CN1228272C - Prepn of doped magnetic ferrite material - Google Patents
Prepn of doped magnetic ferrite material Download PDFInfo
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- CN1228272C CN1228272C CN 03116206 CN03116206A CN1228272C CN 1228272 C CN1228272 C CN 1228272C CN 03116206 CN03116206 CN 03116206 CN 03116206 A CN03116206 A CN 03116206A CN 1228272 C CN1228272 C CN 1228272C
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Abstract
The present invention relates to a method for preparing doped ferrite magnetic materials, which belongs to the technical field of a magnetic material preparing technology. The method of the present invention adopts the technical scheme that firstly, under an acid condition, metal nitrate solution and citric acid solution are mixed; then metal nitrate solution to be doped is added according to requirements, the pH value of the solution is regulated, and one kind of wet gel solution is generated by a liquid phase reaction; after the excessive moisture of the wet gel solution is evaporated on an electric furnace, gel is formed; the formed gel is pre-baked at a certain temperature, and doped nanometer crystalline ferrite powder is obtained; after the doped ferrite powder is pressed into a required shape, the doped ferrite magnetic materials can be prepared by sintering. A doping process of the method of the present invention is carried out in a stoichiometric collosol stage, and thus, the distribution of the prepared doped ferrite magnetic materials is uniform. Simultaneously, because two ball milling processes are omitted, the present invention has the advantages of short production period, low energy consumption, accurate stoichiometry, easy control, high repeatability and good transplantation performance, and is favorable to industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of ferrite doped calcium magneticsubstance, belong to the magneticsubstance preparing technical field.
Background technology
Ferrite be develop the earliest, a most widely used class has the oxidate magnetic material of ferrimagnetism, because of its resistivity far above metallicl magnetic material, and at high frequency, pulse, microwave and optical frequency wave band, obtained aspect scientific and technical using widely in radio electronics, communication, microwave electronics and information storage and processing etc.Along with science and technology development, more and more higher requirement is proposed also the ferrite magnetic material quality.At present, improvement ferrite performance, adjusting magnetic parameter generally are to realize by doping way in ferrite.The adulterating method of prior art all is to adopt traditional solid reaction process, has both used metal oxide, carbonate, as: Fe
2O
3, ZnO, NiO, MnCO
3Deng being raw material, its preparation technology mainly is: batching → ball milling 1 → give burning → ball milling 2 → granulation → moulding → sintering → finished product.And the doping process is generally carried out during ball milling in the second time, and the oxide compound that need to be about to adulterated trace metal joins in the ferritic body material carrying out the second time during ball milling, then through granulation, moulding, sintering, forms finished product at last.But have some critical limitations in traditional processing method: the first, the traditional technology production cycle is long.The second, traditional technology needs a person with the qualifications of a general and expects long-time heating at high temperature, will cause the evaporation of some elements like this and has changed original stoichiometry.For example, in NiZn was ferrite sintered, the volatilization of zinc when high temperature can cause Fe
2+Ionic forms, and has increased the frequent activity of electronics thus and cause the minimizing of specific resistance.The 3rd, the operating process meeting of long period ball milling causes the loss of stoichiometry material and sneaks into the impurity of nonstoichiometric composition.Because the existence of these factors can cause that skew, the technological process on the technical recipe easily introduced impurity, the portability of product, poor repeatability, quality product is wayward, finally causes the change of product performance, and can't reach the performance requriements of expection.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of ferrite doped calcium magneticsubstance, with overcome exist in the traditional technology method sinter phase temperature height into, length, grain-size, doping are difficult for the problem accurately controlled to sintering time relatively.
When solution when the neutral slant acidity, citric acid in the solution can form a kind of reticulated structure, metal or nonmetallic ion can be dispersed in this reticulated structure uniformly, after moisture evaporation is fallen a part in the solution, this structure can form gel, during with gel pre-burning at a certain temperature, the organic composition in the gel can burn, and metal ion has formed in combustion processes through adulterated ferrite powder.The inventive method is utilized this principle exactly, at first under acidic conditions, metal-nitrate solutions is mixed with citric acid solution, add on demand then and want adulterated metal-nitrate solutions, re-adjustment solution pH value, generate a kind of wet gel solution through liquid phase reaction, this wet gel solution is boiled off excessive moisture on electric furnace, when film appears in liquid level, stop heating.Gel pre-burning at a certain temperature with forming just can obtain adulterated nanocrystalline ferrite powder.
