CN102531562A - Method for preparing soft magnetic mesoporous nickel-zinc ferrite microspheres - Google Patents
Method for preparing soft magnetic mesoporous nickel-zinc ferrite microspheres Download PDFInfo
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Abstract
The invention discloses a method for preparing soft magnetic mesoporous nickel-zinc ferrite microspheres and overcomes the disadvantages that steps are fussy, the requirements of reaction conditions are high, the size, morphology and structure of particles are difficult to control, and the reproducibility is low in the conventional method. The method comprises the following steps of: performing hydrothermal reaction on a glucose solution which is taken as a raw material, and centrifuging at high speed to obtain C microspheres; matching the C microspheres which are taken as a template with ammonium acetate, Ni salt, Zn salt and Fe salt in a glycol environment to obtain nickel-zinc ferrite-C precursor composite microspheres; and finally, removing the C microsphere template from the nickel-zinc ferrite-C precursor composite microspheres through calcination to obtain a residual product, namely the soft magnetic mesoporous nickel-zinc ferrite microspheres. The method is low in cost and high in yield and productivity, is easy to operate, can repeat and amplify, can be applied to the fields of medicine carriers, electromagnetic shielding, nano-magnetic packing and the like, and has good potential application value, reaction conditions are mild and pollution-free, and the process is easy to control.
Description
Technical field
The present invention relates to a kind of preparation method of central hole structure magnetic microsphere, be specially a kind of preparation method of soft magnetism mesoporous nickel Zn ferrite microballoon.
Background technology
The mesopore magnetic microsphere is owing to have characteristics such as magnetic and central hole structure, so it has important application in carrier fields such as (like pharmaceutical carriers).From seeing in recent years, the research of targeted drug begins to rise, and the central hole structure magnetic microsphere also becomes one of focus of nanometer material science.
The nickel-zinc ferrite microballoon is a kind of important soft magnetism nano material; Because it has big internal cavities, high saturation magnetization, low coercive force and remanent magnetism, thereby soft magnetism mesoporous nickel Zn ferrite microballoon will can be used as a kind of good carrier and be applied in the research of targeted drug.At present, the preparation method of soft magnetism mesoporous nickel Zn ferrite microballoon has hard template method, sol-gel method etc. usually, adopts above method preparation; Perhaps need remove nuclear, complex steps, the reaction conditions of perhaps having relatively high expectations; Be not easy to control particulate size, pattern and structure, and reproducibility is low.Therefore, develop the method for preparing soft magnetism mesoporous nickel Zn ferrite microballoon that a kind of modern design, easy and simple to handle, process are easy to control, can repeat and amplification, output and productive rate are all higher and just had significance.
Summary of the invention
The objective of the invention is to have complex steps in order to solve the existing method for preparing soft magnetism mesoporous nickel Zn ferrite microballoon; Reaction conditions requires high; Be not easy to control particulate size, pattern and structure; And shortcoming such as reproducibility is low, and provide gentle pollution-free, the process of a kind of with low cost, easy and simple to handle, reaction conditions to be easy to control, can repeat and the novel preparation method of the soft magnetism mesoporous nickel Zn ferrite microballoon that amplification, output and productive rate are all higher.This method can be passed through conditions such as conditioned reaction substrate concentration, temperature of reaction, comes size, aperture etc. to microballoon to regulate and control, thus the excellent product of obtained performance.
