CN108046791B - Method for preparing ferrite from nano MnZn ferrite powder - Google Patents
Method for preparing ferrite from nano MnZn ferrite powder Download PDFInfo
- Publication number
- CN108046791B CN108046791B CN201810030787.4A CN201810030787A CN108046791B CN 108046791 B CN108046791 B CN 108046791B CN 201810030787 A CN201810030787 A CN 201810030787A CN 108046791 B CN108046791 B CN 108046791B
- Authority
- CN
- China
- Prior art keywords
- powder
- ferrite
- dopant
- nano
- source
- 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.)
- Expired - Fee Related
Links
Images
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
- C04B35/2658—Other ferrites containing manganese or zinc, e.g. Mn-Zn ferrites
-
- 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
- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
-
- 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
- C04B2235/3205—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
- C04B2235/34—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
- C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
-
- 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
- C04B2235/65—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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Soft Magnetic Materials (AREA)
- Magnetic Ceramics (AREA)
Abstract
The invention relates to a method for preparing ferrite by nano MnZn ferrite powder. The invention comprises the following steps: mixing an organic binder solution and a dopant solution, then adding manganese-zinc ferrite nano powder containing a coupling agent, and carrying out ultrasonic treatment until the liquid is evaporated to dryness; grinding and sieving the obtained powder, injecting the powder into a mold, pressurizing and molding, heating to 1100-. The invention can ensure the uniformity of the distribution of the dopant in the material, obtain ideal doping effect, and can not generate secondary pollution to the material, thereby ensuring the magnetic performance of the material.
Description
Technical Field
The invention belongs to the technical field of ferrite magnetic materials, and particularly relates to a method for preparing ferrite by using nano MnZn ferrite powder.
Background art:
as an important soft magnetic material, Mn — Zn ferrite has many excellent properties such as high magnetic permeability, high resistivity, low power loss, etc., and is widely used in the fields of electronic industry, information industry, etc. With the rapid development of these industries, electronic complete machine systems are developed in the directions of intellectualization, miniaturization and planar surface mounting, so that the power supply therein is required to be developed in a high frequency manner. The core of the high-frequency power supply is a ferrite material with high frequency and low loss. At high frequency, there are two main ways to reduce the power loss of the material, one is to increase the resistivity, and the other is to control the proper ferrite crystal grain (the crystal grain is too small, P is too small)eWill become smaller, but PhWill increase). The most effective way to control grain size and resistivity isPhysically incorporate additives and improve sintering properties. It is known to dope beneficial additives, such as SnO2、TiO2、Co2O3Etc. the Q value of the material can be further controlled to be very small in a wide temperature range, and CaO and SiO are added in a compounding way2The resistivity of the material can be increased, and the power loss of the material can be reduced.
In the conventional preparation process of Mn-Zn ferrite, various added raw materials are mechanically ground for a long time by a ball mill so as to achieve the aim of uniform mixing. As the raw materials have larger size (micron order), the doping of the Mn-Zn ferrite can basically achieve the expected purpose by adopting the mechanical ball milling way and matching with the improvement of a proper feeding procedure, namely, the added CaO and SiO2The oxide existing in the grain boundary plays a role in inhibiting the growth of ferrite grains, and the oxides of V and Nb are uniformly distributed in the grains. However, the obtained MnZn ferrite bulk material is liable to have unevenness in microscopic composition, structure and properties. In addition, high sintering temperature is likely to cause volatilization of low melting point elements (such as Zn), resulting in large deviation of the actual composition of the material from the designed value. Moreover, the ball milling in the medium environment for a plurality of times is easy to introduce foreign impurities, and secondary pollution is generated to the target product, and all the problems can influence the magnetic property of the final product. The research shows that: the preparation of uniform and fine powder plays an important role in modern ceramics, and especially in the electronic ceramic industry, people tend to adopt a chemical method to prepare powder materials. Although the initial cost of the raw materials prepared by the method is higher than that of the traditional solid-phase reaction method, the material performance is obviously improved, and the added value of the product is improved, so that the increase of the cost of the raw materials can be compensated. (Rozman M, et al, Hydrothermalsynthesis of great importance, J.Am.Ceram.Soc.,2010,78(9):2449-2455.) therefore, the preparation of high performance electronic devices by sintering of nanopowders has become the main direction of future development in this industry.
