CN109231978A - A kind of high frequency high magnetic conductivity ferrite piece and preparation method thereof - Google Patents

A kind of high frequency high magnetic conductivity ferrite piece and preparation method thereof Download PDF

Info

Publication number
CN109231978A
CN109231978A CN201810948155.6A CN201810948155A CN109231978A CN 109231978 A CN109231978 A CN 109231978A CN 201810948155 A CN201810948155 A CN 201810948155A CN 109231978 A CN109231978 A CN 109231978A
Authority
CN
China
Prior art keywords
magnetic conductivity
high frequency
preparation
high magnetic
raw material
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.)
Granted
Application number
CN201810948155.6A
Other languages
Chinese (zh)
Other versions
CN109231978B (en
Inventor
严密
王小雨
金佳莹
白国华
王新华
吴琛
魏中华
张雪峰
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.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
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 Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN201810948155.6A priority Critical patent/CN109231978B/en
Publication of CN109231978A publication Critical patent/CN109231978A/en
Application granted granted Critical
Publication of CN109231978B publication Critical patent/CN109231978B/en
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
    • C04B35/622—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
    • C04B2235/3208—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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3256—Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
    • 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
    • C04B2235/3267—MnO2
    • 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
    • C04B2235/3284—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
    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
    • 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
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6025—Tape casting, e.g. with a doctor blade
    • 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
    • C04B2235/6581—Total pressure below 1 atmosphere, e.g. vacuum

Abstract

The invention discloses a kind of high frequency high magnetic conductivity ferrite pieces and preparation method thereof.It is mainly sintered by doping process and low-pressure low-temperature, adhesion when magnetic sheet being avoided to be sintered, promotes ferrite sheet frequency of use and magnetic conductivity.Preparation process of the invention is its key step are as follows: 1) raw material mix, and 2) pre-burning, 3) doping, slurrying, 4) curtain coating, 5) low-pressure low-temperature sintering.Ferrite sheet cutoff frequency prepared by the present invention is higher than 5MHz, and when initial permeability is higher than 600,13.56MHz when 200KHz, magnetic conductivity is higher than 100, can meet simultaneously the application of wireless charging and near-field communication, while solving the problems, such as bonding die when lamination sintering.