The present invention realizes through following technical scheme:
A kind of preparation method of soft magnetism mesoporous nickel Zn ferrite microballoon comprises the steps:
(1) glucose is dissolved in is mixed with the glucose solution that mass concentration is 0.05-0.2g/ml in the deionized water; Change over to the glucose solution for preparing in the autoclave earlier; And at 180-200 ℃ of following hydro-thermal reaction 8-12h; And then change in the supercentrifuge, and be at least at rotating speed under the condition of 16000rpm and separate 5min at least, obtain solid C microballoon (carbosphere) at last;
(2) get NiCl
26H
2O, ZnCl
26H
2O and FeCl
36H
2O also together is dissolved in the terepthaloyl moietie, is stirred well to few 30min, and then adds ammonium acetate, is stirred well to few 30min again, has obtained orange turbid solution at last, and the molar concentration rate of ionizable metal salt is Ni in this orange turbid solution
2+: Zn
2+: Fe
3+=1:1:4, the addition of ammonium acetate are 0.01-0.05g/ml (being the ammonium acetate that adds 0.01-0.05g in every milliliter of terepthaloyl moietie);
(3) get the C microballoon that obtains in the step (1); And it is dissolved in the orange turbid solution that obtains in the step (2); The orange turbid solution that will be dissolved with the C microballoon then is through ultrasonication (processor for ultrasonic wave) 2min at least; Then be stirred well to few 10min again, obtain black suspension at last, wherein the addition of C microballoon is 0.005-0.01g/ml (being the C microballoon that adds 0.005-0.01g in every milliliter of orange turbid solution);
(4) black suspension that obtains in the step (3) is changed in the autoclave earlier, and at 160-180 ℃ of following hydro-thermal reaction 8-24h, and then change in the supercentrifuge; And be at least at rotating speed under the condition of 10000rpm and separate 2min at least; Obtain the black solid particle, with the black solid particle that obtains with deionized water wash at least 2 times after, again 40-100 ℃ of down oven dry; Obtain the black solid powder at last, be nickel-zinc ferrite-C precursor complex microsphere;
(5) the black solid powder that obtains in the step (4) is put into nickel crucible; And the calcining of in air atmosphere, heating gradually; The calcining top temperature be 500-800 ℃ and after reaching the highest calcining temperature constant temperature 2-4h again, promptly obtain the soft magnetism mesoporous nickel Zn ferrite microballoon of brown at last.
Reaction mechanism of the present invention is: at first, under hydrothermal condition, receive thermal hydrolysis to generate amorphous C (carbon) glucose solution, obtain solid C microballoon (the C microspherulite diameter that the inventive method obtains can between 180-1000nm) through high-speed separation again; Then, in the terepthaloyl moietie environment, be template and cooperate Ammonium Acetate, Ni salt, Zn salt and Fe salt that prepare central hole structure nickel-zinc ferrite microballoon, detailed process is: under the solvent thermal condition, the Ammonium Acetate hydrolysis discharges a large amount of OH with the C microballoon
-Ion, OH
-Ion is with Ni
2+, Zn
2+And Fe
3+Precipitation by metallic ion obtains the elementary nanometer small-particle of nickel-zinc ferrite, i.e. nucleation center at last through reaction.Because C microballoon inside has the duct; And its surface has-and the OH group has the intensive adsorption to the elementary nanometer small-particle of nickel-zinc ferrite; Thereby under violent molecular thermalmotion effect, the elementary nanometer small-particle of nickel-zinc ferrite enters in the middle of the duct, inside of C microsphere template.Along with the carrying out of hydro-thermal reaction, increasing nickel-zinc ferrite generates and enters into C microsphere template inside, finally obtains nickel-zinc ferrite-C precursor complex microsphere.Through calcining, the C microsphere template in nickel-zinc ferrite-C precursor complex microsphere is removed at last, and remaining product is central hole structure nickel-zinc ferrite microballoon.
The inventive method is compared with existing process method, has following beneficial effect:
(1) raw material sources are extensive, and are cheap, and reaction conditions is gentle, and is pollution-free in the reaction process, easy and simple to handle, and SF is high.
(2) the product microballoon has tangible central hole structure, novel structure, and purity is high, and the acquisition of structure only need remove the C template through calcining and can obtain, and need not carry out complicated means such as wet-chemical etching.
