CN105271431B - Method for preparing ferriferrous oxide magnetic material and composite material thereof - Google Patents
Method for preparing ferriferrous oxide magnetic material and composite material thereof Download PDFInfo
- Publication number
- CN105271431B CN105271431B CN201510658488.1A CN201510658488A CN105271431B CN 105271431 B CN105271431 B CN 105271431B CN 201510658488 A CN201510658488 A CN 201510658488A CN 105271431 B CN105271431 B CN 105271431B
- Authority
- CN
- China
- Prior art keywords
- magnetic material
- xerogel
- chelating agent
- product
- colloidal sol
- 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
Abstract
A disclosed method for preparing a ferriferrous oxide magnetic material and a composite material thereof comprises the following steps: adding a ferric salt and a complexing agent into a solvent to form a solution, and adjusting the pH value of the solution to form a sol, wherein the molar ratio of the complexing agent to the ferric salt is 0.1-1.5:1; heating or evaporating at room temperature to 200 DEG C so as to remove the solvent in toe sol and form an xerogel, wherein the xerogel contains a fuel and an oxidizing agent; putting the xerogel into a reactor as a precursor of a spontaneous combustion reaction, and combusting at 150 DEG C or more in a inert atmosphere or weakly oxidizing atmosphere; and continuously cooling the combustion product in the inert atmosphere or the weakling oxidizing atmosphere, so as to obtain the ferriferrous oxide magnetic material. Also, the ferriferrous oxide composite material can be prepared by adding a composite composition into the sol. The prepared product is controllable in magnetic property, the saturation moment is adjustable in the scope of 33 emu/g to 91 emu/g, and the product possesses a porous structure, large specific surface area and ultra-low density, and belongs to a loose-structure large-surface-activity nanometer powder.
Description
Technical field
The present invention relates to a kind of method for preparing magnetic material, and in particular to one kind prepare Fe 3 O 4 magnetic material and
The method of its composite, belongs to field of material technology.
Background technology
Fe 3 O 4 magnetic material due to unique electricity and magnetic performance, in magnetic storage, magnetic liquid, life
The multiple fields such as thing medical science, permanent magnet material have broad application prospects.
The preparation of Fe 3 O 4 magnetic material at present mainly adopts hydro-thermal method, coprecipitation, hydrogen (or other gases)
Reducing process, mini-emulsion process or pyrosol gel method.Fe 3 O 4 magnetic material particles good dispersion prepared by hydro-thermal method, but
Reaction need to be completed under high temperature and high pressure environment, higher to equipment requirements, be unfavorable for large-scale production；The four of coprecipitation preparation
Fe 3 O nanoparticle granule is uniform, particle narrowly distributing, is easy to large-scale production, but particle agglomeration is serious, affect material
Energy；The Fe 3 O 4 magnetic material particles good dispersion of mini-emulsion process preparation, form rule, narrow diameter distribution, but its preparation
Technique is complex, and introduces surfactant, cosurfactant etc. and cleaned with organic solvent repeatedly, and not easy-clear；
Pyrosol gel method prepares that ferriferrous oxide nano-particle purity is higher, uniformity is good, granule is tiny, and due to preparation process
In need high temperature to go the removal of impurity, prepare complex.
Therefore, when Fe 3 O 4 magnetic material is prepared using these common methods, need the equipment of complex and expensive, special
Raw material, or need higher temperature environment, or need to be accurately controlled high temperature and high pressure environment, and some sides
Toxic gas can be produced in the preparation process of method.
Sol-gel processing refer to metal organic or inorganic compound through dissolving, colloidal sol, gel and solidify, then through heat
The method that process forms oxide or other compound solids, the method is because reaction temperature is low, even particle size distribution, simple to operate
The advantages of and receive publicity, but the fatal defects of the method are relatively costly powder body easily reunites and is difficult drying.Spontaneous combustion skill
Art is come a kind of technology of synthetic material using the self-heating of high chemical reaction heat between reactant and from conduction.