Description

A kind of high frequency high magnetic conductivity ferrite piece and preparation method thereof
Technical field
The present invention relates to a kind of high frequency high magnetic conductivity ferrite pieces and preparation method thereof, belong to electronic component new material neck Domain.
Background technique
With the rapid advances of electronic information technology, the equipment such as mobile phone, tablet computer, intelligence wearing have obtained extensive general And.Wherein near-field communication and wireless charging are consumer electronics field two application fields with fastest developing speed at present.Near-field communication can So that equipment it is close to each other without contacting in the case where carry out data exchange, and wireless charging then can largely be alleviated The small drawback of electronic product battery capacity.Both technologies are all using near field electromagnetic wave, and near-field communication generally utilizes 13.56MHz frequency is realized, and wireless charging is realized using 200KHz frequency.Both technologies are when implementing, all Ferrite sheet is needed to prevent influence of the electromagnetic wave to adjacent devices, while improving working efficiency.At present for near-field communication and Wireless charging needs to use the ferrite sheet of two kinds of different sizes simultaneously due to the difference of frequency of use, so that electronic equipment is multiple Hydridization, an effective solution method are exactly to obtain a kind of ferrite sheet still under high frequency of use with high magnetic permeability, Meets the needs of two kinds of applications simultaneously.Meanwhile ferrite sheet is often folded the method burnt using multi-disc, protected under high temperature in sintering Wen Shi, the generation of a large amount of liquid phases can make adjacent magnetic sheet adhesion, it is difficult to produce the ferrite sheet of large area.
Summary of the invention
The purpose of the present invention is technological trend and the lamination sintering for above-mentioned wireless charging and near-field communication high frequency Adhesion problems existing for ferrite provide a kind of high frequency high magnetic conductivity ferrite piece and preparation method thereof.Iron provided by the invention Oxysome piece cutoff frequency in 5MHz or more, 200KHz initial permeability be higher than 600,13.56MHz when, magnetic conductivity be higher than 100.
In order to achieve the above object, the present invention is implemented as follows:
1) raw material mixes
Preferably, starting oxides carry out ingredient according to following weight ratio: Fe2O3: 68-72wt%, ZnO:5-9wt%, MnO2: surplus.Raw material in the ball mill, using deionized water as ball-milling medium, dries after ball milling 1-5h, obtains pre- milling.
2) pre-burning
Preferably, pre- milling calcines 2-4h between 780-940 DEG C, pre-burning powder is obtained.
3) doping, slurrying
One of adulterate In, Co, Ca, Si, Ti in pre-burning powder, while adulterating V, Mo, Bi, doping accounts for principal component Weight percent are as follows: In2O3For 0.001-0.55%, CoO 0.001-0.25%, CaO 0.001-0.35%, SiO2For 0.001-0.25%, TiO2For 0.001-0.3%, V2O5、Mo2O3、Bi2O3One of, doping 0.05-0.5%.Then Organic solvent, plasticizer, binder is added in pre-burning powder, in the ball mill 8~20h of ball milling, ultrasonic disperse, the screen to filtrate, very Empty deaeration, obtains slurry, and identical organic solvent is finally used to adjust viscosity as 10~100mPas.
Preferably, dopant mass percent are as follows: In2O3For 0.05-0.35%, CoO 0.05-0.20%, CaO For 0.05-0.30%, SiO2For 0.05-0.20%, TiO2For 0.05-0.25%, V2O5、Mo2O3、Bi2O3One of, doping Amount is 0.05-0.30%.
The organic solvent is one of ethyl alcohol, acetone, dimethylbenzene, accounts for the 40~60% of slurry gross mass.It is described Binder be one of polyvinyl alcohol or polyvinyl butyral, quality for the pre-burning powder being added 1-5%.It is described Plasticizer be that dioctyl phthalate or dibutyl phthalate are a kind of, quality for the pre-burning powder being added 0.5- 3%.
4) it is cast
Slurry to be injected in casting machine storage tank, the height of scraper is 0.05~1mm, control casting machine speed is 0.1~ 2cm/s is used as substrate using PET film or steel band when curtain coating, obtains raw material band, and raw material band obtains after 60 DEG C of baking ovens drying Cast sheet.
5) it is sintered
By cast sheet after substrate desquamation, it is placed on aluminium oxide or zirconium oxide plate and carries out air calcination.In 300-400 0.1-2h is kept the temperature between DEG C carries out degumming process, then sintered heat insulating 1-5h in a low temperature of 800-900 DEG C, atmosphere when sintering Using low pressure atmosphere, air pressure 100Pa-2000Pa completes sintering process.
In the present invention, dopant is selectively used for target, wherein In2O3It can effectively improve cutoff frequency；CoO And TiO2High valence ion can be provided to enter in the interstitial site of spinel structure, iron can be improved by changing site occupancy The initial permeability of oxysome；And V2O5、Mo2O3、Bi2O3All it is the oxide with low melting point, selects one of addition, it can be with The liquid-phase sintering of part is formed, crystal grain homogenization is promoted, cooperation environment under low pressure reduces sintering temperature jointly, is effectively improved lamination and exists The case where adhesion is generated when sintering.
Compared with prior art, the present invention having the advantages that:
For application fields such as wireless charging and near-field communications, it is often desirable that ferrite sheet its can be in higher frequency of use There is down higher magnetic conductivity, the cutoff frequency of ferrite sheet is prepared by doping process using the method for curtain coating in the present invention Rate in 5MHz or more, 200KHz initial permeability be higher than 600,13.56MHz when, magnetic conductivity be higher than 100, can meet simultaneously The requirement of wireless charging and near-field communication, simultaneously because the low-pressure low-temperature sintering used, what when sintered heat insulating generated avoids tradition High temperature generates liquid phase, the probability of bonding die when substantially reducing lamination sintering.
Specific embodiment
Below with reference to specific example, the present invention will be further described, but the present invention is not limited only to following implementation Example.
Embodiment 1:
Starting oxides are according to Fe2O3: 68wt%, ZnO:5wt%, MnO2Surplus carrys out ingredient.Then in ball mill, to go Ionized water is ball-milling medium, is dried after ball milling 2h, and pre- milling is obtained.Pre- milling calcines 4h between 780 DEG C, obtains pre-burning powder. In, Co, Ca, Si, Ti, Mo are adulterated in pre-burning powder, doping accounts for the weight percent of principal component are as follows: In2O3For 0.15%, CoO For 0.05%, CaO 0.15%, SiO2For 0.05%, TiO2For 0.15%, Mo2O3It is 0.25%.Then it is total to account for slurry for addition The polyvinyl alcohol of pre-burning silty amount 1% is added in the ethyl alcohol of quality 40%, and the phthalic acid two of pre-burning silty amount 0.5% is added Monooctyl ester, in the ball mill ball milling 8h, ultrasonic disperse, the screen to filtrate, vacuum defoamation, obtains slurry, is finally adjusted using ethyl alcohol glutinous Degree is 60mPas, obtains casting slurry.Slurry is injected in casting machine storage tank, the height of scraper is 0.15mm, control stream Prolonging machine speed is 0.5cm/s, is used as substrate using steel band when curtain coating, obtains raw material band, raw material band is after 60 DEG C of baking ovens drying Obtain cast sheet.By cast sheet after substrate desquamation, it is placed on alumina plate and carries out air calcination.It is kept the temperature between 300 DEG C 0.5h carries out degumming process, is then sintered 3h in 800 DEG C, 1000Pa.
The ferrite sheet prepared carries out magnetism testing, when cutoff frequency is 14MHz, initial permeability 650, The magnetic conductivity of 14MHz is greater than 300, and under 25 DEG C, the test condition of 5MHz, 10mT, power loss is 160kW m-3。
Embodiment 2:
Starting oxides are according to Fe2O3: 70wt%, ZnO:6wt%, CuO:5wt%, MnO2Surplus carrys out ingredient.Then ball milling In machine, using deionized water as ball-milling medium, is dried after ball milling 2.5h, obtain pre- milling.Pre- milling calcines 4h between 800 DEG C, Obtain pre-burning powder.In, Co, Ca, Si, Ti, Bi are adulterated in pre-burning powder, doping accounts for the weight percent of principal component are as follows: In2O3 For 0.25%, CoO 0.15%, CaO 0.20%, SiO2For 0.15%, TiO2For 0.25%, Bi2O3It is 0.25%.Then The acetone for accounting for slurry gross mass 50% is added, the polyvinyl alcohol of pre-burning silty amount 1.5% is added, pre-burning silty amount 0.6% is added Dibutyl phthalate, ball milling 6h, ultrasonic disperse, the screen to filtrate, vacuum defoamation in the ball mill obtain slurry, finally It uses acetone to adjust viscosity as 80mPas, obtains casting slurry.Slurry is injected in casting machine storage tank, the height of scraper is 0.45mm, control casting machine speed are 0.7cm/s, are used as substrate using steel band when curtain coating, obtain raw material band, raw material band is by 60 Cast sheet is obtained after the drying of DEG C baking oven.By cast sheet after substrate desquamation, it is placed on alumina plate and carries out air calcination.350 0.5h is kept the temperature between DEG C and carries out degumming process, is then sintered 4h in 850 DEG C, 500Pa.
The ferrite sheet prepared carries out magnetism testing, when cutoff frequency is 15MHz, initial permeability 870, The magnetic conductivity of 14MHz is greater than 500, and under 25 DEG C, the test condition of 5MHz, 10mT, power loss is 145kW m-3。
Embodiment 3:
Starting oxides are according to Fe2O3: 70wt%, ZnO:8wt%, CuO:4wt%, NiO surplus carry out ingredient.Then ball milling In machine, using deionized water as ball-milling medium, is dried after ball milling 3h, obtain pre- milling.Pre- milling calcines 4.5h between 850 DEG C, Obtain pre-burning powder.In, Co, Ca, Si, Ti, Bi are adulterated in pre-burning powder, doping accounts for the weight percent of principal component are as follows: In2O3 For 0.45%, CoO 0.25%, CaO 0.25%, SiO2For 0.10%, TiO2For 0.35%, V2O5It is 0.25%.Then The dimethylbenzene for accounting for slurry gross mass 45% is added, the polyvinyl butyral of pre-burning silty amount 1.5% is added, pre-burning powder is added The dibutyl phthalate of quality 0.6%, ball milling 5.5h, ultrasonic disperse, the screen to filtrate, vacuum defoamation obtain in the ball mill To slurry, finally uses dimethylbenzene to adjust viscosity as 90mPas, obtain casting slurry.Slurry is injected into casting machine storage tank In, the height of scraper is 0.65mm, and control casting machine speed is 1cm/s, and when curtain coating uses PET film as substrate, obtains raw material Band, raw material band obtain cast sheet after 60 DEG C of baking ovens are dried.By cast sheet after substrate desquamation, it is placed on alumina plate and carries out Air calcination.0.5h is kept the temperature between 380 DEG C and carries out degumming process, is then sintered 3.5h in 900 DEG C, 200Pa.