According to above-mentioned principle, the inventive method adopts following technical scheme:
A. raw material is equipped with: take by weighing iron nitrate, nickelous nitrate, zinc nitrate according to required proportioning, the nitrate of adulterated metal an amount of and with metal nitrate with etc. the citric acid of mol ratio configuration, and be mixed with the aqueous solution respectively;
B. preparing gel: reactor is fixed in the thermostatted, temperature is controlled at 40-90 ℃, with iron nitrate, nickelous nitrate, zinc nitrate, citric acid and want the nitrate solution of adulterated metal to add in the reactor successively, constant temperature stirred 30-120 minute, when stirring, drip basic solution, to the pH value of solution value be 5-7, form cyan wet gel solution this moment;
The preparation of c. nanocrystalline pre-burning powder: above-mentioned wet gel solution is evaporated to remove most water, when film appears in liquid level, stop heating, this moment, wet gel will become gel, this gel is placed in the sintering oven, and at 300-600 ℃ of following pre-burning 10-30 minute, this moment, gel became fluffy powder russet, be the ferrite doped calcium powder, its grain-size is 20-60nm;
D. the preparation of ferrite magnetic material: with above-mentioned ferrite doped calcium powder, after grinding, granulation, after being pressed into required shape, put into atmosphere furnace, with per hour 130 degree speed intensification, and 1000 ℃ of-1300 ℃ of sintering temperatures 30 minutes, furnace cooling can make the ferrite doped calcium magneticsubstance then.
Compare with prior art, the inventive method has following conspicuous outstanding feature and remarkable advantage:
1. be entrained in stoichiometric sol phase and carry out, be uniformly dispersed; Omit two mechanical milling processes, shortened the production cycle, cut down the consumption of energy, helped suitability for industrialized production;
2. owing to save traditional ball-milling technology, thus the present invention to put the prescription stoichiometry of sending out accurate, control easily, good reproducibility, transplantability is good, particularly the needs trace is added adulterated ferrite technology operation commonly used, and control very accurately can be arranged.
3. sintering temperature is starkly lower than traditional technology, and sintering time shortens greatly.Directly granulation of nano crystal iron oxysome after the pre-burning, moulding, sintering; Can control grain-size by different sintering temperatures, thereby reach needed microtexture, obtain the polycrystalline material of the electromagnetic performance that requires.
Description of drawings
Fig. 1 is for mixing in difference under cobalt (0,0.1wt%, 0.4wt%, 0.8wt%, the 1.2wt%) situation, and sample is at 30 minutes magnetic spectrum of 1200 ℃ of sintering.
Fig. 2 is for to mix under copper (0.1wt%, 0.4wt%, 0.8wt%, the 1.2wt%) situation in difference, and sample is at 30 minutes magnetic spectrum of 1100 ℃ of sintering.
Embodiment
Embodiment one: take by weighing chemical purity and be 98% Ni (NO
3)
26H
2O 112.66 grams, purity is 99% Zn (NO
3)
26H
20 76.06 grams, purity is 98% Fe (NO
3)
39H
2O 521.76 grams, purity is 99% C
6H
8O
7H
2O 400.89 grams and the salt Co (NO that wants adulterated metal ion
3) 6H
2O is an amount of; Be configured to the aqueous solution respectively with deionized water 354ml.Wide mouth cup is fixed in the thermostatted, and temperature is controlled at best 60 ℃, slowly pours in regular turn in the wide mouth cup at the solution that will prepare, and constant temperature stirred about 60 minutes, when stirring, splashes into quadrol with dropper, regulator solution pH value to 5～7.At this moment wet gel solution becomes blackish green.The wet gel solution of preparation directly is put on the electric furnace and evaporates, remove most of moisture content after, gel is placed in the sintering oven, as required 500 ℃ of pre-burnings 15 minutes.At this moment, gel becomes fluffy powder russet, and grain-size is 20～60nm.With the powder of preparation through grinding, after the granulation, be pressed into external diameter φ 13, internal diameter φ 7, thickness 3mm annular sample heats up with 130 degree speed per hour, and insulation 30 minutes under 1200 ℃ of temperature.Furnace cooling then.
Embodiment two: the preparation method is identical with embodiment one, and different is doping metals nitrate, adopts cupric nitrate, and sintering temperature is 1100 ℃.
Difference prepared according to the methods of the invention is mixed cobalt and is mixed the magnetic spectrum of the ferrite magnetic material of copper, referring to Fig. 1 and Fig. 2.As can be seen, adopt the ferrite doped calcium magneticsubstance of the inventive method preparation from Fig. 1 and Fig. 2, the variation of its hotchpotch trace all can detect and control the influence of the electromagnetic performance of final sample, and process stabilizing, is easy to repetition, stable performance.
The inventive method is not only applicable to the various soluble salt solute dopings of alkaline-earth metal, main metal, transition metal, nonmetal, rare earth element, and can also carry out the mixing and doping of two or more element as required.In addition, the inventive method ferrite doping process of also can be used for the adulterated technology of other ferrite magnetic materials and needing atmosphere control.