(3) can pass through conditions such as conditioned reaction substrate concentration, temperature of reaction, the size of product microballoon, aperture etc. are regulated and control, thus the excellent product of obtained performance.The saturation magnetization of product microballoon can reach 85emu/g, and the obvious height of magnetic property has the solid nanometer nickel-zinc ferrite of the solid particle in the report.
(4) this technology can repeat and amplify, and output and productive rate are all higher, is fit to amplify produce and practical application.
(5) the inventive method is a synthetic good approach and the thinking of providing of central hole structure magnetic microsphere, can be applicable to fields such as pharmaceutical carrier, electromagnetic shielding, nano-magnetic filler, has good potential using value.
Description of drawings
Fig. 1 is the TEM shape appearance figure of the C microballoon that obtains among the embodiment 1.
Fig. 2 is the TEM shape appearance figure of nickel-zinc ferrite-C precursor complex microsphere of obtaining among the embodiment 1.
The SEM shape appearance figure of the soft magnetism mesoporous nickel Zn ferrite microballoon that Fig. 3 makes for embodiment 1.
The TEM shape appearance figure of the soft magnetism mesoporous nickel Zn ferrite microballoon that Fig. 4 makes for embodiment 1.
The XRD figure spectrum of the soft magnetism mesoporous nickel Zn ferrite microballoon that Fig. 5 makes for embodiment 1.
Fig. 6 is the TGA collection of illustrative plates of nickel-zinc ferrite-C precursor complex microsphere of obtaining among the embodiment 1.
The VSM collection of illustrative plates of the soft magnetism mesoporous nickel Zn ferrite microballoon that Fig. 7 makes for embodiment 1.
The TEM shape appearance figure of the soft magnetism mesoporous nickel Zn ferrite microballoon that Fig. 8 makes for embodiment 2.
Fig. 9 is the TGA collection of illustrative plates of nickel-zinc ferrite-C precursor complex microsphere of obtaining among the embodiment 2.
The VSM collection of illustrative plates of the soft magnetism mesoporous nickel Zn ferrite microballoon that Figure 10 makes for embodiment 2.
The TEM collection of illustrative plates of the soft magnetism mesoporous nickel Zn ferrite microballoon that Figure 11 makes for embodiment 3.
The VSM collection of illustrative plates of the soft magnetism mesoporous nickel Zn ferrite microballoon that Figure 12 makes for embodiment 3.
The TEM collection of illustrative plates of the soft magnetism mesoporous nickel Zn ferrite microballoon that Figure 13 makes for embodiment 4.
The VSM collection of illustrative plates of the soft magnetism mesoporous nickel Zn ferrite microballoon that Figure 14 makes for embodiment 4.
Embodiment
Below in conjunction with specific embodiment and respective drawings the present invention is further described:
Embodiment 1
A kind of preparation method of soft magnetism mesoporous nickel Zn ferrite microballoon comprises the steps:
(1) glucose is dissolved in is mixed with the glucose solution that mass concentration is 0.1g/ml in the deionized water; Change over to the glucose solution for preparing in the autoclave earlier; And at 180 ℃ of following hydro-thermal reaction 8h; And then change in the supercentrifuge, and be to separate 10min under the condition of 16000rpm at rotating speed, obtain solid C microballoon at last;
(2) get NiCl
26H
2O, ZnCl
26H
2O and FeCl
36H
2O also together is dissolved in the terepthaloyl moietie, fully stirs 40min, and then adds ammonium acetate, fully stirs 30min again, has obtained orange turbid solution at last, and the molar concentration rate of ionizable metal salt is Ni in this orange turbid solution
2+: Zn
2+: Fe
3+=1:1:4, the addition of ammonium acetate are 0.05g/ml;
(3) get the C microballoon that obtains in the step (1); And it is dissolved in the orange turbid solution that obtains in the step (2); The orange turbid solution that will be dissolved with the C microballoon then is through ultrasonication 2min; Then fully stir 15min again, obtain black suspension at last, wherein the addition of C microballoon is 0.01g/ml;
(4) black suspension that obtains in the step (3) is changed in the autoclave earlier, and at 160 ℃ of following hydro-thermal reaction 18h, and then change in the supercentrifuge; And be to separate 2min under the condition of 11000rpm at rotating speed; Obtain the black solid particle, with the black solid particle that obtains with deionized water wash 2 times after, again 60 ℃ of down oven dry; Obtain the black solid powder at last, be nickel-zinc ferrite-C precursor complex microsphere;
(5) the black solid powder that obtains in the step (4) is put into nickel crucible; And the calcining of in air atmosphere, heating gradually; Calcining temperature be up to 700 ℃ and after reaching 700 ℃ of the highest calcining temperatures constant temperature 3h again, promptly obtain the soft magnetism mesoporous nickel Zn ferrite microballoon of brown at last.