The present invention is directed to defect of the prior art, is in depth studied, sol-gel process is mutually tied with spontaneous combustion
Close, define the technology of the present invention, both avoided the shortcoming of sol-gal process, developed the excellent of spontaneous combustion and sol-gal process again
Point.
The content of the invention
Goal of the invention：The first object of the present invention is to provide a kind of method for preparing Fe 3 O 4 magnetic material, this
The second bright purpose is to provide a kind of method that use the method prepares ferriferrous oxide composite material.Four oxygen obtained in of the invention
Change three-iron magnetic material magnetic is controllable, excellent performance, can be widely used for magnetic storage, soft magnetic materials, lightweight absorbing material, catalysis
The aspects such as agent, sewage disposal, ferrofluid, medical imaging, medicine delivery.
Technical scheme：A kind of method for preparing Fe 3 O 4 magnetic material of the present invention, comprises the following steps：
(1) iron salt, chelating agent are added in solvent and forms solution, the pH value for adjusting the solution is allowed to form colloidal sol, wherein,
Chelating agent is added to be 0.1～1.5 with the mol ratio of iron salt：1；
(2) solvent in the colloidal sol is removed under the temperature conditionss of room temperature to 200 DEG C, xerogel, the xerogel is formed
In contain fuel and oxidant simultaneously；
(3) put xerogel as the presoma that spontaneous combustion is reacted in the reactor, control the indifferent gas more than 150 DEG C
Burn in atmosphere or weak oxide atmosphere；
(4) product after burning continues to cool down in inert atmosphere or weak oxide atmosphere, obtains Fe 3 O 4 magnetic
Material.
The present invention is combined with auto-combustion method using sol-gel process and prepares Fe 3 O 4 magnetic material, chelating agent point
Son generates complex with iron ion in iron salt solutions, and the polycondensation that is cross-linked with each other between complex gradually forms network structure, with
The evaporation colloidal sol of moisture and other solvents slowly loses flowability so as to be formed after to gel conversion, being further dehydrated and lower the temperature
Xerogel；When sol-gel auto-combustion burns and reacts because the Main Ingredients and Appearance of chelating agent decomposes can produce reducing atmosphere, I
These compositions of chelating agent are called fuel, and because the Main Ingredients and Appearance of iron salt decomposes can produce oxidizing atmosphere, I
These compositions in iron salt are called oxidant just, therefore, contain fuel and oxidant in the xerogel simultaneously, in indifferent gas
Can light under atmosphere or weak oxide atmosphere protection carries out spontaneous combustion, it is not necessary to extraneous to provide oxygen；Meanwhile, the present invention is by adjusting
Save the ratio of chelating agent and iron salt to control product component, so as to the magnetic for controlling obtained Fe 3 O 4 magnetic material is strong
Weak, the saturation magnetic moment of products therefrom can be adjusted in the range of 33emu/g to 91emu/g.
Wherein, in step (1), the pH value for forming colloidal sol is 6～9.
Preferably, chelating agent is added to be 0.5～0.9 with the mol ratio of iron salt in step (1)：1.Now obtained product
Component is pure ferroso-ferric oxide, and its relatively high magnetism, saturation magnetic moment are more than 70emu/g, reach as high as 91emu/g.
Preferably, chelating agent is citric acid, oxalic acid, tartaric acid, salicylic acid, EDTA, dimercaptopropanol, BAL, mercaptoethylmaine, mercapto
Guanidine-acetic acid, thiourea, ammonium fluoride, 8-hydroxyquinoline, cyanide, acetylacetone,2,4-pentanedione, triethanolamine, EGTA, ethylenediamine tetrapropionic acid, three second
Support tetramine, carboxylic acid, aminoacid, polyvinyl alcohol, hydrazine and hydrazine derivative, ethylenediamine, one or several the mixing in carbamide
Thing.
It is furthermore preferred that chelating agent is citric acid and/or aminoacid.