Claims (2)
1. the preparation method of a ferrite doped calcium magneticsubstance is characterized in that, this method may further comprise the steps:
A. raw material is equipped with: take by weighing iron nitrate, nickelous nitrate, zinc nitrate according to required proportioning, the nitrate of adulterated metal an amount of and with metal nitrate with etc. the citric acid of mol ratio configuration, and be mixed with the aqueous solution respectively;
B. preparing gel: reactor is fixed in the thermostatted, temperature is controlled at 40-90 ℃, with iron nitrate, nickelous nitrate, zinc nitrate, citric acid and want the nitrate solution of adulterated metal to add in the reactor successively, constant temperature stirred 30-120 minute, when stirring, drip basic solution, to the pH value of solution value be 5-7, form cyan wet gel solution this moment;
The preparation of c. nanocrystalline pre-burning powder: above-mentioned wet gel solution is evaporated to remove most water, when film appears in liquid level, stop heating, this moment, wet gel will become gel, this gel is placed in the sintering oven, and at 300-600 ℃ of following pre-burning 10-30 minute, this moment, gel became fluffy powder russet, be the ferrite doped calcium powder, its grain-size is 20-60nm;
D. the preparation of ferrite magnetic material: with above-mentioned ferrite doped calcium powder, after grinding, granulation, after being pressed into required shape, put into atmosphere furnace, with per hour 130 degree speed intensification, and 1000 ℃ of-1300 ℃ of sintering temperatures 30 minutes, furnace cooling can make the ferrite doped calcium magneticsubstance then.
2. the preparation method of a kind of ferrite doped calcium magneticsubstance according to claim 1 is characterized in that, the nitrate that is used for adulterated metal is cupric nitrate, Xiao Suangu; Regulating the used basic solution of pH value is ethylenediamine solution.
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| CN 03116206 CN1228272C (en) | 2003-04-01 | 2003-04-01 | Prepn of doped magnetic ferrite material |
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|---|---|---|---|
| CN 03116206 CN1228272C (en) | 2003-04-01 | 2003-04-01 | Prepn of doped magnetic ferrite material |
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| CN1486958A CN1486958A (en) | 2004-04-07 |
| CN1228272C true CN1228272C (en) | 2005-11-23 |
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| CN 03116206 Expired - Fee Related CN1228272C (en) | 2003-04-01 | 2003-04-01 | Prepn of doped magnetic ferrite material |
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297511C (en) * | 2004-07-09 | 2007-01-31 | 北京化工大学 | Porous magnetic ferrite and its preparation method |
| CN1321898C (en) * | 2005-10-19 | 2007-06-20 | 清华大学 | Prepn process of nanometer ferromagnetic oxide particle |
| CN100401434C (en) * | 2005-11-10 | 2008-07-09 | 上海大学 | Preparation method of high-loss compound structure magnetic material |
| CN1328211C (en) * | 2005-12-15 | 2007-07-25 | 哈尔滨工程大学 | Nanometer ferrite powder preparation method |
| CN101710516B (en) * | 2009-09-27 | 2011-08-03 | 武汉理工大学 | Method for preparing magnetic material taking leopard palm as matrix |
| CN101710515B (en) * | 2009-09-27 | 2011-08-03 | 武汉理工大学 | Preparation method of magnetic material with konjac as matrix |
| CN102417349B (en) * | 2011-09-05 | 2013-07-17 | 常州大学 | Samarium-ferrite radar absorbing material and preparation method thereof |
| CN103184033B (en) * | 2011-12-27 | 2016-04-13 | 宁波杉杉新材料科技有限公司 | A kind of Barium ferrite composite material and its preparation method and application |
| CN102992753B (en) * | 2012-11-23 | 2014-05-21 | 天长市昭田磁电科技有限公司 | Low power consumption preparation method of Mn-Zn soft magnetic ferrite material |
| CN102992752B (en) * | 2012-11-23 | 2014-06-04 | 天长市昭田磁电科技有限公司 | Method for preparing manganese-zinc (MnZn) soft magnetic ferrite |
| CN104891981B (en) * | 2015-05-14 | 2017-11-14 | 江苏有能新能源有限公司 | A kind of bank base variable-frequency power sources magnetic materials for general purpose and preparation method thereof |
| CN104882240B (en) * | 2015-05-14 | 2017-11-14 | 江苏有能新能源有限公司 | A kind of magnetic material for photovoltaic inverter and preparation method thereof |
| CN106950275A (en) * | 2017-04-12 | 2017-07-14 | 吉林大学 | With Co1‑xZnxFe2O4Acetone sensor for sensitive electrode material and preparation method thereof |
| CN108324031A (en) * | 2018-02-10 | 2018-07-27 | 深圳市晟达机械设计有限公司 | A kind of hotel's antibiosis anti-acarien damping pillow |
| CN110395976B (en) * | 2019-08-22 | 2022-09-23 | 安阳师范学院 | Preparation method of lithium-aluminum co-doped nickel-zinc ferrite ceramic material |
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Assignee: Tongxiang Yaorun Electric Co., Ltd. Assignor: Shanghai University Contract record no.: 2010330000654 Denomination of invention: Prepn of doped magnetic ferrite material Granted publication date: 20051123 License type: Exclusive License Open date: 20040407 Record date: 20100428 |
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