Because the nano powder prepared by a chemical method forms the target product MnZn ferrite, theoretically, the whole sintering process is to reduce the physical distance between particles, namely a densification process, so as to obtain the MnZn ferriteAnd the conventional processes such as calcination (pre-reaction between raw materials) and chemical reaction in the sintering process are omitted. In addition, the surface area of the nano particles is large, the reaction activity is high, the sintering temperature can be effectively reduced, and the energy consumption is saved. Nevertheless, a problem that must be faced is that, when the particle size of the ferrite main component becomes nanometer-scale, the particle size of the dopant to be added must be correspondingly reduced and should be smaller than that of the matrix component, otherwise for the particles such as CaO, SiO2Such high melting point dopants are difficult to be present at the intended designated locations, and there is a possibility that ferrite particles surround it, thereby causing deterioration in the magnetic properties of the material. The invention patent CN105016395B discloses a nano ferrite material and a preparation method thereof, which adopts nano ferrite particles (the particle diameter is less than or equal to 100nm) prepared by a hydrothermal method as a raw material, the uniformity of the main component of the ferrite can be ensured, but the auxiliary component B2O3And MoO3But is added by mechanical grinding. Since the patent does not report the details of these dopants, it is known that the particle size of these doped oxides should be relatively large (typically in the order of microns). It is thought that mixing of particles having a small addition amount (not more than 0.5 wt%) and a large size with nanoparticles having a small size and a total amount far exceeding that of the former (more than 99.5 wt%) by simple mechanical grinding is difficult to achieve uniform distribution of the former in the final mixed product. This should be the primary reason that the embodiments provided in this patent are not magnetically high. The invention patent CN101481243A discloses a method for directly preparing Mn-Zn ferrite material from nanocrystalline Mn-Zn ferrite powder, which adopts a sol-gel method to prepare Mn-Zn ferrite powder. The dopants CaO, V introduced in the patent claims2O5、TiO2And Nb2O5During the preparation of the nano powder, the nano powder is dissolved in a nitrate solution of Fe, Mn and Zn, and a uniform and transparent brown solution is formed by mixing and stirring. However, based on the chemical nature of these dopants, we know that TiO is the most important dopant2、Nb2O5Such oxides are not soluble in water at all, but only in hydrofluoric acid or concentrated acids. Thereby can beIt is inferred that these oxides, too, have a low solubility in the above-mentioned salt solutions and are present in the form of suspended particles during the above-mentioned nitrate solutions and the subsequent sol-gel formation (the formation of transparent solutions as described in the claims is questionable). The second phase particles in this form are also difficult to distribute uniformly in the final sintered material due to lack of subsequent processes such as mechanical grinding, and the properties of the material are difficult to develop sufficiently. The invention patent CN102731079A 'a method for preparing MnZn ferrite' relates to the coating modification of Mn-Zn ferrite nano powder prepared by a chemical coprecipitation method by using a silane coupling agent and a titanate coupling agent, and on one hand, the agglomeration of nano particles can be reduced and the fluidity and the forming capability of the nano particles can be improved by using the characteristic that hydrophilic groups of the coupling agent and the nano powder have better wettability; on the other hand, the characteristic that the oleophylic group in the coupling agent and the organic binder have better wettability is utilized, so that the utilization rate of the binder is improved; in a third aspect, the residual product SiO of the two coupling agents after high-temperature sintering2、TiO2And the ferrite can be used as a doping agent of ferrite, so that the aim of 'one dose for multiple purposes' can be fulfilled. This doping is inherently good, but not all dopants can be made into coupling agents. From the above analysis, it is known that the nano-sized MnZn ferrite prepared by the chemical method as the main component raw material can significantly reduce the unevenness of the chemical components and the structure of the ferrite and can reduce the sintering temperature. However, if the minor component is still mixed with the major component in the form of a micron-sized oxide having a larger size by mechanical milling, it is difficult to uniformly disperse the minor component in the major component because the amount thereof is small and the particle size is at least 1 to 2 orders of magnitude larger than that of the major component. If the doped oxide is added into the precursor solution of the main component, the doped oxide is almost insoluble in the salt solution of the precursor, thereby increasing the difficulty of uniformly dispersing the dopant in the main component, and consequently, the magnetic performance of the finally prepared power manganese-zinc ferrite is still poor.
The invention patents Z L201110237910.8 and CN1012731079A mainly add coupling agents for improving the dispersibility and the filling property of nano powder, and organic groups in the coupling agents areIs burned off during heating, and the residual inorganic component (such as SiO)2、TiO2) Although the MnZn ferrite can be doped and modified, the coupling agent has a large gas production amount after being heated and decomposed, so that the material is easy to crack, and the addition amount cannot be large, so that the doping and modifying effect is limited. In addition, the production cost of the coupling agent is high, and the kinds of coupling agents that can be produced are limited, and a coupling agent containing V, B, Mo and Ca is almost nonexistent. Thus, the use of this method is very limited.
The invention content is as follows:
the invention aims to provide a method for preparing ferrite by using nano MnZn ferrite powder aiming at the defects in the prior art. The method cancels the limitation on the specific preparation condition of the MnZn ferrite nano powder, and prepares the adulterant to be added into a uniform transparent water or ethanol solution to be mixed with the nano powder, thereby not only ensuring the distribution uniformity of the adulterant in the material and obtaining the ideal doping effect, but also not generating secondary pollution to the material, thereby ensuring the magnetic performance of the material.