Products therefrom soft magnetism mesoporous nickel Zn ferrite microballoon is carried out appearance structure with XRD, TEM, TGA and VSM etc. respectively to be characterized and performance study.
Fig. 1 is the TEM shape appearance figure of C microballoon in the present embodiment, from figure, can find out that the C microballoon has comparatively regular spherical morphology, and particle diameter is about about 180nm, narrow diameter distribution, good dispersivity.
Fig. 2 is the TEM shape appearance figure of nickel-zinc ferrite in the present embodiment-C precursor complex microsphere; From figure, can find out that nickel-zinc ferrite-C precursor complex microsphere has kept spherical morphology; Particle diameter is about about 180nm; With C microspherulite diameter basically identical, explain that the elementary nanometer small-particle of nickel-zinc ferrite is adsorbed to C microballoon inside, has formed nickel-zinc ferrite-C precursor complex microsphere.
The SEM shape appearance figure of the soft magnetism mesoporous nickel Zn ferrite microballoon that Fig. 3 makes for present embodiment can find out that the soft magnetism mesoporous nickel Zn ferrite microballoon for preparing has spherical morphology from figure, particle diameter is about about 180nm, narrow diameter distribution, good dispersivity.
The TEM shape appearance figure of the soft magnetism mesoporous nickel Zn ferrite microballoon that Fig. 4 makes for present embodiment; From figure, can find out that the soft magnetism mesoporous nickel Zn ferrite microballoon for preparing has tangible central hole structure, microballoon is an almost spherical, and particle diameter is about about 180nm; Narrow diameter distribution, monodispersity is good.
Fig. 5 composes for the XRD figure of the soft magnetism mesoporous nickel Zn ferrite microballoon that present embodiment makes; From figure, can find out that the soft magnetism mesoporous nickel Zn ferrite microballoon product for preparing is pure, diffraction peak is sharp-pointed, and diffraction peak intensity is higher; Explain that product is the spinel type nickel-zinc ferrite, better crystallinity degree.
Fig. 6 is the TGA collection of illustrative plates of nickel-zinc ferrite in the present embodiment-C precursor complex microsphere, can find out that from figure nickel-zinc ferrite-C precursor complex microsphere is weightless for the first time in the time of 50 ℃-200 ℃, and this is to contain free water to cause; For the second time weightless in the time of 200 ℃-700 ℃, this be the C microsphere template by high-temperature calcination remove cause.
The VSM collection of illustrative plates of the soft magnetism mesoporous nickel Zn ferrite microballoon that Fig. 7 makes for present embodiment can find out that the soft magnetism mesoporous nickel Zn ferrite microballoon saturation magnetization for preparing is 80emu/g from figure, coercive force is 0, explains that it is a superparamagnetism.