Preferably, iron salt is ferric nitrate.Now the nitrate anion in ferric nitrate can be used as in the xerogel formed in step (2)
Oxidant.
Preferably, solvent be water, ethanol, ethylene glycol, methanol, ether, amine, nitrile, ketone, dioxane, in tetrahydrofuran one
Plant or several mixture.
Preferably, select ammonia, carbamide or ammonium salt to adjust solution ph in step (1).
Preferably, weak oxide atmosphere can be pure gases or mixed gas.
It is of the present invention to prepare ferriferrous oxide composite material using the method for preparing Fe 3 O 4 magnetic material
Method, be included in the colloidal sol that step (1) is formed the compounding ingredients source that adds, then according to the method system of step (2)～(4)
It is standby, obtain final product the composite of ferroso-ferric oxide.
Beneficial effect：The present invention is had the advantage that compared with prior art：
(1) magnetic of product obtained in the present invention is controllable, by controlling different iron salt with chelating agent in preparation process
Mol ratio, can prepare the ferroso-ferric oxide of different magnetic strengths, and its saturation magnetic moment can enter in the range of 33emu/g to 91emu/g
Row is adjusted；And prepared product has foam-like porous structures, with big specific surface area and extremely-low density, belong to structure and dredge
The big nano-powder of pine, surface activity；
(2) present invention uses spontaneous combustion burning technology, and course of reaction is temperature required relatively low, and spontaneous combustion process is tieed up by self-heat generation
Hold, in addition to lighting xerogel and needing to provide very small amount heat, course of reaction outside need not be provided and continue heat, and light dry
The heat of gel need to only use alcohol burner or lighter provide, and greatly save the energy consumption in production process；
(3) raw material is easy to get, device simple, low production cost, preparation process are quick, safe, simple：It is main needed for of the invention
Raw material is the iron salt and chelating agent for providing Fe ions, is common chemical reagent, simple and easy to get；Whole preparation process of the present invention
Expensive high-temperature high-pressure apparatus is not needed, it is not necessary to which high-power power equipment, production cost are relatively low；Course of reaction also without
Hydrogen annealing, or even can be carried out in atmosphere, production process is safe and reliable；Meanwhile, spontaneous combustion burning technology response speed quickly,
It is short the time required to preparing product, substantially reduce the time prepared needed for product；After the completion of reaction, allow product voluntarily in indifferent gas
Cooling under atmosphere or weak oxide atmosphere obtains final product product.
Description of the drawings
Fig. 1 is the scanning electron microscopic picture of Fe 3 O 4 magnetic material prepared by the present invention.
Fig. 2 is the hysteresis curve of Fe 3 O 4 magnetic material prepared by the present invention.
Fig. 3 is the chelating agent for adding different mol ratio with the X-ray diffraction of Fe 3 O 4 magnetic material obtained in iron salt
Collection of illustrative plates.
The X-ray diffraction of obtained Fe 3 O 4 magnetic material when Fig. 4 is 0.5 for mol ratio Φ of chelating agent and iron salt
Collection of illustrative plates.
Fig. 5 is the saturation magnetic moment of product with chelating agent and the change curve of mol ratio Φ of iron salt.
Specific embodiment
Below in conjunction with the accompanying drawings technical scheme is described further.
The present invention provides a kind of method for preparing Fe 3 O 4 magnetic material, comprises the following steps：
(1) iron salt, chelating agent are added in solvent and forms solution, the pH value for adjusting the solution is allowed to form colloidal sol, wherein,
Chelating agent is added to be 0.1～1.5 with the mol ratio of iron salt in iron salt：1；
(2) solvent in the colloidal sol is removed under the temperature conditionss of room temperature to 200 DEG C, xerogel, the xerogel is formed
In contain fuel and oxidant simultaneously；
(3) put xerogel as the presoma that spontaneous combustion is reacted in the reactor, control the indifferent gas more than 150 DEG C
Burn in atmosphere or weak oxide atmosphere；
(4) product after burning continues to cool down in inert atmosphere or weak oxide atmosphere, obtains Fe 3 O 4 magnetic
Material.
