
(1)原料混合：根据单元铁氧体含量百分比计算出三种主原料的投料量，称量好后使用
振磨机混合，使三种原材料分布均匀；
(2)预烧：混合好的原料进入回转窑预烧，清除原料内的酸根离子和其他杂质，并初步
反应生成铁氧体；
(3)砂磨：将预烧后的粉料加入添加剂组合、纯水、PVA、消泡剂后进行砂磨，粉料砂磨粒径控制在0.7～1.2μm；
(4)喷雾造粒：将砂磨后的浆料在喷雾塔中进行喷雾造粒；
(5)将喷雾造粒的粉料使用成型机压制成生坯，在钟罩窑中使用1340℃～1360℃之间
的温度烧结7～10小时，降温过程中气氛使用平衡方程进行设定，冷却后即得到铁氧体材料。
4.根据权利要求3所要求的宽温高Tc高磁导率锰锌铁氧体材料的制备方法，其特征在
于：所述步骤(5)中的烧结时间为8小时。
5.根据权利要求4所要求的宽温高Tc高磁导率锰锌铁氧体材料的制备方法，其特征在
于：所述步骤(5)中的烧结温度为1360℃。
CN202211326098.0A 2022-10-27 2022-10-27 一种宽温高Tc高磁导率锰锌铁氧体材料及其制备方法 Active CN115611624B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211326098.0A CN115611624B (zh) 2022-10-27 2022-10-27 一种宽温高Tc高磁导率锰锌铁氧体材料及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211326098.0A CN115611624B (zh) 2022-10-27 2022-10-27 一种宽温高Tc高磁导率锰锌铁氧体材料及其制备方法

Publications (2)

Publication Number Publication Date
CN115611624A CN115611624A (zh) 2023-01-17
CN115611624B true CN115611624B (zh) 2023-07-25

Family

ID=84863802

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211326098.0A Active CN115611624B (zh) 2022-10-27 2022-10-27 一种宽温高Tc高磁导率锰锌铁氧体材料及其制备方法

Country Status (1)

Country Link
CN (1) CN115611624B (zh)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7195717B2 (en) * 2003-07-28 2007-03-27 Kyocera Corporation Ferrite core for RFID application, method of manufacturing the same, and ferrite coil using the same
JP2010173888A (ja) * 2009-01-29 2010-08-12 Tdk Corp ＭｎＺｎ系フェライトの製造方法
CN104150540B (zh) * 2014-07-14 2016-01-20 河南大学 一种重金属离子吸附剂铁氧体空心球MFe2O4
CN110339843B (zh) * 2019-08-08 2021-06-29 重庆大学 一种磁性氧化铋/钒酸铋复合光催化剂的制备方法
CN113087515B (zh) * 2021-03-26 2022-08-02 重庆上甲电子股份有限公司 高饱和磁感应强度和宽温低磁芯损耗锰锌铁氧体及其制备方法和四氟铝酸钾的应用
CN113831119B (zh) * 2021-09-30 2022-09-06 海宁辉恒磁业有限公司 一种超高Bs低损耗锰锌铁氧体材料及其制备方法

Also Published As

Publication number Publication date
CN115611624A (zh) 2023-01-17

Similar Documents

Publication Publication Date Title
CN107311637B (zh) 一种基于核壳结构晶粒制备低功率损耗锰锌铁氧体的方法
CN100533609C (zh) 一种高饱和磁通密度低损耗MnZn功率铁氧体及其制备方法
CN100345226C (zh) 锰－锌铁氧体磁体材料及其用该材料制备高导锰－锌铁氧体的方法
CN110128124B (zh) 一种宽温超低损耗软磁铁氧体材料及其制备方法
CN112979301B (zh) 高频高温低损耗MnZn功率铁氧体材料及其制备方法
EP0980856A1 (en) A Mn-Zn Ferrite
CN111233452B (zh) 一种高频高阻抗的贫铁锰锌铁氧体及其制备方法
CN113831119B (zh) 一种超高Bs低损耗锰锌铁氧体材料及其制备方法
CN107352993A (zh) 一种高频锰锌软磁铁氧体材料及其制备方法
CN102211929A (zh) 一种低温烧结高磁导率NiCuZn铁氧体材料
CN108610037B (zh) 一种宽温高叠加高居里温度的锰锌高磁导率材料及其制备方法
US7238298B2 (en) Ni-Cu-Zn-based ferrite material and process for the production thereof
EP4378910A1 (en) Mn-zn ferrite material and preparation method therefor
CN113327736B (zh) 一种宽频、五高性能的软磁铁氧体材料及其制备方法
EP0980857B1 (en) A Mn-Zn ferrite
CN115611624B (zh) 一种宽温高Tc高磁导率锰锌铁氧体材料及其制备方法
CN103956247A (zh) 高频低衰减磁性材料及其生产方法
WO2012151714A1 (zh) 一种高磁导率NiCuZn铁氧体材料
CN113284731B (zh) 一种高频大磁场软磁铁氧体材料及其制备方法
CN112441828B (zh) 一种铁氧体材料及其制备方法
CN115650719B (zh) 一种高Tc高磁导率锰锌铁氧体材料及其制备方法
CN113735574A (zh) 一种超高Bs低损耗锰锌铁氧体材料及其制备方法
CN115745592B (zh) 一种宽频高Tc高磁导率锰锌铁氧体材料及其制备方法
CN113636838A (zh) 一种镍锌铁氧体材料及制备方法和应用
JPH08310856A (ja) Ｎｉ−Ｃｕ−Ｚｎフェライト焼結体

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
GR01 Patent grant
GR01 Patent grant