The technical scheme adopted by the invention is as follows:
1. a method for preparing ferrite by nano MnZn ferrite powder comprises the following steps:
1) dissolving a coupling agent in absolute ethyl alcohol, performing ultrasonic dispersion for 20-30min, then adding manganese-zinc ferrite nano powder, continuing ultrasonic dispersion and stirring for 1-2h, and drying to obtain dried powder;
wherein, 5g of manganese zinc ferrite nano powder is added into 10-30ml of absolute ethyl alcohol, and the mass of the coupling agent is 2-5% of the mass of the nano powder;
2) preparing a dopant solution, namely dissolving a dopant in water or absolute ethyl alcohol to prepare the dopant solution with the mass concentration of 0.05-60 g/L;
the dopant is one or more of a silicon source, a titanium source, a calcium source, a boron source, a vanadium source and a molybdenum source; the silicon source is ethyl silicate, vinyl trimethoxy silane or vinyl triethoxy silane; the calcium source is calcium acetate or calcium nitrate; the titanium source is titanium alkoxide or titanium monoalkoxytricarboxylate; the boron source is boric acid or trimethyl borate, the vanadium source is ammonium vanadate, and the molybdenum source is ammonium molybdate;
3) adding an organic binder into deionized water, carrying out ultrasonic treatment for 30-60min to obtain an organic binder solution, then adding the dopant solution obtained in the step 2), and stirring to form a mixed solution;
wherein, volume ratio dopant solution: organic binder solution 1: 0.5-2; the mass percentage concentration of the binder solution is 0.8-1.6%;
4) adding the dried powder in the step 1) into the mixed solution in the step 3), and carrying out ultrasonic treatment at 65-75 ℃ until the liquid is evaporated to dryness; grinding and sieving the obtained powder, and injecting the powder into a mold for pressure molding to obtain a biscuit;
wherein, the organic binder is manganese zinc ferrite nano powder with the mass of 4-8 percent;
5) and (3) sintering: and heating the biscuit to 1100-1250 ℃ in a protective atmosphere, preserving the heat for 3-5h, and then cooling to room temperature to obtain the ferrite.
The organic binder is polyvinyl alcohol (PVA for short).
The protective atmosphere is nitrogen, argon or carbon dioxide.
The coupling agent is KH-171 silane coupling agent, L D-139 aluminum zirconium coupling agent or PF-901 aluminum titanium composite coupling agent.
In the dopant solution, the concentration is 0.05-0.27 g/L when the dopant is a silicon source, 5-60 g/L when the dopant is a titanium source, 1.4-8.5 g/L when the dopant is a calcium source, 0.4-4.5 g/L when the dopant is a boron source, 0.3-2.7 g/L when the dopant is a vanadium source, and 0.3-3.2 g/L when the dopant is a molybdenum source.
The titanium alkoxide is butyl titanate, propyl titanate or ethyl titanate.
The nano MnZn ferrite powder is a known material and has a structural formula of Mn1-xZnxFe2O4(0.2<x<0.5), particle size: 20-100 nm.
The invention has the technical characteristics that:
the invention utilizes Mn-Zn ferrite nano powderAccording to the magnetic property requirement of the ferrite with low loss power, the doped oxides and the compounds for forming the oxides are selected in a targeted manner, so that the doped oxides and the compounds for forming the oxides can be fully dissolved in water or ethanol to form a uniform transparent solution, then the uniform transparent solution is mixed with uniformly dispersed nano ferrite powder, and the ferrite with uniform microstructure and good magnetic property can be prepared through the treatment processes of drying, pressurizing, forming, sintering and the like. On one hand, the dopant is added into the nano powder in a liquid mode, and the dispersion degree of the dopant is far higher than that of the dopant in a mechanical mixing mode; on the other hand, the dopant is not directly added in the form of an oxide, but is mixed with the nanopowder in the form of a compound that is easily decomposed by heat. These compounds are susceptible to decomposition during sintering, with the resulting water or organic components escaping from the material and the remaining inorganic components becoming doped oxides (e.g. SiO) which improve the ferrite properties2、TiO2、CaO、B2O3、V2O5、MoO3) Finally, the magnetic performance of the prepared ferrite is obviously improved.
The invention has the beneficial effects that:
1. the MnZn ferrite nano powder adopted by the invention is not limited to a special chemical preparation method, and the application range of the invention is widened, so that the dependence on certain raw materials in the process of preparing the nano powder is reduced.
2. The invention firstly prepares the adulterant to be added into a uniform solution and then mixes the solution with the Mn-Zn ferrite nano powder, thereby firstly increasing the uniformity of the dispersion of the adulterant in the nano powder and secondly decomposing the adulterant to form the adulterant required by the power MnZn ferrite in the heating process. The problems of low doping efficiency and the like caused by excessively large and thick sizes of the dopants can be avoided, the dosage of the dopants can be saved, and the utilization rate of materials is improved.
3. Compared with the patents (Z L201110237910.8 and CN102731079A) of the invention that the MnZn ferrite nano powder prepared by a chemical coprecipitation method is used as a raw material to prepare the bulk material in recent years, the Bs of the power MnZn ferrite prepared by the invention is improved under the condition that the density is basically the same or is improved, and the initial magnetic permeability is more than 850. compared with the patent (CN101481243A) of the invention that the MnZn ferrite nano powder is used as a raw material, the power MnZn ferrite prepared by the invention can reach or exceed the magnetic performance level of the patent of the invention of CN101481243A only by adding one or two oxides, the density of the obtained material is improved by about 4.5 percent, the service life of the material is prolonged, the manufacturing cost of the material is saved, and compared with the patent (CN105016395B) of the invention that the NiZn ferrite nano material is used as a raw material, the MnZn ferrite provided by the invention has the initial magnetic permeability improved by at least 3 times under the condition that the saturation magnetic induction intensity Bs is similar or is improved.
