CN101552064B - Method for preparing hollow magnetic ball - Google Patents
Method for preparing hollow magnetic ball Download PDFInfo
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- CN101552064B CN101552064B CN2008102397227A CN200810239722A CN101552064B CN 101552064 B CN101552064 B CN 101552064B CN 2008102397227 A CN2008102397227 A CN 2008102397227A CN 200810239722 A CN200810239722 A CN 200810239722A CN 101552064 B CN101552064 B CN 101552064B
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Abstract
The invention relates to a method for preparing a hollow magnetic ball (tube) of metal and alloy, which belongs to the field of magnetic material preparation, in particular to the preparation of lightmagnetic particles. The method comprises the following steps of: adopting metallic iron particles as a template, depositing or plating a layer of metal cobalt, nickel or an alloy layer of the metal c obalt and the nickel on the surface thereof for preparing a 'core-shell' composite structure, and then using the reaction of primary cell to melt the iron core for further obtaining the hollow magnetic ball of the metal cobalt, nickel and the alloy. As the metallic iron particles are taken as the template, surface sensitizing processing is not needed to be implemented to the template, thereby simplifying the preparation process; and simultaneously, by controlling the size of the iron core, the size of the hollow ball can be controlled. When a linear or chain-shaped iron core is taken as the template, tubes of the metal cobalt, nickel and the alloy thereof can also be prepared. The hollow magnetic ball prepared by adopting the process is characterized by low density and high specific saturation magnetization strength, and can be used as magnetorheological intelligent material and military stealth material.
Description
Technical field
The present invention relates to the method for a kind of hollow magnetic ball (pipe) preparation, belong to the magnetic material preparation field, particularly the preparation of lightweight magnetic-particle.
Background technology
Along with the development that material science and technology makes rapid progress, the kind of magnetic material is increasing, and its function is also in continuous expansion, such as field application prospect light such as novel intelligent magnetorheological materials, medical target medicine carrier and stealth materials.But traditional magnetic material to have density higher, this has limited their application in some fields, as in magnetic flow liquid, the density of magnetic-particle is big, then cause its settlement stability variation in carrier fluid, thereby influence the serviceability of magnetic flow liquid, complete failure even; Equally, in the research of military invisbile plane, the microwave absorbing coating that is additive with present prepared magnetic metal particle does not often reach gratifying lightweight, wideband is inhaled the ripple requirement, is difficult to adapt to the requirement of modernized war.Therefore, exploitation lightweight magnetic-particle has become a frontier of magnetic material research, particularly prepares to have more low-density magnetic hollow microballoon.
The typical method of preparation hollow ball is a template at present, basic principle is to be nuclear with the template, outside template core, coat the shell of the certain thickness material requested of one deck (or its predecessor) by means such as assembling, absorption, precipitation reaction, chemical platings, form surface coated core/shell structure, remove the nuclear template with the method for heating or chemical reaction, just obtained hollow ball structure, the size of ball is by the size decision of template particles.High-temperature heating is decomposed and can therefore usually be used as the template of nucleocapsid structure, by obtaining the nucleocapsid composite construction at polymeric particles surface deposition, plating shell material by organic solvent dissolution because polymeric particles has.
But, when preparing the tiny balloon of magnetic shell as the template of nucleocapsid composite construction with the organic polymer particle, because magnetic material commonly used is generally iron, cobalt, metal simple-substances such as nickel, inorganic material such as alloy or its oxide, make that on the high-molecular organic material surface directly the metal or alloy shell of deposition or plating magnetic becomes difficult, must be through overactivation, sensitization is handled, increased preparation technology's complexity, adopt the technology of the method removal macromolecule template of pyrolysis simultaneously, can only obtain the metal oxide magnetic shell, reduce the specific saturation magnetization of magnetic hollow particle in a way.
The present invention adopts metallic iron nuclear to be template, can directly directly deposit or plating magnetic metal or alloy shell on iron nuclear surface, and need not complicated activation, sensitization treatment process, can prepare hollow magnetic ball or magnetic tube by changing iron nuclear shape (sphere or wire, chain) simultaneously.
Summary of the invention
The objective of the invention is provides a kind of method for preparing hollow magnetic ball or magnetic tube for the deficiency that overcomes prior art.
The objective of the invention is to be achieved through the following technical solutions.
