CN103896342B - A kind of preparation method of bar-shaped spinel type ferrite - Google Patents
A kind of preparation method of bar-shaped spinel type ferrite Download PDFInfo
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- CN103896342B CN103896342B CN201410069390.8A CN201410069390A CN103896342B CN 103896342 B CN103896342 B CN 103896342B CN 201410069390 A CN201410069390 A CN 201410069390A CN 103896342 B CN103896342 B CN 103896342B
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Abstract
The invention provides a kind of preparation method of bar-shaped spinel type ferrite.Particular content, the metal salt solution of first compounding high concentration, regulate with ammoniacal liquor and to add after pH as inorganicss such as the needle-like alpha-feooh of template and raw material or carbonyl polycrystalline iron fibers, after dipping for some time, metal-salt is separated out and is deposited on template surface, obtains presoma after super-dry; Presoma can obtain bar-shaped spinel type ferrite after high-temperature roasting (topotactic reaction).This method technical process is simple, simple to operate and be easy to control, and cost is lower, is applicable to industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of magneticsubstance, particularly relate to a kind of method being prepared bar-shaped spinel type ferrite magnetic powder by steeping process at hard template surface deposition metal-salt.
Background technology
Spinel type ferrite MFe
2o
4be the magneticsubstance that a kind of operating frequency is high, magnetic spectrum characteristic is good, magnetic core bearing, information storage, biological medicine, microwave absorbing, catalysis technique and magnetic fluid have a wide range of applications.Ferrite nanometer particle chemical constitution, granule-morphology and size have material impact to ferritic magnetic property and application.Positively charged ion M(M=Zn
2+,
2+, Co
2+, Mn
2+, Cu
2+deng) of a great variety, when it enters spinel type MFe
2o
4during structure, just there is dissimilar nano-ferrite material.These dissimilar spinel type magnetic moments vary in size, and therefore magnetocrystalline anisotropy is different with saturation magnetization.Ferrite pattern to two dimension, even to one dimension future development, can obtain the anisotropic ferrite of different shapes by three-dimensional.D.E.Zhang etc. adopt the method for sol-tgel self-propagating, by soft template PEG-400, have prepared bar-shaped NiFe
2o
4, its diameter and length-to-diameter ratio are about 80nm and 12 respectively, and its coercive force (Hc) is obviously greater than the irregular and nearly spherical nano-Ni/Fe adopting sol-gel method to prepare at ambient temperature
2o
4.(D.E.Zhang, X.J.Zhang.etal.J.Magn.Magn.Mater.2005,292:79-82) ChaoLiu take Sodium dodecylbenzene sulfonate as tensio-active agent, obtains with the reverse microemulsion micelle of toluene and water the MnFe that particle size is 4-14nm
2o
4nano particle, its Hc all increases with the increase of particle size in critical temperature and at 20K temperature.(ChaoLiu,Z.JohnZhang.Chem.Mater.,2001,13(6):2092)
Conventional preparation method's primary chemical coprecipitation method, sol-gel method, hydrothermal method, ball milled, microemulsion method, molten-salt growth method etc. of spinel type ferrite, the preparation method wherein for one dimension spinel type ferrite is mainly following several.One, hydrothermal method.Refer in encloses container, original stock is soluble in water, to reaction system heating and pressurizing, realize a kind of method of the growth of crystal.Usual indissoluble or insoluble substance dissolves, recrystallization.Its advantage is that particle is not reunited, and particle dispersion is good, better crystallinity degree, and product purity is high.The ferrite nano material of required particle diameter, pattern and chemical constitution is prepared by Control release condition.Shortcoming is that requirement material purity is high, and cost is high, and technique is more complicated.Although can prepare nano level one-dimensional rod-like spinel type ferrite, particle is generally nano level spherical or nearly two-dimensional appearance (ZhuZR, ZhaoQD, LiXY.Chem.Eng.J., 2012,203:43-51).Two, sol-gel process.Sol-gel method is by metal organic salt and inorganic salt hydrolysis, is polymerized, and form colloidal sol, evaporating solvent forms gel, obtains xerogel, obtain final product after high-temperature roasting after drying.This method advantage is that product grain is thin and be uniformly dispersed, and technique is simple, and reaction time is short.Shortcoming is that reaction conditions is wayward, and conditional request is higher to external world, and may generate other crystalline