A kind of preparation method of soft magnetism mesoporous nickel Zn ferrite microballoon comprises the steps:
(1) glucose is dissolved in is mixed with the glucose solution that mass concentration is 0.05g/ml in the deionized water; Change over to the glucose solution for preparing in the autoclave earlier; And at 190 ℃ of following hydro-thermal reaction 10h; And then change in the supercentrifuge, and be to separate 5min under the condition of 16000rpm at rotating speed, obtain solid C microballoon at last;
(2) get NiCl
26H
2O, ZnCl
26H
2O and FeCl
36H
2O also together is dissolved in the terepthaloyl moietie, fully stirs 30min, and then adds ammonium acetate, fully stirs 35min again, has obtained orange turbid solution at last, and the molar concentration rate of ionizable metal salt is Ni in this orange turbid solution
2+: Zn
2+: Fe
3+=1:1:4, the addition of ammonium acetate are 0.025g/ml;
(3) get the C microballoon that obtains in the step (1); And it is dissolved in the orange turbid solution that obtains in the step (2); The orange turbid solution that will be dissolved with the C microballoon then is through ultrasonication 3min; Then fully stir 10min again, obtain black suspension at last, wherein the addition of C microballoon is 0.005g/ml;
(4) black suspension that obtains in the step (3) is changed in the autoclave earlier, and at 180 ℃ of following hydro-thermal reaction 8h, and then change in the supercentrifuge; And be to separate 3min under the condition of 10000rpm at rotating speed; Obtain the black solid particle, with the black solid particle that obtains with deionized water wash 4 times after, again 40 ℃ of down oven dry; Obtain the black solid powder at last, be nickel-zinc ferrite-C precursor complex microsphere;
(5) the black solid powder that obtains in the step (4) is put into nickel crucible; And the calcining of in air atmosphere, heating gradually; Calcining temperature be up to 500 ℃ and after reaching 500 ℃ of the highest calcining temperatures constant temperature 4h again, promptly obtain the soft magnetism mesoporous nickel Zn ferrite microballoon of brown at last.
Products therefrom soft magnetism mesoporous nickel Zn ferrite microballoon is carried out appearance structure with TEM, TGA and VSM etc. respectively to be characterized and performance study.
The TEM shape appearance figure of the soft magnetism mesoporous nickel Zn ferrite microballoon that Fig. 8 makes for present embodiment.From figure, can find out that the soft magnetism mesoporous nickel Zn ferrite microballoon for preparing has tangible central hole structure, microballoon is an almost spherical, and particle diameter is about about 300nm, narrow diameter distribution, and monodispersity is good.
The TGA collection of illustrative plates of the nickel-zinc ferrite that Fig. 9 makes for present embodiment-C precursor complex microsphere.From figure, can find out that the weightlessness of nickel-zinc ferrite-C precursor complex microsphere also can be divided into two steps, weightless for the first time in the time of about 50 ℃-200 ℃, this is to contain free water to cause; For the second time weightless in the time of about 200 ℃-500 ℃, this be the C microsphere template by high-temperature calcination remove cause.
The VSM collection of illustrative plates of the soft magnetism mesoporous nickel Zn ferrite microballoon that Figure 10 makes for present embodiment.From figure, can find out that the soft magnetism mesoporous nickel Zn ferrite microballoon saturation magnetization for preparing is 45emu/g, coercive force is 0, explains that it is a superparamagnetism.Result's reason that decreases shown in Figure 7 is that the calcining temperature reduction causes among product saturation magnetization and the embodiment 1.