Drawings
FIG. 1 is an XRD spectrum of manganese zinc ferrite nanopowder.
Fig. 2 is an XRD spectrum of the sintered bulk material doped with different kinds of oxides obtained in example 1, example 3, example 7 and example 8.
FIG. 3 shows doping B in example 42O3The microstructure of the sample.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
In the materials related to the invention, the coupling agent is a commercially available KH-171 silane coupling agent, L D-139 aluminum zirconium coupling agent and PF-901 aluminum titanium composite coupling agent;
the nano MnZn ferrite powder is a known material and has a structural formula of Mn1-xZnxFe2O4(0.2<x<0.5) this example is Mn0.7Zn0.3Fe2O4. The material can be prepared by a chemical coprecipitation method, a sol-gel method, a hydrothermal synthesis method or the like, and is powder with uniform chemical components, wherein the particle size is as follows: 20-100 nm.
Example 1
Step 1), weighing 5g of manganese zinc ferrite nano powder (shown in figure 1a, the powder diameter is about 70nm) prepared by a chemical coprecipitation method, weighing L D-139 aluminum zirconium coupling agent according to the mass ratio of 3.5% of the manganese zinc ferrite nano powder, dissolving the powder in 20ml of absolute ethyl alcohol, carrying out ultrasonic vibration for 20min, then adding the manganese zinc ferrite nano powder, carrying out ultrasonic dispersion and stirring for 2h, and drying.
Step 2), 0.003g of ethyl silicate was added to 20ml of an anhydrous ethanol solution (containing SiO)2The mass is 0.02 percent of the MnZn ferrite nano powder mass).
And 3) weighing 0.4g of organic binder according to the proportion that PVA accounts for 8% of the mass of the manganese-zinc ferrite nano powder, adding 25ml of deionized water (the mass percentage concentration of the folded PVA is 1.6%), and carrying out ultrasonic treatment for 30 min. And adding the solution obtained in the step 2), and stirring to form a uniform solution.
And 4) adding all the dried powder in the step 1) into the uniform solution in the step 3), and carrying out ultrasonic treatment at 70 ℃ until the liquid is evaporated to dryness. And grinding the obtained powder, sieving the powder by a 100-mesh sieve, injecting the powder into a mould, and performing pressure molding to obtain the annular biscuit.
Step 5), sintering the molded sample at 1200 ℃ for × 3h in argon atmosphere, wherein the XRD spectrum of the obtained material is shown as figure 2a, and the XRD peak completely corresponds to the MnZn ferrite standard substance, which shows that SiO is generated2The addition of (a) does not change the crystal structure of the material, and the product formed after sintering is still MnZn ferrite. The density of the resulting ring-shaped sample was 5.02g/cm3The initial permeability was 850, and the saturation magnetic induction Bs was 425 mT.
Example 2
Step 1), weighing 5g of manganese-zinc ferrite nano powder (shown in figure 1a, the diameter of the powder is about 70nm) prepared by a chemical coprecipitation method, weighing a KH-171 silane coupling agent according to the mass ratio of 2.5% to the nano powder, dissolving the KH-171 silane coupling agent in 15ml of absolute ethyl alcohol, and ultrasonically vibrating for 30 min. Then adding manganese zinc ferrite nano powder, carrying out ultrasonic dispersion and stirring for 1.5h, and drying.
Step 2), 0.255g of tetrabutyl titanate is added into 20ml of absolute ethanol solution (containing TiO)2The mass is 1.2 percent of the MnZn ferrite nano powder mass).
Step 3), weighing 0.25g of organic binder according to the proportion that PVA accounts for 5% of the mass of the manganese-zinc ferrite nano powder, adding 23.1ml of deionized water (the mass percentage concentration of the PVA is 1.1%), and carrying out ultrasonic treatment for 45 min. And adding the solution obtained in the step 2), and stirring to form a uniform solution.
And 4) adding all the dried powder in the step 1) into the uniform solution in the step 3), and carrying out ultrasonic treatment at 70 ℃ until the liquid is evaporated to dryness. And grinding the obtained powder, sieving the powder by a 100-mesh sieve, injecting the powder into a mould, and performing pressure molding to obtain the annular biscuit.
Step 5), putting the molded sample in CO2Sintering at 1150 deg.C for × 5h in atmosphere to obtain ring sample with density of 5.01g/cm3The initial permeability is 850, and the saturation magnetic induction Bs is 420 mT.
Example 3
Step 1), weighing 5g of manganese-zinc ferrite nano powder prepared by a sol-gel method (the powder diameter is about 75nm in figure 1 b), weighing a PF-901 aluminum-titanium composite coupling agent according to the proportion of 5% of the mass of the nano powder, dissolving the PF-901 aluminum-titanium composite coupling agent in 30ml of absolute ethyl alcohol, and ultrasonically vibrating for 20 min. Then adding manganese zinc ferrite nano powder, carrying out ultrasonic dispersion and stirring for 1h, and drying.