phases, and cost is higher, severe reaction conditions, is not suitable for suitability for industrialized production.Particle major part is nano-grade or nearly three-dimensional appearance, and small part is nano level one-dimensional rod-like spinelle ferrite (GuoLP, ShenXQ, SongFZ.etal., Mater.Chem.Phys.2011,129:943-947).Three, microemulsion method.Two kinds of immiscible solvents form the dispersion system be made up of tensio-active agent, cosurfactant, solvent and water (or aqueous solution) under the effect of tensio-active agent.Its advantage is particle diameter, the distribution that effectively can be controlled particulate by the ratio of adjustment sheet surface-active agent and water.Deficiency is the aftertreatment difficulty of organic solvent, and production cost is high, is difficult to obtain pure substance, prepared particle be generally nano level spherical or nearly two-dimensional appearance (Feng Guangfeng, Li Hansheng. material Leader, 2007,21 (5): 36).Four, chemical precipitation-local structured's method.This method possesses the advantage of chemical precipitation method, has also shown the unique advantage that additive method can not replace, namely by the product of the reactant controlledly synthesis specific morphology of specific morphology.Therefore, the ferritic pattern of end product can be controlled and the purity of product is higher.The shortcoming of this method affects larger by one dimension template and deposition condition, demixing phenomenon may be produced in preparation process, throw out composition with the initial composition that feeds intake may exist certain deviation (Cao Xiaohui, Meng Jinhong, Dong Hongfei etc. Chinese patent .201010512661.4).
Based on the present Research of spinel type ferrite, the preparation method of a kind of simple, low cost, the bar-shaped spinel type ferrite of synthesizing one-dimensional that industrialization possibility is high is proposed, for improving the performance of spinel type ferrite and expanding its application, there is important practical significance.
Summary of the invention
The object of this invention is to provide a kind of preparation method of bar-shaped spinel type ferrite, the method is for hard template with needle-like or bar-shaped inorganics, obtain presoma by steeping process at hard template surface deposition metal-salt, after roasting, obtain spinel type ferrite magnetic powder.
The present invention is realized by subordinate's technical scheme:
A preparation method for bar-shaped spinel type ferrite, comprises following processing step:
(1) with molar ratio computing metal-salt: the ratio of template=1:1-4:1 gets metal-salt and template is for subsequent use;
(2) be dissolved in water by the metal-salt that step (1) takes, be mixed with the aqueous solution of 1.5-4.5mol/L, then regulate pH=6-9 with ammoniacal liquor, obtained salts solution is for subsequent use;
(3) template step (1) taken joins in the salts solution that step (2) prepares in water after ultrasonic disperse 0.5-1 hour, under normal temperature, volatilization 8-10 hour is left standstill after stirring, metal-salt is folded and is deposited in template, dry at 50-100 DEG C, through grind into powder, obtained metal-salt presoma.Ultrasound working frequency 30-50KH
z, ultrasonic time 5-60 minute.
(4) the metal-salt presoma that step (3) is obtained is incubated 0-5 hour at 250-500 DEG C of temperature, then at 600-900 DEG C of roasting temperature 0.5-6 hour, obtains final product.
Above-mentioned metal-salt is Zn salt, Ni salt, Co salt, Mn salt or Cu salt.
Above-mentioned template is needle-like alpha-feooh, needle-like γ-FeOOH, needle-like or bar-shaped α-Fe
2o
3, needle-like or bar-shaped γ-Fe
2o
3, corner acicular type zinc oxide, hydroxyl polycrystalline iron fiber or other there is iron, nickel, the zinc oxide of one dimension pattern.
Advantage of the present invention and feature are mainly: (1) can prepare one-dimensional rod-like spinel type ferrite by the technology of the present invention; (2) stock liquid preparation is simple and easy, and without the need to controlling the reaction conditionss such as feed rate, temperature, pH value in precursor power process, thus the method reaction process obviously simplifies, and simple to operate.(3) synthesis condition such as maturing temperature or time by template and the proportioning of metal-salt, the calcined temperature of presoma or time, presoma regulates the length-to-diameter ratio of prepared bar-shaped spinel type ferrite, purity and pattern, and then can carry out modulation to the magnetic property of bar-shaped spinel type ferrite; (4) require lower to conversion unit, process stabilizing, is easy to repetition, and cost is lower, and product performance are stablized.