Embodiment 3
A kind of preparation method of soft magnetism mesoporous nickel Zn ferrite microballoon comprises the steps:
(1) glucose is dissolved in is mixed with the glucose solution that mass concentration is 0.15g/ml in the deionized water; Change over to the glucose solution for preparing in the autoclave earlier; And at 200 ℃ of following hydro-thermal reaction 12h; And then change in the supercentrifuge, and be to separate 8min under the condition of 17000rpm at rotating speed, obtain solid C microballoon at last;
(2) get NiCl
26H
2O, ZnCl
26H
2O and FeCl
36H
2O also together is dissolved in the terepthaloyl moietie, fully stirs 35min, and then adds ammonium acetate, fully stirs 40min again, has obtained orange turbid solution at last, and the molar concentration rate of ionizable metal salt is Ni in this orange turbid solution
2+: Zn
2+: Fe
3+=1:1:4, the addition of ammonium acetate are 0.01g/ml;
(3) get the C microballoon that obtains in the step (1); And it is dissolved in the orange turbid solution that obtains in the step (2); The orange turbid solution that will be dissolved with the C microballoon then is through ultrasonication 5min; Then fully stir 20min again, obtain black suspension at last, wherein the addition of C microballoon is 0.009g/ml;
(4) black suspension that obtains in the step (3) is changed in the autoclave earlier, and at 160 ℃ of following hydro-thermal reaction 24h, and then change in the supercentrifuge; And be to separate 4min under the condition of 13000rpm at rotating speed; Obtain the black solid particle, with the black solid particle that obtains with deionized water wash 4 times after, again 80 ℃ of down oven dry; Obtain the black solid powder at last, be nickel-zinc ferrite-C precursor complex microsphere;
(5) the black solid powder that obtains in the step (4) is put into nickel crucible; And the calcining of in air atmosphere, heating gradually; Calcining temperature be up to 600 ℃ and after reaching 600 ℃ of the highest calcining temperatures constant temperature 3h again, promptly obtain the soft magnetism mesoporous nickel Zn ferrite microballoon of brown at last.
Products therefrom soft magnetism mesoporous nickel Zn ferrite microballoon is carried out appearance structure with TEM and VSM respectively to be characterized and performance study.
The TEM collection of illustrative plates of the soft magnetism mesoporous nickel Zn ferrite microballoon that Figure 11 makes for present embodiment.Can find out among the figure that the soft magnetism mesoporous nickel Zn ferrite microballoon for preparing has tangible central hole structure, microballoon is an almost spherical, and particle diameter is about about 1000nm, narrow diameter distribution, and monodispersity is good.
The VSM collection of illustrative plates of the soft magnetism mesoporous nickel Zn ferrite microballoon that Figure 12 makes for present embodiment.From figure, can find out that the soft magnetism mesoporous nickel Zn ferrite microballoon saturation magnetization for preparing is 62emu/g, coercive force is 0, explains that it is a superparamagnetism.Result's reason that decreases shown in Figure 7 is that the calcining temperature reduction causes equally among product saturation magnetization and the embodiment 1; Otherwise with embodiment 2 results rising shown in Figure 10, its reason is that calcining temperature raises to some extent.
Embodiment 4
A kind of preparation method of soft magnetism mesoporous nickel Zn ferrite microballoon comprises the steps:
(1) glucose is dissolved in is mixed with the glucose solution that mass concentration is 0.2g/ml in the deionized water; Change over to the glucose solution for preparing in the autoclave earlier; And at 180 ℃ of following hydro-thermal reaction 10h; And then change in the supercentrifuge, and be to separate 13min under the condition of 20000rpm at rotating speed, obtain solid C microballoon at last;
(2) get NiCl
26H
2O, ZnCl
26H
2O and FeCl
36H
2O also together is dissolved in the terepthaloyl moietie, fully stirs 45min, and then adds ammonium acetate, fully stirs 45min again, has obtained orange turbid solution at last, and the molar concentration rate of ionizable metal salt is Ni in this orange turbid solution
2+: Zn
2+: Fe
3+=1:1:4, the addition of ammonium acetate are 0.04g/ml;
(3) get the C microballoon that obtains in the step (1); And it is dissolved in the orange turbid solution that obtains in the step (2); The orange turbid solution that will be dissolved with the C microballoon then is through ultrasonication 4min; Then fully stir 30min again, obtain black suspension at last, wherein the addition of C microballoon is 0.01g/ml;
(4) black suspension that obtains in the step (3) is changed in the autoclave earlier, and at 170 ℃ of following hydro-thermal reaction 10h, and then change in the supercentrifuge; And be to separate 3min under the condition of 15000rpm at rotating speed; Obtain the black solid particle, with the black solid particle that obtains with deionized water wash 6 times after, again 100 ℃ of down oven dry; Obtain the black solid powder at last, be nickel-zinc ferrite-C precursor complex microsphere;
(5) the black solid powder that obtains in the step (4) is put into nickel crucible; And the calcining of in air atmosphere, heating gradually; Calcining temperature be up to 800 ℃ and after reaching 800 ℃ of the highest calcining temperatures constant temperature 2h again, promptly obtain the soft magnetism mesoporous nickel Zn ferrite microballoon of brown at last.