The ferrite sheet prepared carries out magnetism testing, when cutoff frequency is 15MHz, initial permeability 1000, The magnetic conductivity of 14MHz is greater than 500, and under 25 DEG C, the test condition of 5MHz, 10mT, power loss is 155kW m-3。
Comparative example 1:
Starting oxides are according to Fe2O3: 68wt%, ZnO:5wt%, MnO2Surplus carrys out ingredient.Then in ball mill, to go Ionized water is ball-milling medium, is dried after ball milling 2h, and pre- milling is obtained.Pre- milling calcines 4h between 780 DEG C, obtains pre-burning powder. In, Co, Ca, Si, Ti, Mo are adulterated in pre-burning powder, doping accounts for the weight percent of principal component are as follows: CoO 0.05%, CaO For 0.15%, SiO2For 0.05%, TiO2For 0.15%, Mo2O3It is 0.25%.Then the second for accounting for slurry gross mass 40% is added The polyvinyl alcohol of pre-burning silty amount 1% is added in alcohol, the dioctyl phthalate of pre-burning silty amount 0.5% is added, in ball mill Middle ball milling 8h, ultrasonic disperse, the screen to filtrate, vacuum defoamation obtain slurry, finally use ethyl alcohol adjusting viscosity for 60mPas, Obtain casting slurry.Slurry is injected in casting machine storage tank, the height of scraper is 0.15mm, and control casting machine speed is 0.5cm/s is used as substrate using steel band when curtain coating, obtains raw material band, and raw material band obtains cast sheet after 60 DEG C of baking ovens drying. By cast sheet after substrate desquamation, it is placed on alumina plate and carries out air calcination.0.5h is kept the temperature between 300 DEG C to carry out at degumming Then reason is sintered 3h in 800 DEG C, 1000Pa.
The ferrite sheet prepared carries out magnetism testing, when cutoff frequency is 10MHz, initial permeability 630, The magnetic conductivity of 14MHz is less than 100, and under 25 DEG C, the test condition of 5MHz, 10mT, power loss is 197kW m-3。
Comparative example 2:
Starting oxides are according to Fe2O3: 70wt%, ZnO:6wt%, CuO:5wt%, MnO2Surplus carrys out ingredient.Then ball milling In machine, using deionized water as ball-milling medium, is dried after ball milling 2.5h, obtain pre- milling.Pre- milling calcines 4h between 800 DEG C, Obtain pre-burning powder.In, Co, Ca, Si, Ti, Bi are adulterated in pre-burning powder, doping accounts for the weight percent of principal component are as follows: In2O3 For 0.25%, CaO 0.20%, SiO2For 0.15%, Bi2O3It is 0.25%.Then it is added and accounts for the third of slurry gross mass 50% The polyvinyl alcohol of pre-burning silty amount 1.5% is added in ketone, the dibutyl phthalate of pre-burning silty amount 0.6% is added, in ball milling Ball milling 6h in machine, ultrasonic disperse, the screen to filtrate, vacuum defoamation obtain slurry, and acetone is finally used to adjust viscosity as 80mPa S obtains casting slurry.Slurry is injected in casting machine storage tank, the height of scraper is 0.45mm, and control casting machine speed is 0.7cm/s is used as substrate using steel band when curtain coating, obtains raw material band, and raw material band obtains cast sheet after 60 DEG C of baking ovens drying. By cast sheet after substrate desquamation, it is placed on alumina plate and carries out air calcination.0.5h is kept the temperature between 350 DEG C to carry out at degumming Then reason is sintered 4h in 850 DEG C, 500Pa.
The ferrite sheet prepared carries out magnetism testing, when cutoff frequency is 12MHz, initial permeability 610, The magnetic conductivity of 14MHz is less than 100, and under 25 DEG C, the test condition of 5MHz, 10mT, power loss is 167kW m-3。
Comparative example 3:
Starting oxides are according to Fe2O3: 70wt%, ZnO:8wt%, CuO:4wt%, NiO surplus carry out ingredient.Then ball milling In machine, using deionized water as ball-milling medium, is dried after ball milling 3h, obtain pre- milling.Pre- milling calcines 4.5h between 850 DEG C, Obtain pre-burning powder.In, Co, Ca, Si, Ti, Bi are adulterated in pre-burning powder, doping accounts for the weight percent of principal component are as follows: In2O3 For 0.45%, CoO 0.25%, CaO 0.25%, SiO2For 0.10%, TiO2For 0.35%, V2O5It is 0.25%.Then plus Enter to account for the dimethylbenzene of slurry gross mass 45%, the polyvinyl butyral of pre-burning silty amount 1.5% is added, pre-burning silty is added The dibutyl phthalate of amount 0.6%, ball milling 5.5h, ultrasonic disperse, the screen to filtrate, vacuum defoamation obtain in the ball mill Slurry finally uses dimethylbenzene to adjust viscosity as 90mPas, obtains casting slurry.Slurry is injected in casting machine storage tank, The height of scraper is 0.65mm, and control casting machine speed is 1cm/s, uses PET film as substrate when curtain coating, obtains raw material band, Raw material band obtains cast sheet after 60 DEG C of baking ovens are dried.By cast sheet after substrate desquamation, it is placed on alumina plate and carries out sky Gas sintering.0.5h is kept the temperature between 380 DEG C and carries out degumming process, then in 1130 DEG C of sintering 3.5h.
The ferrite sheet prepared carries out magnetism testing, when cutoff frequency is 11MHz, initial permeability 840, The magnetic conductivity of 14MHz is less than 100, and under 25 DEG C, the test condition of 5MHz, 10mT, power loss is 214kW m-3。