Accompanying drawing explanation
The SEM figure of Fig. 1 embodiment presoma.
Fig. 2 embodiment 1 product X RD spectrogram.
Fig. 3 embodiment 1 product S EM schemes.
Fig. 4 embodiment 1 product magnetic hysteresis loop figure.
Fig. 5 embodiment 2 product X RD spectrogram.
Fig. 6 embodiment 2 product S EM schemes.
Fig. 7 embodiment 2 product magnetic hysteresis loop figure.
Fig. 8 embodiment 3 product X RD spectrogram.
Fig. 9 embodiment 3 product S EM schemes.
Embodiment
Embodiment 1
By nickelous nitrate: alpha-feooh=3:2(mol ratio) take nickelous nitrate and needle-like alpha-feooh respectively; By alpha-feooh ultrasonic disperse 0.5 hour in water; Nickelous nitrate is made into the aqueous solution of 3mol/L, regulates pH=8 with ammoniacal liquor; Being added by scattered alpha-feooh regulates in the nickel nitrate solution of pH, leaves standstill evaporation 8 hours after stirring under normal temperature, and then in 80 DEG C of dryings, grinding, obtains NiFe
2o
4presoma.By precursor 350 DEG C of insulations 2 hours, then 900 DEG C of roastings 2 hours, obtain product of roasting NiFe
2o
4.
Accompanying drawing 1 is the SEM figure of presoma, and it illustrates that presoma is obvious one-dimensional rod-like.Accompanying drawing 2, accompanying drawing 3 and accompanying drawing 4 is XRD figure, the SEM figure and magnetic hysteresis loop figure of product.They illustrate obtained by product be the nano-Ni/Fe of pure phase, Rod-like shape
2o
4, its particle length is 200nm ~ 800nm, and length-to-diameter ratio is 3 ~ 9.Gained NiFe
2o
4specific saturation magnetization (Ms) be 35.28emu/g, coercive force (Hc) is 370.98Oe.
The present embodiment illustrates, adopts preparation method of the present invention can prepare one-dimensional rod-like nanometer spinel type ferrite.
Document (XiaohuiCao, HongfeiDong, JinhongMeng.etal.Solid-StateSci.2011,13 (9): 1804) adopts chemical precipitation-local structured's legal system for bar-shaped NiFe
2o
4, itself Ms and Hc is respectively 33.80emm/g and 225Oe.Bar-shaped NiFe prepared by the present invention
2o
4ms and Hc all increase compared with it, and preparation method comparatively literature method obviously simplify and be easy to control.
Embodiment 2
The nano-Ni/Fe of Rod-like shape is prepared by the step of embodiment 1
2o
4, difference is: replace alpha-feooh using carbonyl polycrystalline iron fiber as template, and nickelous nitrate and carbonyl polycrystalline iron fiber mol ratio are 1.2:1, pH=9.
Accompanying drawing 5, accompanying drawing 6 and accompanying drawing 7 is XRD figure, the SEM figure and magnetic hysteresis loop figure of end product.They illustrate obtained by product be the nano-Ni/Fe of pure phase, Rod-like shape
2o
4, particle longest dimension can reach 9 μm.Gained NiFe
2o
4ms be 37.28emu/g, Hc be 167.55Oe.
The present embodiment illustrates, adopts different templates also can prepare one-dimensional rod-like nanometer spinel type ferrite.Compared with embodiment 1, the present embodiment also illustrates by modulation templating species and/or other synthesis condition, can the rod-shpaed particle size of spinel type ferrite prepared by modulation and performance.
Embodiment 3
By the step of embodiment 1, by metallic element Zn:Fe=1.8:2(mol ratio), take a certain amount of zinc nitrate, alpha-feooh, ammoniacal liquor adds alpha-feooh after regulating pH=8 ~ 9.