Wherein, in step (1), iron salt can be iron chloride, ferrous chloride, iron acetate, iron sulfate, ferrous sulfate etc.；Iron salt
Alternatively ferric nitrate, now, the nitrate anion in ferric nitrate can be used as the oxidant of the xerogel formed in step (2).Chelating agent
May be selected from citric acid, oxalic acid, tartaric acid, salicylic acid, EDTA, dimercaptopropanol, BAL, mercaptoethylmaine, TGA, thiourea, fluorination
Ammonia, 8-hydroxyquinoline, cyanide, acetylacetone,2,4-pentanedione, triethanolamine, EGTA, ethylenediamine tetrapropionic acid, triethylenetetramine, carboxylic acid, amino
Acid, polyvinyl alcohol, hydrazine and hydrazine derivative, ethylenediamine, one or several the mixture in carbamide, preferred chelating agent are lemon
Lemon acid and/or aminoacid.Solvent be water, ethanol, ethylene glycol, methanol, ether, amine, nitrile, ketone, dioxane, in tetrahydrofuran one
Plant or several mixture.Iron salt, chelating agent are added in solvent and forms solution, can select ammonia, carbamide or ammonium salt to adjust
Solution ph is allowed to form colloidal sol, and the pH value for forming colloidal sol is 6～9.
Colloidal sol obtained by step (1) can remove solvent under the temperature conditionss of room temperature to 200 DEG C, without the need for specially providing high temperature
The heating devices such as stove.Complexation agent molecule generates complex with iron ion in iron salt solutions, and be cross-linked with each other between complex polycondensation
Network structure is gradually formed, as the evaporation colloidal sol of moisture and other solvents slowly loses flowability so as to gel conversion, enter
One step is dehydrated and forms xerogel after lowering the temperature；When sol-gel auto-combustion burns and reacts because the Main Ingredients and Appearance of chelating agent decomposes meeting
Reducing atmosphere is produced, so we call fuel these compositions of chelating agent, and because the Main Ingredients and Appearance of iron salt decomposes meeting
Oxidizing atmosphere is produced, so we just call oxidant these compositions in iron salt, therefore, in the xerogel of formation in itself
Contain fuel and oxidant, as presoma, under the inert atmosphere or weak oxide atmosphere protection more than 150 DEG C i.e.
Can light makes which carry out spontaneous combustion, it is not necessary to extraneous to provide oxygen, and lights temperature required relatively low, with lighter or alcohol burner is
Can, it is not required to be additionally provided heat.
In step (2), the moisture in colloidal sol can be removed by way of heating or evaporating.
Inert atmosphere can be the mixed gas of one or more in the noble gases such as helium, neon, argon.Weak oxide
Atmosphere refers to atmosphere of the oxidability less than oxygen, and the Fe 3 O 4 magnetic material of the present invention cannot be obtained in pure oxygen atmosphere
Material.The weak oxide atmosphere can be the weaker pure gases of oxidisability, such as nitrogen, hydrogen, CO (carbon monoxide converter) gas, carbon dioxide gass
Body, alkanes gas etc.；Alternatively mixed gas, such as air, or nitrogen, hydrogen, CO (carbon monoxide converter) gas, carbon dioxide, alkane
The mixed gas of one or more in the weaker gas of the oxidisability such as class gas, or it is the weaker gas of oxidisability and oxygen, lazy
The mixed gas of one or more in property gas.Wherein, obtained product relatively high magnetism under inert atmosphere.
The present invention by adjusting raw material chelating agent and the mol ratio of iron salt to obtain the product of different compositions, product difference its
Magnetic strength also, can control product generation according to different magnetic demands.It is preferably added to the mol ratio of chelating agent and iron salt
For 0.5～0.9：1, now the component of obtained Fe 3 O 4 magnetic material be pure ferroso-ferric oxide, its relatively high magnetism, saturation
Magnetic moment is more than 70emu/g, reaches as high as 91emu/g.