It is template that a kind of method for preparing hollow magnetic ball of the present invention adopts the iron nuclear with spherical or subsphaeroidal iron nuclear or employing chain or wire, utilize the ultrasonic echography vibration or utilize mechanical agitation, obtain " nuclear-shell " composite construction at its surface deposition or plating one deck magnetic metal or alloy shell; Be placed on then in the acid solution, adopt principle of electrochemical reaction, the soluble iron nuclear template for preparing magnetic metal of corrosion " nuclear-shell " structure or the hollow ball or the magnetic tube of alloy shell;
The internal diameter size scope of described hollow ball is between 30 nanometers to 9 micron; Magnetic tube pipe inner diameter size scope is between 30 nanometers to 9 micron.
Prepared magnetic shell is metallic cobalt, metallic nickel or is other magnetic alloy material of main body composition with cobalt, nickel.
Preparation principle of the present invention is that employing soluble metal iron particle is a template; at iron nuclear surface deposition or plating layer of metal cobalt, nickel or with nickel, cobalt is the alloy of main component; be prepared into " nuclear-shell " composite construction; utilize the primary cell reaction principle again (when having two kinds of metals with different electrode potentials simultaneously; when electrochemical corrosion takes place; the metal that electrode potential is lower at first is corroded, and the low metal of electrode potential is protected.), adopt hydrochloric acid solution or sulfuric acid solution as molten nuclear agent, owing to be coated on the iron of the electrode potential of the outer field cobalt of iron particle (nickel) greater than its inside, in the middle of acid solution, just formed primary cell, inner iron is consumed as the positive pole of battery, then is retained as the cobalt (nickel) of negative electrode, by the control acid etching time, finally obtain pure crust of cobalt layer, pure nickel shell or be the magnetic hollow microballoon of other magnetic alloy shell of main body composition with cobalt, nickel.
Adopt the disclosed technical process of this patent, the preparation cobalt, during the hollow magnetic ball of nickel and alloy thereof, after can adopting chemical method (reducing process) self-control iron nuclear, directly deposit or plating cobalt (nickel on its surface, cobalt-nickel alloy) layer, do not need its surface is activated, sensitization is handled, and when adopting the iron nuclear of outsourcing, only need roughening treatment is carried out on iron nuclear surface, can deposit or plating technic, therefore, have characteristic of simple process, need carry out complicated activation when having avoided being template with macromolecular material or Inorganic Non-metallic Materials, sensitization is handled and could be deposited or the problem of metal lining shell.Simultaneously, by the size of control iron nuclear, it is little to 30 nanometers, greatly to the hollow magnetic ball of 9 microns cobalt, nickel and alloy thereof to prepare internal diameter size, promptly has the controlled and prepared wide characteristics of hollow ball particle diameter range scale of hollow ball particle diameter.Adopt the iron nuclear of chain or wire to be template, also can prepare the magnetic tube of the metal or alloy shell of pipe inner diameter size scope between 30 nanometers to 9 micron.
Beneficial effect
When (1) adopting the hollow magnetic ball of the disclosed prepared cobalt of this patent, nickel and alloy thereof, has characteristic of simple process.
Contrasting existing is that template is when preparing hollow magnetic ball with polymer microsphere or with the inorganic non-metallic hollow ball, after adopting chemical method self-control iron nuclear, can directly deposit or plating magnetic metal or alloy shell on its surface, do not need to its surface activate, sensitization handles, and when adopting the iron nuclear of outsourcing, only need carry out roughening treatment to iron nuclear surface, can deposit or plating technic, therefore, characteristic of simple process.
(2) hollow magnetic ball can be prepared and magnetic tube can be prepared again.
By control iron nuclear shape is sphere or wire, chain, adopts the disclosed prepared of this patent promptly can prepare hollow magnetic ball and can prepare magnetic tube again.
Description of drawings
Fig. 1 cobalt hollow ball forms the process schematic diagram.
Fig. 2 sonochemistry cobalt plating experimental rig.
Embodiment
The invention will be further described to engage drawings and Examples below.