Claims (7)

1. a kind of preparation method of high frequency high magnetic conductivity ferrite piece, it is characterised in that include the following steps:
1) raw material mixes；
2) pre-burning；
3) doping, slurrying
One of adulterate In, Co, Ca, Si, Ti in pre-burning powder, while adulterating V, Mo, Bi, wherein in terms of oxide, each member Plain doping accounts for the weight percent of principal component are as follows: In2O3It is for 0.001-0.55%, CoO 0.001-0.25%, CaO 0.001-0.35%, SiO2For 0.001-0.25%, TiO2For 0.001-0.3%, V2O5、Mo2O3、Bi2O3One of, doping Amount is 0.001-0.5%；Then organic solvent, plasticizer, binder is added in the pre-burning powder after doping oxide, in ball mill Middle 8~20h of ball milling, ultrasonic disperse, the screen to filtrate, vacuum defoamation obtain slurry, are finally adjusted using identical organic solvent glutinous Degree is 10~100mPas；
4) it is cast
Slurry is injected in casting machine storage tank, the height of scraper is 0.05~1mm, and control casting machine speed is 0.1~2cm/ S is used as substrate using PET film or steel band when curtain coating, obtains raw material band, and raw material band is cast after 60 DEG C of baking ovens drying Piece；
5) low-pressure low-temperature is sintered
By cast sheet after substrate desquamation, lamination, which is placed on alumina plate, carries out air calcination, keeps the temperature between 300-400 DEG C 0.1-2h carries out dumping processing, then sintered heat insulating 1-5h in a low temperature of 800-900 DEG C, and atmosphere uses low pressure gas when sintering Atmosphere, air pressure 100Pa-2000Pa complete sintering process.
2. the preparation method of high frequency high magnetic conductivity ferrite piece as described in claim 1, it is characterised in that the raw material is Iron oxide, zinc oxide also include one or both of manganese oxide, copper oxide, nickel oxide.
3. the preparation method of high frequency high magnetic conductivity ferrite piece as described in claim 1, it is characterised in that described is organic molten Agent be one of ethyl alcohol, acetone, dimethylbenzene, total dosage of organic solvent account for viscosity adjust after slurry gross mass 40~ 60%.
4. the preparation method of high frequency high magnetic conductivity ferrite piece as described in claim 1, it is characterised in that the binder For one of polyvinyl alcohol or polyvinyl butyral, quality is the 1-5% of pre-burning powder.
5. such as the preparation method of claim 1 high frequency high magnetic conductivity ferrite piece, it is characterised in that the plasticizer is adjacent benzene Diformazan dioctyl phthalate or dibutyl phthalate are a kind of, and additional amount is the 0.5-3% of pre-burning powder.
6. a kind of high frequency high magnetic conductivity ferrite piece, it is characterised in that be prepared by any one of claim 1-4 the method.
7. high frequency high magnetic conductivity ferrite piece as claimed in claim 6, it is characterised in that the cutoff frequency of the ferrite sheet Rate is higher than 5MHz, and when initial permeability is higher than 600,13.56MHz when 200KHz, magnetic conductivity is higher than 100.
CN201810948155.6A 2018-08-20 2018-08-20 High-frequency high-permeability ferrite sheet and preparation method thereof Active CN109231978B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810948155.6A CN109231978B (en) 2018-08-20 2018-08-20 High-frequency high-permeability ferrite sheet and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810948155.6A CN109231978B (en) 2018-08-20 2018-08-20 High-frequency high-permeability ferrite sheet and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109231978A true CN109231978A (en) 2019-01-18
CN109231978B CN109231978B (en) 2020-10-27