Step 2), 0.071g of calcium acetate is added into 20ml of the aqueous solution (the mass of CaO contained is 0.5 percent of the mass of MnZn ferrite nano powder).
Step 3), weighing 0.2g of organic binder according to the proportion that PVA accounts for 4% of the mass of the manganese-zinc ferrite nano powder, adding 22.5ml of deionized water (the mass percentage concentration of the PVA is 0.89%), and carrying out ultrasonic treatment for 60 min. And adding the solution obtained in the step 2), and stirring to form a uniform solution.
And 4) adding all the dried powder in the step 1) into the uniform solution in the step 3), and carrying out ultrasonic treatment at 70 ℃ until the liquid is evaporated to dryness. And grinding the obtained powder, sieving the powder by a 100-mesh sieve, injecting the powder into a mould, and performing pressure molding to obtain the annular biscuit.
Step 5), sintering the molded sample at 1250 ℃ for × 3h in nitrogen atmosphere, wherein the XRD spectrum of the obtained material is shown as figure 2b, the XRD peak completely corresponds to that of MnZn ferrite standard substance, which indicates that the addition of CaO does not change the crystal structure of the material, the product formed after sintering is still MnZn ferrite, and the density of the obtained annular sample is 5.03g/cm3Initial permeability of 900, saturation magnetic induction Bs 450mT。
Example 4
Step 1), weighing 5g of manganese zinc ferrite nano powder prepared by a sol-gel method (the powder diameter is about 75nm in figure 1 b), weighing L D-139 aluminum zirconium coupling agent according to the proportion of 3% of the mass of the nano powder, dissolving the coupling agent in 30ml of absolute ethyl alcohol, carrying out ultrasonic vibration for 30min, then adding the manganese zinc ferrite nano powder, carrying out ultrasonic dispersion and stirring for 2h, and drying.
Step 2), 0.022g of trimethyl borate was added to 20ml of an anhydrous ethanol solution (containing B)2O3The mass is 0.15 percent of the MnZn ferrite nano powder mass).
And 3) weighing 0.2g of organic binder according to the proportion that PVA accounts for 4% of the mass of the manganese-zinc ferrite nano powder, adding 22.5ml of deionized water (the mass percentage concentration of the PVA is 0.89%), and carrying out ultrasonic treatment for 45 min. And adding the solution obtained in the step 2), and stirring to form a uniform solution.
And 4) adding all the dried powder in the step 1) into the uniform solution in the step 3), and carrying out ultrasonic treatment at 70 ℃ until the liquid is evaporated to dryness. And grinding the obtained powder, sieving the powder by a 100-mesh sieve, injecting the powder into a mould, and performing pressure molding to obtain the annular biscuit.
Step 5), putting the molded sample in CO2The density of the obtained annular sample is 5.06g/cm after the sintering treatment at the middle temperature of 1200 ℃ for × 3 hours3The initial permeability is 1100, and the saturation magnetic induction Bs is 460 mT. The microstructure of the sample is shown in fig. 3, wherein the defects such as uniform grain size and small pores are small, which should be the main reasons for high compactness and good magnetic performance. Description of B2O3The boric acid is introduced into the manganese-zinc ferrite in the form of boric acid, so that excessive defects of the material can not be generated, and an ideal microstructure can be obtained by reasonably controlling a sintering process.
Example 5
Step 1), weighing 5g of manganese-zinc ferrite nano powder (shown in figure 1c, the powder diameter is about 80nm) prepared by a solvothermal method, weighing a PF-901 aluminum-titanium composite coupling agent according to the proportion of 4% of the mass ratio of the powder to the nano powder, dissolving the coupling agent in 20ml of absolute ethyl alcohol, and ultrasonically vibrating for 20 min. Then adding manganese zinc ferrite nano powder, carrying out ultrasonic dispersion and stirring for 1.2h, and drying.
Step 2), 0.032g of ammonium vanadate and 0.035g of boric acid are added to 20ml of the aqueous solution (containing V)2O5And B2O3The mass is 0.5 percent and 0.4 percent of MnZn ferrite nano powder respectively).
Step 3), weighing 0.25g of organic binder according to the proportion that PVA accounts for 5% of the mass of the manganese-zinc ferrite nano powder, adding 23.1ml of deionized water (the mass percentage concentration of the PVA is 1.1%), and carrying out ultrasonic treatment for 50 min. And adding the solution obtained in the step 2), and stirring to form a uniform solution.
And 4) adding all the dried powder in the step 1) into the uniform solution in the step 3), and carrying out ultrasonic treatment at 70 ℃ until the liquid is evaporated to dryness. And grinding the obtained powder, sieving the powder by a 100-mesh sieve, injecting the powder into a mould, and performing pressure molding to obtain the annular biscuit.
Step 5), putting the molded sample in N2The density of the obtained annular sample is 5.02g/cm after the sintering treatment at the middle 1200 ℃ for × 4h3The initial permeability was 1160, and the saturation magnetic induction Bs was 500 mT.