Embodiment 1
(1) preparation of nanometre grade cobalt hollow ball
The preparation process of nanometre grade cobalt hollow ball as shown in Figure 1, when being template with iron nuclear, coating surface one deck crust of cobalt, form " nuclear-shell " composite construction of cobalt iron clad, when this composite construction is in the acid solution, the primary cell reaction takes place, at this moment, iron nuclear is the positive pole of battery, with H
+Reaction, releasing hydrogen gas, and be consumed, and crust of cobalt is retained as negative electrode, as iron nuclear and H
+When reaction was over, " nuclear-shell " composite construction of cobalt iron clad became the cobalt hollow ball.Concrete operations technology is:
The first step, the preparation of nanometer iron nuclear (iron particle)
At volume is the 0.1molL of 40ml
-1FeSO
4The 0.2molL that dropwise adds equal volume in the solution
-1NaBH
4Solution, the pH value of control mixed liquor is about 9～12, dropwises the back and continues reaction 10min, until reacting completely, gets black nano iron particle.
Second step, the preparation of cobalt iron clad Nano composite granules
Continuation drips 0.1molL simultaneously in above-mentioned reaction solution
-1CoSO
4Solution and 0.1molL
-1NaBH
4Each 20ml of solution after dropwising, continues reaction 10min, obtains black precipitate, with its successively water and absolute ethyl alcohol wash behind the several times dry, the nano particle of cobalt iron clad " nuclear-shell " composite construction.
The 3rd step, the removal of iron nuclear template
The nano particle of cobalt iron clad " nuclear-shell " composite construction that obtains and watery hydrochloric acid reaction reddened a little until solution, and (volume fraction is that the consumption of 1～5% watery hydrochloric acid is that every 50mg black powder is with 10～50ml), at last with after the final reacting product that obtains water successively and the absolute ethyl alcohol cleaning, drying the nanometre grade cobalt hollow ball.
Embodiment 2
(2) preparation of micron order cobalt hollow ball
Employing is carried out electroless cobalt plating and is formed cobalt iron clad " nuclear-shell " composite construction on the carbonyl iron dust surface, can prepare micron order cobalt hollow ball.
The first step, the carbonyl iron dust surface preparation
Test select for use on the market the average grain diameter of selling at 3 microns, the carbonyl iron dust of spherical shape as template, iron-holder is 97%.For removing the oxide-film on carbonyl iron dust surface, adopt watery hydrochloric acid that preliminary treatment is carried out on its surface, eliminate the oxide that generates, the activation matrix surface.Pretreatment fluid composition and process conditions are as shown in table 1, and preprocessing process is as follows:
Table 1 pretreatment fluid is formed and process conditions
A certain amount of carbonyl iron dust is put in the certain density hydrochloric acid solution by table 1 proportioning, and at room temperature intense mechanical stirred 150 seconds, and followed sonic oscillation; Carbonyl iron dust after the processing that obtains cleaned up with distilled water and air-dry.
Second step, carbonyl iron surface chemistry cobalt plating
Carbonyl iron surface chemistry cobalt plating process is carried out in sonochemistry cobalt plating experimental rig (shown in the accompanying drawing 2).The ultimate constituent and the process conditions of carbonyl iron dust electroless cobalt plating reactant liquor are as shown in table 2.
The ultimate constituent of table 2 carbonyl iron dust electroless cobalt plating reactant liquor and process conditions (continuous table)
Chemical plating process is as follows in the technical process of carbonyl iron coating surface crust of cobalt:
1. use deionized water dissolve sulfur acid cobalt, and filter, obtain red solution;
2. dissolve sodium potassium tartrate tetrahydrate and EDTA disodium respectively with deionized water, two kinds of solution that obtain are mixed;
3. the mixed solution that the solution that makes in inciting somebody to action 1. obtains in being added drop-wise to 2. while stirring generates red complex salt solution;
4. behind the 5min, in the solution that previous step obtains, slowly add hydrazine hydrate, red precipitation then in clear solutions, occurs;
5. adjust the pH value with NaOH solution, add water volumetric flask constant volume then.
The surface obtains " nuclear-shell " complex microsphere of cobalt iron clad behind electroless cobalt plating, behind its usefulness distillation washing several times, and kept dry.
The 3rd step, the removal of carbonyl iron template
Get cobalt iron clad " nuclear-shell " complex microsphere of the above-mentioned carbonyl iron of 1g surface cobalt plating, put in the certain density hydrochloric acid solution for preparing, concentration of hydrochloric acid is as shown in table 3, mechanical agitation in addition, and the dissolving certain hour (can obtain micron order cobalt tiny balloon after 30～80min).
Table 3 template is removed liquid (pickling solution) concentration proportioning
(3) other explanation
1. when in the above-mentioned test divalent cobalt being replaced with divalent nickel salt, can prepare the nickel hollow ball.