Family

ID=65071759

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810948155.6A Active CN109231978B (en) 2018-08-20 2018-08-20 High-frequency high-permeability ferrite sheet and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109231978B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109678481A (en) * 2019-02-15 2019-04-26 苏州世诺新材料科技有限公司 A kind of preparation method of complex ferrite piece
CN113716950A (en) * 2021-11-01 2021-11-30 天通控股股份有限公司 Low-temperature sintered flexible magnetic sheet and preparation method thereof
CN115368127A (en) * 2022-08-22 2022-11-22 深圳顺络电子股份有限公司 Ferrite material, preparation method and common-mode inductor

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101388268A (en) * 2008-07-11 2009-03-18 临沂中瑞电子有限公司 High magnetic conductive low temperature sintered NiCuZn ferrite material
CN102390985A (en) * 2011-08-06 2012-03-28 江苏华兴电子有限公司 Broadband and high-magnetic-permeability ferrite teflon tape and production method thereof
CN103360042A (en) * 2012-04-01 2013-10-23 比亚迪股份有限公司 Nickel-zinc soft magnetic ferrite and preparation method thereof
CN104556994A (en) * 2014-12-19 2015-04-29 江门安磁电子有限公司 Ni-free manganese zinc ferrite material applied to (-20)-140 DEG C and manufacturing method thereof
CN104844184A (en) * 2015-04-27 2015-08-19 厦门大学 Near field communication magnetic sheet with low magnetic permeability and temperature coefficient and preparation method thereof
CN107352992A (en) * 2017-07-04 2017-11-17 浙江大学 A kind of powder size control method of wideband wide-temperature and low-consumption manganese-zinc ferrite
CN108164260A (en) * 2018-01-15 2018-06-15 上海安费诺永亿通讯电子有限公司 A kind of wireless charging Ni-Zn soft magnetic ferrite and preparation method thereof, application