Example 6
Step 1), weighing 5g of manganese-zinc ferrite nano powder (with the powder diameter being about 80nm in figure 1 c) prepared by a solvothermal method, weighing a KH-171 silane coupling agent according to the mass ratio of 2.5% to the nano powder, dissolving the KH-171 silane coupling agent in 15ml of absolute ethyl alcohol, and ultrasonically vibrating for 20 min. Then adding manganese zinc ferrite nano powder, carrying out ultrasonic dispersion and stirring for 1.5h, and drying.
Step 2), 0.034g of ammonium molybdate and 0.028g of calcium acetate were added to 20ml of the aqueous solution (containing MoO)3And CaO in an amount of 0.5% and 0.2% by mass, respectively, based on the mass of the MnZn ferrite nanopowder).
Step 3), weighing 0.275g of organic binder according to the proportion that PVA accounts for 5.5 percent of the mass of the manganese-zinc ferrite nano powder, adding 23.4ml of deionized water (the mass percentage concentration of the PVA is 1.2 percent), and carrying out ultrasonic treatment for 60 min. And adding the solution obtained in the step 2), and stirring to form a uniform solution.
And 4) adding all the dried powder in the step 1) into the uniform solution in the step 3), and carrying out ultrasonic treatment at 70 ℃ until the liquid is evaporated to dryness. And grinding the obtained powder, sieving the powder by a 100-mesh sieve, injecting the powder into a mould, and performing pressure molding to obtain the annular biscuit.
Step 5), sintering the molded sample at 1200 ℃ for × 3h in argon atmosphere to obtain an annular sample with the density of 5.06g/cm3The initial permeability is 1170, and the saturation induction Bs is 475 mT.
Example 7
Step 1), weighing 5g of manganese-zinc ferrite nano powder (shown in figure 1a, the powder diameter is about 70nm) prepared by a chemical coprecipitation method, weighing L D-139 aluminum-zirconium coupling agent according to the proportion of 4% of the mass of the nano powder, dissolving the obtained product in 10ml of absolute ethyl alcohol, carrying out ultrasonic vibration for 20min, then adding the manganese-zinc ferrite nano powder, carrying out ultrasonic dispersion and stirring for 1h, and drying.
Step 2) 0.03g of trimethyl borate and 0.881g of titanium monoalkoxytricarboxylate were added to 20ml of an anhydrous ethanol solution (containing B)2O3And TiO2The mass of the MnZn ferrite nano powder is 0.2 percent and 1.5 percent respectively
Step 3), weighing 0.35g of organic binder according to the proportion that PVA accounts for 7% of the mass of the manganese-zinc ferrite nano powder, adding 24.4ml of deionized water (the mass percentage concentration of the PVA is 1.4%), and carrying out ultrasonic treatment for 60 min. And adding the solution obtained in the step 2), and stirring to form a uniform solution.
And 4) adding all the dried powder in the step 1) into the uniform solution in the step 3), and carrying out ultrasonic treatment at 70 ℃ until the liquid is evaporated to dryness. And grinding the obtained powder, sieving the powder by a 100-mesh sieve, injecting the powder into a mould, and performing pressure molding to obtain the annular biscuit.
Step 5), putting the molded sample in CO2The XRD spectrum of the obtained material is shown in figure 2c when the sintering treatment is carried out at 1220 ℃ for × 5h, wherein the XRD peak completely corresponds to that of MnZn ferrite standard substance, which shows that B2O3And TiO2The addition of (a) does not change the crystal structure of the material, and the product formed after sintering is still MnZn ferrite. The density of the resulting ring-shaped sample was 5.10g/cm3The initial permeability is 1200, and the saturation magnetic induction Bs is 512 mT.
Example 8
Step 1), weighing 5g of manganese-zinc ferrite nano powder prepared by a sol-gel method (the powder diameter is about 75nm in figure 1 b), weighing KH-171 silane coupling agent according to the mass ratio of 3.5% to the nano powder, dissolving the KH-171 silane coupling agent in 15ml of absolute ethyl alcohol, and ultrasonically vibrating for 20 min. Then adding manganese zinc ferrite nano powder, carrying out ultrasonic dispersion and stirring for 1.5h, and drying.
Step 2) 0.003g of ethyl silicate and 0.063g of calcium nitrate are added to 20ml of absolute ethanol solution (containing SiO)2And CaO in an amount of 0.02% and 0.3% by mass, respectively, of the MnZn ferrite nanopowder.
Step 3), weighing 0.3g of organic binder according to the proportion that PVA accounts for 6% of the mass of the manganese-zinc ferrite nano powder, adding 23.8ml of deionized water (the mass percentage concentration of the PVA is 1.3%), and carrying out ultrasonic treatment for 60 min. And adding the solution obtained in the step 2), and stirring to form a uniform solution.
And 4) adding all the dried powder in the step 1) into the uniform solution in the step 3), and carrying out ultrasonic treatment at 70 ℃ until the liquid is evaporated to dryness. And grinding the obtained powder, sieving the powder by a 100-mesh sieve, injecting the powder into a mould, and performing pressure molding to obtain the annular biscuit.