Accompanying drawing 8 and accompanying drawing 9 are XRD figure and the SEM figure of end product.They illustrate obtained by product be the nanometer Zn Fe of pure phase, Rod-like shape
2o
4, its particle length can reach 0.6 ~ 1.8 μm, and its length-to-diameter ratio is 2 ~ 14.
Compared with embodiment 1, the present embodiment illustrates the ferrospinel can being prepared different chemical composition by the technology of the present invention, also illustrate by modulation metal-salt kind and/or other synthesis condition, can the rod-shpaed particle size of spinel type ferrite prepared by modulation and performance.
Claims (2)
1. a preparation method for bar-shaped spinel type ferrite, comprises following processing step: it is characterized in that:
(1) with molar ratio computing metal-salt: the ratio of template=1:1-4:1 gets metal-salt and template is for subsequent use;
(2) be dissolved in water by the metal-salt that step (1) takes, be mixed with the aqueous solution of 1.5-4.5mol/L, then regulate pH=6-9 with ammoniacal liquor, obtained salts solution is for subsequent use;
(3) template step (1) taken joins in the salts solution that step (2) prepares in water after ultrasonic disperse 0.5-1 hour, under normal temperature, volatilization 8-10 hour is left standstill after stirring, metal-salt is separated out to be deposited in template, dry at 50-100 DEG C, through grind into powder, obtained metal-salt presoma; Ultrasound working frequency 30-50KHZ, ultrasonic time 5-60 minute;
(4) the metal-salt presoma that step (3) is obtained is incubated 0-5 hour at 250-500 DEG C of temperature, then at 600-900 DEG C of roasting temperature 0.5-6 hour, obtains final product.
2. the preparation method of a kind of bar-shaped spinel type ferrite according to claim 1, is characterized in that: above-mentioned metal-salt is Zn salt, Ni salt, Co salt, Mn salt or Cu salt;
Above-mentioned template is needle-like alpha-feooh, needle-like γ-FeOOH, needle-like or bar-shaped α-Fe2O3, needle-like or bar-shaped γ-Fe2O3, corner acicular type zinc oxide, hydroxyl polycrystalline iron fiber or other there is iron, nickel, the zinc oxide of one dimension pattern.
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| CN106486241B (en) * | 2015-08-28 | 2019-09-03 | 湖南博海新材料股份有限公司 | Nanometer magneto-rheological fluid |
| CN113428903A (en) * | 2021-07-21 | 2021-09-24 | 中国科学院电工研究所 | Method for preparing nano manganese-zinc ferrite fiber |
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|---|---|---|---|---|
| JP3328017B2 (en) * | 1993-08-16 | 2002-09-24 | 関東電化工業株式会社 | Method for producing acicular hexagonal ferrite magnetic powder having perpendicular magnetic anisotropy |
| CN102010190A (en) * | 2010-10-20 | 2011-04-13 | 沈阳理工大学 | Method for preparing one-dimensional rod-like spinelle ferrite |
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| JP2897794B2 (en) * | 1991-06-21 | 1999-05-31 | 戸田工業株式会社 | Method for producing cobalt-coated magnetic iron oxide particles |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3328017B2 (en) * | 1993-08-16 | 2002-09-24 | 関東電化工業株式会社 | Method for producing acicular hexagonal ferrite magnetic powder having perpendicular magnetic anisotropy |
| CN102010190A (en) * | 2010-10-20 | 2011-04-13 | 沈阳理工大学 | Method for preparing one-dimensional rod-like spinelle ferrite |
Non-Patent Citations (3)
| Title |
|---|
| Study on the synthesis and magnetic properties of rod-shaped NiFe2O4 ferrites via precipitation–toptactic reaction employing Na2C2O4 and NaOH as precipitants;Xiaohui Cao, et al.;《Materials Research Bulletin》;20130828;第49卷;全文 * |
| Synthesis of Cobalt Ferrite Nanowires Using FeOOH as a Template;Jose G Camacho Meza, et al.;《Solid State Phenomena》;20091231;第151卷;全文 * |
| 化学沉淀-局部规整法制备棒状M型钡铁氧体的形成历程;谭玉琢等;《无机化学学报》;20081231;第23卷(第12期);全文 * |
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