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101388268A (en) * 2008-07-11 2009-03-18 临沂中瑞电子有限公司 High magnetic conductive low temperature sintered NiCuZn ferrite material
CN102390985A (en) * 2011-08-06 2012-03-28 江苏华兴电子有限公司 Broadband and high-magnetic-permeability ferrite teflon tape and production method thereof
CN103360042A (en) * 2012-04-01 2013-10-23 比亚迪股份有限公司 Nickel-zinc soft magnetic ferrite and preparation method thereof
CN104556994A (en) * 2014-12-19 2015-04-29 江门安磁电子有限公司 Ni-free manganese zinc ferrite material applied to (-20)-140 DEG C and manufacturing method thereof
CN104844184A (en) * 2015-04-27 2015-08-19 厦门大学 Near field communication magnetic sheet with low magnetic permeability and temperature coefficient and preparation method thereof
CN107352992A (en) * 2017-07-04 2017-11-17 浙江大学 A kind of powder size control method of wideband wide-temperature and low-consumption manganese-zinc ferrite
CN108164260A (en) * 2018-01-15 2018-06-15 上海安费诺永亿通讯电子有限公司 A kind of wireless charging Ni-Zn soft magnetic ferrite and preparation method thereof, application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
夏德贵: "《软磁铁氧体制造原理与技术》", 31 December 2010, 陕西科学技术出版社 *
林其壬: "《铁氧体工艺原理》", 30 April 1987, 上海科学技术出版社 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109678481A (en) * 2019-02-15 2019-04-26 苏州世诺新材料科技有限公司 A kind of preparation method of complex ferrite piece
CN113716950A (en) * 2021-11-01 2021-11-30 天通控股股份有限公司 Low-temperature sintered flexible magnetic sheet and preparation method thereof
CN115368127A (en) * 2022-08-22 2022-11-22 深圳顺络电子股份有限公司 Ferrite material, preparation method and common-mode inductor

Also Published As

Publication number Publication date
CN109231978B (en) 2020-10-27

Similar Documents

Publication Publication Date Title
CN109231978A (en) A kind of high frequency high magnetic conductivity ferrite piece and preparation method thereof
CN101807463B (en) MnZn ferrite material of high initial permeability and low loss and preparation method thereof
JP2018125286A (en) Electrode laminate and all-solid lithium battery
CN107555992B (en) Microwave dielectric ceramic material and preparation method thereof
CN101880167A (en) Base metal inner electrode multi-layer ceramic wafer type capacitor medium material prepared by chemical coating of water system
CN103214235B (en) A kind of preparation method of microwave dielectric ceramic materials
CN101183610B (en) Chemical coating prepared base metal internal electrode multi-layer ceramic chip capacitor dielectric material
KR101773942B1 (en) Complex oxide-coated metal powder, production method therefor, conductive paste using complex oxide-coated metal powder, and multilayer ceramic electronic component
CN105036734A (en) High-dielectric-constant X8R type dielectric material for multilayer porcelain capacitor, and preparation method for dielectric material
CN104230322A (en) M-type calcium permanent magnetic ferrite and preparation method thereof
CN104341146A (en) Zinc oxide voltage-sensitive ceramic material for high-performance lightning arrester
CN113603152A (en) 4.7V-grade lithium cobaltate positive electrode material, preparation method thereof and corresponding battery
JP2016072241A (en) Lithium cobaltate orientated sintered plate and manufacturing method thereof, and method for forming solid electrolyte layer on lithium cobaltate orientated sintered plate
CN110444756B (en) Lithium ion battery anode material prepared by high-temperature reaction device, preparation method and application
CN102437326B (en) Method for preparing large-grain-size lithium cobaltate as cathode material for lithium-ion secondary battery
CN104557027A (en) CoFe2O4/BaTiO3 layered magnetoelectric composite material and preparation method thereof
CN102087898A (en) Method for preparing zinc oxide varistor by using pure silver as inner electrode
JP2023158013A (en) Ni-Zn-Cu-BASED FERRITE POWDER, SINTERED COMPACT, FERRITE SHEET
CN105218082B (en) Preparation method of anti-metal nickel copper zinc ferrite separating magnetic sheet material
JP2005179172A (en) Method of dispersing and coating additive on dielectric ceramic powder
CN108503351B (en) Magnetic separation sheet for wireless charging and preparation method thereof
CN107935583A (en) A kind of manufacture method of varistor
CN103224393B (en) A kind of preparation method of microwave dielectric ceramic materials
JP2014164836A (en) Method of forming crystal-oriented cathode active material plate
CN104575887B (en) A kind of patch type varistor low temperature diffusion slurry and preparation method thereof

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