Step 5), putting the molded sample in N2The XRD spectrum of the obtained material is shown in figure 2d when the sintering treatment is carried out at 1240 ℃ for × 4h, wherein the XRD peak completely corresponds to that of MnZn ferrite standard substance, which indicates that SiO is2And the addition of CaO does not change the crystal structure of the material, and the product formed after sintering is still MnZn ferrite. The density of the resulting ring-shaped sample was 5.06g/cm3The initial permeability is 1050, and the saturation magnetic induction Bs is 455 mT.
The MnZn ferrite prepared by the embodiment has a remarkable characteristic of high density rho (the relative theoretical density is more than 95 percent), which is inseparable from the addition form of the dopant of the invention. In addition, for power ferrite, in order to ensure low power loss and high saturation magnetic induction, it is often necessary to add a proper amount of oxide (e.g., SiO)2、TiO2CaO, etc.) to control the grain size of the material and increase its resistivity. However, these dopants are all non-magnetic materialsWhen the power MnZn ferrite is prepared by the traditional method, the introduction of the MnZn ferrite often causes the great reduction of the magnetic permeability of the material. It is noted that the invention adds only 0.15% B to example 4 when only one dopant is added2O3The MnZn ferrite can simultaneously obtain higher saturation magnetic induction intensity and initial magnetic permeability. Inventive example 5 (0.5% V) when both dopants were added simultaneously2O5-0.4％B2O3Composite addition), example 6 (0.5% MoO)30.2% CaO complex addition) and example 7 (0.2% B)2O3-1.5％TiO2Compound addition) can be obtained, and the saturation magnetic induction intensity and the initial magnetic permeability of the obtained ferrite are improved to different degrees. Of these, the MnZn ferrite density obtained in example 7 is already very close to the theoretical value (5.12 g/cm)3) And the initial permeability and saturation induction are also at the highest level. These values are compared with the simple addition of SiO2The results of example 1 are 1.6%, 26.3% and 20.5%, which shows that the doping effect of the simultaneous addition of multiple oxides is better. This should be beneficial in that when uniformly distributed oxide particles are present in the MnZn ferrite at the same time, their interaction allows further amplification of their beneficial effect on the magnetic properties of the material. On the other hand, the significant reduction in particle size in turn allows the adverse effect on the magnetic properties of the material to be significantly reduced.
The invention is not the best known technology.
Claims (6)
1. A method for preparing ferrite by nano MnZn ferrite powder is characterized by comprising the following steps:
(1) dissolving a coupling agent in absolute ethyl alcohol, performing ultrasonic dispersion for 20-30min, then adding manganese-zinc ferrite nano powder, continuing ultrasonic dispersion and stirring for 1-2h, and drying to obtain dried powder;
wherein, 5g of manganese zinc ferrite nano powder is added into 10-30ml of absolute ethyl alcohol, and the mass of the coupling agent is 2-5% of the mass of the nano powder;
(2) preparing a dopant solution, namely dissolving a dopant in water or absolute ethyl alcohol to prepare the dopant solution with the mass concentration of 0.05-60 g/L;
the dopant is one or more of a silicon source, a titanium source, a calcium source, a boron source, a vanadium source and a molybdenum source; the silicon source is ethyl silicate, vinyl trimethoxy silane or vinyl triethoxy silane; the calcium source is calcium acetate or calcium nitrate; the titanium source is titanium alkoxide or titanium monoalkoxytricarboxylate; the boron source is boric acid or trimethyl borate, the vanadium source is ammonium vanadate, and the molybdenum source is ammonium molybdate;
(3) adding an organic binder into deionized water, carrying out ultrasonic treatment for 30-60min to obtain an organic binder solution, then adding the dopant solution obtained in the step 2), and stirring to form a mixed solution;
wherein, volume ratio dopant solution: organic binder solution =1: 0.5-2; the mass percentage concentration of the binder solution is 0.8-1.6%;
(4) adding the dried powder in the step 1) into the mixed solution in the step 3), and carrying out ultrasonic treatment at 65-75 ℃ until the liquid is evaporated to dryness; grinding and sieving the obtained powder, and injecting the powder into a mold for pressure molding to obtain a biscuit;
wherein, the organic binder is manganese zinc ferrite nano powder with the mass of 4-8 percent;
(5) and (3) sintering: and heating the biscuit to 1100-1250 ℃ in a protective atmosphere, preserving the heat for 3-5h, and then cooling to room temperature to obtain the ferrite.
2. The method for preparing ferrite using nano MnZn ferrite powder as claimed in claim 1, wherein said organic binder is polyvinyl alcohol.
3. The method for preparing ferrite using nano MnZn ferrite powder as claimed in claim 1, wherein the protective atmosphere is nitrogen, argon or carbon dioxide.
4. The method for preparing ferrite from nano MnZn ferrite powder as claimed in claim 1, wherein the coupling agent is KH-171 silane coupling agent, L D-139 aluminum zirconium coupling agent or PF-901 aluminum titanium composite coupling agent.
5. The method for preparing ferrite using nano MnZn ferrite powder as claimed in claim 1, wherein the dopant solution has a concentration of 0.05-0.27 g/L when the dopant is a silicon source, a concentration of 5-60 g/L when the dopant is a titanium source, a concentration of 1.4-8.5 g/L when the dopant is a calcium source, a concentration of 0.4-4.5 g/L when the dopant is a boron source, a concentration of 0.3-2.7 g/L when the dopant is a vanadium source, and a concentration of 0.3-3.2 g/L when the dopant is a molybdenum source.