Products therefrom soft magnetism mesoporous nickel Zn ferrite microballoon is carried out appearance structure with TEM and VSM respectively to be characterized and performance study.
The TEM collection of illustrative plates of the soft magnetism mesoporous nickel Zn ferrite microballoon that Figure 13 makes for present embodiment.Can find out among the figure that the soft magnetism mesoporous nickel Zn ferrite microballoon for preparing has tangible central hole structure, microballoon is an almost spherical, and particle diameter is about about 600nm; The size distribution broad; Calcining temperature is higher, so it is more abundant to reunite, the process of crystal growth has taken place product.
The VSM collection of illustrative plates of the soft magnetism mesoporous nickel Zn ferrite microballoon that Figure 14 makes for present embodiment.From figure, can find out that the soft magnetism mesoporous nickel Zn ferrite microballoon saturation magnetization for preparing is 85emu/g, coercive force is 0, explains that it is a superparamagnetism.Result's reason that raises to some extent shown in Figure 7 is that the calcining temperature rising causes equally among product saturation magnetization and the embodiment 1.
Claims (1)
1. the preparation method of a soft magnetism mesoporous nickel Zn ferrite microballoon is characterized in that comprising the steps:
(1) glucose is dissolved in is mixed with the glucose solution that mass concentration is 0.05-0.2g/ml in the deionized water; Change over to the glucose solution for preparing in the autoclave earlier; And at 180-200 ℃ of following hydro-thermal reaction 8-12h; And then change in the supercentrifuge, and be at least at rotating speed under the condition of 16000rpm and separate 5min at least, obtain solid C microballoon at last;
(2) get NiCl
26H
2O, ZnCl
26H
2O and FeCl
36H
2O also together is dissolved in the terepthaloyl moietie, is stirred well to few 30min, and then adds ammonium acetate, is stirred well to few 30min again, has obtained orange turbid solution at last, and the molar concentration rate of ionizable metal salt is Ni in this orange turbid solution
2+: Zn
2+: Fe
3+=1:1:4, the addition of ammonium acetate are 0.01-0.05g/ml;
(3) get the C microballoon that obtains in the step (1); And it is dissolved in the orange turbid solution that obtains in the step (2); The orange turbid solution that will be dissolved with the C microballoon then is through ultrasonication 2min at least; Then be stirred well to few 10min again, obtain black suspension at last, wherein the addition of C microballoon is 0.005-0.01g/ml;
(4) black suspension that obtains in the step (3) is changed in the autoclave earlier, and at 160-180 ℃ of following hydro-thermal reaction 8-24h, and then change in the supercentrifuge; And be at least at rotating speed under the condition of 10000rpm and separate 2min at least; Obtain the black solid particle, with the black solid particle that obtains with deionized water wash at least 2 times after, again 40-100 ℃ of down oven dry; Obtain the black solid powder at last, be nickel-zinc ferrite-C precursor complex microsphere;
(5) the black solid powder that obtains in the step (4) is put into nickel crucible; And the calcining of in air atmosphere, heating gradually; The calcining top temperature be 500-800 ℃ and after reaching the highest calcining temperature constant temperature 2-4h again, promptly obtain the soft magnetism mesoporous nickel Zn ferrite microballoon of brown at last.