The method of the present invention can also be used for the various composites for preparing ferroso-ferric oxide.Can step (1) formed it is molten
Addition compounding ingredients source in glue, such as silicon source, manganese source etc., then according to the method for step (2)-(4), you can prepare four oxidations three
The various composites of ferrum.For example：Silicon source (such as tetraethyl orthosilicate) is added in the colloidal sol that step (1) is formed, four oxygen can be obtained
Change the composite of three-iron and silicon dioxide；In the colloidal sol that step (1) is formed, manganese addition source (as nitric acid is violent), can be obtained four oxidations
The composite of three-iron and manganese dioxide.
Embodiment 1
Chelating agent is 0.5 with the mol ratio of iron salt：1, Fe 3 O 4 magnetic material is prepared under argon protection
Weigh during 4.040g ferric nitrates, 1.051g citric acids add 50ml water and solution is formed after stirring 20 minutes, add ammonia
Water adjusts the pH value of the solution and is allowed to form colloidal sol, and the pH value of colloidal sol is adjusted to 6；Then at 95 DEG C, evaporation is removed in colloidal sol
Moisture, forms xerogel, contains fuel and oxidant in xerogel.Xerogel is put in quartz ampoule, is protected by argon,
Light at 300 DEG C.After xerogel spontaneous combustion, continue to cool down under argon protection, after being cooled to room temperature, product is four oxidations three
Ferrimagnet.
Embodiment 2
Chelating agent is 0.9 with the mol ratio of iron salt：1, Fe 3 O 4 magnetic material is prepared under air conservation
Weigh during 2.020g ferric nitrates, 0.263g glycines add 25ml water and 5ml ethanol and form solution, add carbamide
The pH value for adjusting the solution is allowed to form colloidal sol, and the pH value of colloidal sol is 6.2；The evaporation at 90 DEG C removes water and second in colloidal sol
Alcohol, forms xerogel.Contain fuel and oxidant in xerogel.Xerogel is put in quartz ampoule, in atmosphere point at 200 DEG C
Combustion.After xerogel spontaneous combustion, continuation is cooled down in atmosphere, and after cooling, product is Fe 3 O 4 magnetic material.
Fig. 1 is the scanning electron microscopic picture of Fe 3 O 4 magnetic material prepared by above-described embodiment.As shown in Figure 1, this
The Fe 3 O 4 magnetic material of bright preparation has loose structure, and with big specific surface area and extremely-low density, aperture averaging is
500nm, density is：0.07g/cm3, belong to the big nano-powder of short texture, surface activity.
Fig. 2 is the hysteresis curve of Fe 3 O 4 magnetic material prepared by above-described embodiment.As shown in Figure 2, present invention system
Standby Fe 3 O 4 magnetic material has obvious ferromagnetism, and saturation magnetic moment is 73emu/g；Coercivity is 220Oe, illustrates this
Product is soft magnetic materials.
In above-mentioned reaction, iron salt is alternatively iron chloride, ferrous chloride, iron acetate, iron sulfate, ferrous sulfate etc.；Chelating agent
Alternatively oxalic acid, tartaric acid, salicylic acid, EDTA, dimercaptopropanol, BAL, mercaptoethylmaine, TGA, thiourea, ammonium fluoride, 8- hydroxyls
Quinoline, cyanide, acetylacetone,2,4-pentanedione, triethanolamine, EGTA, ethylenediamine tetrapropionic acid, triethylenetetramine, carboxylic acid, polyvinyl alcohol, hydrazine and
Hydrazine derivative, ethylenediamine, one or several the mixture in carbamide, chelating agent can be obtained when being citric acid or aminoacid
The higher product of magnetic；Solvent be alternatively ethylene glycol, methanol, ether, amine, nitrile, ketone, dioxane, the one kind in tetrahydrofuran or
Several mixture.