6. The method for preparing ferrite using nano MnZn ferrite powder as claimed in claim 1, wherein the titanium alkoxide is butyl titanate, propyl titanate or ethyl titanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810030787.4A CN108046791B (en) | 2018-01-12 | 2018-01-12 | Method for preparing ferrite from nano MnZn ferrite powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810030787.4A CN108046791B (en) | 2018-01-12 | 2018-01-12 | Method for preparing ferrite from nano MnZn ferrite powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108046791A CN108046791A (en) | 2018-05-18 |
| CN108046791B true CN108046791B (en) | 2020-08-04 |
Family
ID=62127145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810030787.4A Expired - Fee Related CN108046791B (en) | 2018-01-12 | 2018-01-12 | Method for preparing ferrite from nano MnZn ferrite powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108046791B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087516B (en) * | 2021-03-31 | 2022-07-22 | 重庆上甲电子股份有限公司 | Low-temperature sintering method for preparing manganese-zinc ferrite by using industrial wastes |
| CN114195501B (en) * | 2022-01-10 | 2022-06-28 | 深圳信义磁性材料有限公司 | High-permeability high-impedance manganese-zinc ferrite and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311262A (en) * | 2011-08-18 | 2012-01-11 | 河北工业大学 | Method for preparing MnZn ferrite with adding silane coupling agent |
| CN102731079A (en) * | 2012-07-02 | 2012-10-17 | 河北工业大学 | Method for preparing MnZn ferrite |
| CN103165881A (en) * | 2011-12-12 | 2013-06-19 | 张健 | Lithium iron phosphate doped nanometer anode material and preparation method thereof |
-
2018
- 2018-01-12 CN CN201810030787.4A patent/CN108046791B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311262A (en) * | 2011-08-18 | 2012-01-11 | 河北工业大学 | Method for preparing MnZn ferrite with adding silane coupling agent |
| CN103165881A (en) * | 2011-12-12 | 2013-06-19 | 张健 | Lithium iron phosphate doped nanometer anode material and preparation method thereof |
| CN102731079A (en) * | 2012-07-02 | 2012-10-17 | 河北工业大学 | Method for preparing MnZn ferrite |
Non-Patent Citations (1)
| Title |
|---|
| 偶联剂对Mn-Zn铁氧体颗粒分散性及磁性能的影响;侯强;《人工晶体学报》;20130131;第42卷(第1期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108046791A (en) | 2018-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104230323B (en) | M type calcium lanthanum cobalt permanent-magnet ferrite and preparation method thereof | |
| TWI245742B (en) | Method for manufacturing highly-crystallized oxide powder | |
| CN102923770B (en) | Preparation method of yttrium-stabilized nanometer zirconium dioxide powder | |
| CN101698609B (en) | Method for preparing spherical, monodisperse and single-size yttrium oxide nano-powder | |
| CN101152981B (en) | Application of nano material in ferrite | |
| CN104230326B (en) | The preparation method of M type calcium permanent ferrite | |
| CN102190499A (en) | Preparation method of transparent yttria ceramic | |
| CN108046791B (en) | Method for preparing ferrite from nano MnZn ferrite powder | |
| CN104230325A (en) | Preparation method of permanent magnetic ferrite pre-sintering material and preparation method of permanent magnetic ferrite | |
| Jing et al. | High efficiency synthesis of Nd: YAG powder by a spray co-precipitation method for transparent ceramics | |
| CN104230321B (en) | M type calcium permanent ferrites and preparation method thereof | |
| CN109052450B (en) | Preparation method of high-purity gadolinium oxide | |
| CN109036753A (en) | A kind of amorphous nano-crystalline composite magnetic powder core and preparation method thereof | |
| CN101844784A (en) | Alpha-Al2O3 nanostructure aggregate material and preparation method thereof | |
| WO2011115128A1 (en) | Manufacturing method for ferrite sintered magnet, magnetic powder, kneaded product and molded article | |
| CN104230322A (en) | M-type calcium permanent magnetic ferrite and preparation method thereof | |
| CN102190484A (en) | Preparation method for YAG (yttrium aluminum garnet) transparent ceramic | |
| CN101905971A (en) | Method for preparing rare-earth ion doped yttrium aluminum garnet laser ceramics | |
| CN102992377A (en) | Method for preparing nano rare earth oxide through microwave sol-gel technology | |
| CN115180945A (en) | Iron-based garnet magneto-optical transparent ceramic and preparation method thereof | |
| CN103864425B (en) | Preparation method of microwave dielectric ceramic material | |
| CN112591801A (en) | Preparation method of Z-shaped hexaferrite ultrafine powder | |
| CN112194482A (en) | Ultralow-loss wide-temperature-power MnZn ferrite, preparation method and application thereof in 5G communication field | |
| CN111039669A (en) | High-strength anti-deformation manganese-zinc ferrite and preparation method thereof | |
| CN111253152B (en) | Fast-attenuation high-light-efficiency scintillation material 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200804 Termination date: 20220112 |