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| CN109422531A (en) * | 2017-08-25 | 2019-03-05 | 仝丹丹 | A kind of ferritic preparation method of nickel tungsten |
| CN113192717A (en) * | 2021-04-22 | 2021-07-30 | 兰州大学 | Metal soft magnetic composite material and preparation method thereof |
| CN116789444A (en) * | 2023-05-11 | 2023-09-22 | 中国科学院宁波材料技术与工程研究所 | Hollow microsphere nickel-zinc ferrite wave-absorbing material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347855A (en) * | 2001-11-27 | 2002-05-08 | 南京大学 | Zinc ferrite material with giant magnetic resistance effect and its prepn |
| CN1414576A (en) * | 2001-10-24 | 2003-04-30 | 阿尔卑斯电气株式会社 | Garnet ferrite and manufacture method and garnet ferrite irreversible element |
| CN1750182A (en) * | 2004-09-13 | 2006-03-22 | 广东风华高新科技集团有限公司 | Nickel-zinc soft magnet ferrite material, inductor product and its producing method |
| JP2008143744A (en) * | 2006-12-11 | 2008-06-26 | Jfe Ferrite Corp | MnCoZn FERRITE AND MAGNETIC CORE FOR TRANSFORMER |
| CN101593595A (en) * | 2009-04-10 | 2009-12-02 | 临沂中瑞电子有限公司 | A kind of low-temperature sintering high performance soft magnetic ferrite material and manufacture method |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1414576A (en) * | 2001-10-24 | 2003-04-30 | 阿尔卑斯电气株式会社 | Garnet ferrite and manufacture method and garnet ferrite irreversible element |
| CN1347855A (en) * | 2001-11-27 | 2002-05-08 | 南京大学 | Zinc ferrite material with giant magnetic resistance effect and its prepn |
| CN1750182A (en) * | 2004-09-13 | 2006-03-22 | 广东风华高新科技集团有限公司 | Nickel-zinc soft magnet ferrite material, inductor product and its producing method |
| JP2008143744A (en) * | 2006-12-11 | 2008-06-26 | Jfe Ferrite Corp | MnCoZn FERRITE AND MAGNETIC CORE FOR TRANSFORMER |
| CN101593595A (en) * | 2009-04-10 | 2009-12-02 | 临沂中瑞电子有限公司 | A kind of low-temperature sintering high performance soft magnetic ferrite material and manufacture method |
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| CN108698841A (en) * | 2015-12-22 | 2018-10-23 | 巴斯夫公司 | The method for preparing the zeolite compositions of iron (III) exchange |
| CN109422531A (en) * | 2017-08-25 | 2019-03-05 | 仝丹丹 | A kind of ferritic preparation method of nickel tungsten |
| CN108648833A (en) * | 2018-05-11 | 2018-10-12 | 哈尔滨工业大学 | A kind of device and operating method of achievable microballoon any angle overturning |
| CN108648833B (en) * | 2018-05-11 | 2019-05-17 | 哈尔滨工业大学 | A kind of device and operating method of achievable microballoon any angle overturning |
| CN108795379A (en) * | 2018-07-09 | 2018-11-13 | 安徽理工大学 | A kind of preparation method of three-dimensional netted multi-walled carbon nanotube/Ni ferrite composite wave-suction material |
| CN108795379B (en) * | 2018-07-09 | 2021-03-19 | 安徽理工大学 | Preparation method of three-dimensional reticular multi-walled carbon nanotube/nickel ferrite composite wave-absorbing material |
| CN113192717A (en) * | 2021-04-22 | 2021-07-30 | 兰州大学 | Metal soft magnetic composite material and preparation method thereof |
| CN116789444A (en) * | 2023-05-11 | 2023-09-22 | 中国科学院宁波材料技术与工程研究所 | Hollow microsphere nickel-zinc ferrite wave-absorbing material and preparation method and application thereof |
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