2. when in deposition or chemical plating process, utilize ultrasonic echography vibration simultaneously when the nickel of deposition or the different proportionings of plating and cobalt, can obtain " nuclear-shell " composite construction that cobalt-nickel alloy coats iron nuclear, behind heating crystallization, pass through acid etching again, removal iron nuclear obtains the cobalt-nickel alloy hollow ball.
3. when adopting iron nuclear for chain or wire, by above-mentioned processing step, be the alloy shell of main component at the iron nuclear surface deposition of chain or wire or plating magnetic cobalt, nickel or with cobalt, nickel after, remove iron nuclear through acid etching again, can obtain corresponding magnetic tube.
Claims (3)
1. hollow magnetic ball or magnetic tube preparation method, it is characterized in that: adopting the iron nuclear with spherical or subsphaeroidal iron nuclear or employing chain or wire is template, at its surface deposition or plating one deck magnetic metal or alloy shell, magnetic metal or alloy shell are metallic cobalt, metallic nickel or are the magnetic alloy material of main body composition with cobalt, nickel, obtain " nuclear-shell " composite construction; Be placed on then in the acid solution, adopt the primary cell reaction principle, the soluble iron nuclear above-mentioned magnetic metal of template for preparing of corrosion " nuclear-shell " structure or the hollow ball or the magnetic tube of alloy shell.
2. a kind of hollow magnetic ball according to claim 1 or magnetic tube preparation method is characterized in that: the internal diameter size scope of hollow ball is between 30 nanometers to 9 micron; Magnetic tube inner diameter size scope is between 30 nanometers to 9 micron.
3. a kind of hollow magnetic ball according to claim 1 or magnetic tube preparation method is characterized in that: utilize the ultrasonic echography vibration or utilize mechanical agitation to carry out described deposition or plating on iron nuclear surface.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102515086B (en) * | 2011-11-21 | 2015-08-19 | 台州学院 | There is the preparation method of the Co nano-structure array material of morphologic correlation magnetic |
| CN103421470B (en) * | 2012-05-24 | 2016-01-20 | 中国科学院理化技术研究所 | A kind of cooling fluid comprising rigid hollow particle |
| CN103449538B (en) * | 2013-07-02 | 2014-09-24 | 南京吉安特环保技术有限公司 | Preparation method of nano palladium oxide hollow spheres |
| CN103586460A (en) * | 2013-11-11 | 2014-02-19 | 山东大学 | Magnetic porous cobalt hollow ball electromagnetic wave absorption material, preparation method and application thereof |
| CN109021573B (en) * | 2018-06-20 | 2021-03-16 | 北京航数车辆数据研究所有限公司 | Intelligent material composed of thin-wall hollow sphere and magnetosensitive elastomer |
| CN116333699B (en) * | 2023-03-16 | 2024-03-29 | 中南大学 | Well filling material for in-situ leaching uranium extraction well and application method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1761003A (en) * | 2005-11-22 | 2006-04-19 | 武汉理工大学 | Method for fabricating magnetic hollow ball |
| CN101086911A (en) * | 2007-04-16 | 2007-12-12 | 华东理工大学 | Magnetic hollow micro-ball including Mn-Fe and its making method and application |
| CN101183588A (en) * | 2007-10-18 | 2008-05-21 | 上海交通大学 | Method of preparing magnetic hollow micro-nano ball with template of high molecule micro-nano ball |
| CN101318709A (en) * | 2008-06-25 | 2008-12-10 | 华东理工大学 | Method for preparing nano-gamma-Fe2O3 hollow magnetic microsphere |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1761003A (en) * | 2005-11-22 | 2006-04-19 | 武汉理工大学 | Method for fabricating magnetic hollow ball |
| CN101086911A (en) * | 2007-04-16 | 2007-12-12 | 华东理工大学 | Magnetic hollow micro-ball including Mn-Fe and its making method and application |
| CN101183588A (en) * | 2007-10-18 | 2008-05-21 | 上海交通大学 | Method of preparing magnetic hollow micro-nano ball with template of high molecule micro-nano ball |
| CN101318709A (en) * | 2008-06-25 | 2008-12-10 | 华东理工大学 | Method for preparing nano-gamma-Fe2O3 hollow magnetic microsphere |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2007-9278A 2007.01.18 |
| JP特开2008-106301A 2008.05.08 |
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