Impact of the mol ratio of 3 chelating agent of embodiment and iron salt to product
6 groups of parallel laboratory tests are carried out, and addition in Fe 3 O 4 magnetic material, step (1) are prepared with reference to the method for embodiment 1
Citric acid is respectively 0.1,0.3,0.5,0.9,1.2 and 1.5 with the mol ratio of ferric nitrate, and the product for preparing gained is penetrated by X
Line diffraction, is analyzed to gained collection of illustrative plates.
Fig. 3 is the chelating agent for adding different mol ratio with the X-ray diffraction of Fe 3 O 4 magnetic material obtained in iron salt
Collection of illustrative plates.As seen from the figure, when mol ratio Φ of chelating agent and iron salt is 0.1, in product, the diffraction maximum of ferroso-ferric oxide is weaker；With
The increase of Φ, the diffraction maximum of ferroso-ferric oxide constantly strengthens, but still contain a certain amount of iron sesquioxide；When Φ is 0.5,
The diffraction maximum of ferroso-ferric oxide reaches most strong, the diffraction maximum disappearance of iron sesquioxide, illustrates that now product is only ferroso-ferric oxide；
When Φ continues to increase, with the increase of Φ, the diffraction peak intensity of ferroso-ferric oxide gradually weakens, when particularly Φ is more than 0.9,
The diffraction peak intensity of ferroso-ferric oxide is very weak, and when this explanation Φ is more than 0.9, product is ferroso-ferric oxide and amorphous carbon
Complex；When Φ rises to 1.5, the intensity of ferroso-ferric oxide diffraction maximum is almost equal to zero.
The X-ray diffraction of obtained Fe 3 O 4 magnetic material when Fig. 4 is 0.5 for mol ratio Φ of chelating agent and iron salt
Collection of illustrative plates.The diffracting spectrum is met with powder diffraction standard card (JCPDS card No.008-4511) very much, illustrates that product is
Ferroso-ferric oxide with inverse spinel structure.
Fig. 5 is the saturation magnetic moment of product with chelating agent and the change curve of mol ratio Φ of iron salt.As seen from the figure, product
Magnetic can be adjusted with mol ratio Φ of iron salt by changing chelating agent, the saturation magnetic moment of product can be 33emu/g extremely
91emu/g.When Φ is 0.5～0.9, saturation magnetic moment is all higher than 70emu/g, now, the relatively high magnetism of product；When Φ is 0.5
When, saturation magnetic moment is maximum, is 91emu/g, the theoretical value of this numerical value closely saturation magnetic moment of ferroso-ferric oxide.
Claims (4)
1. a kind of method for preparing Fe 3 O 4 magnetic material, it is characterised in that comprise the following steps：
(1) iron salt, chelating agent are added in solvent and forms solution, the pH value for adjusting the solution is allowed to form colloidal sol, forms colloidal sol
PH value be 6～9, wherein, the mol ratio for adding chelating agent and iron salt is 0.5～0.9：1；The chelating agent is citric acid, grass
Acid, thiourea, aminoacid, one or several mixture of ethylenediamine, the iron salt are ferric nitrate, and the solvent is water, second
The mixture of one or more in alcohol, ethylene glycol, methanol, ether, amine, nitrile, ketone, dioxane, tetrahydrofuran；
(2) solvent in the colloidal sol is removed under the temperature conditionss of room temperature to 200 DEG C, xerogel is formed, it is same in the xerogel
Shi Hanyou fuel and oxidant；
(3) put the xerogel as the presoma that spontaneous combustion is reacted in the reactor, control in the air more than 150 DEG C
Burning；
(4) product after burning continues to cool down in atmosphere, obtains Fe 3 O 4 magnetic material.
2. the method for preparing Fe 3 O 4 magnetic material according to claim 1, it is characterised in that the chelating agent is
Citric acid and/or aminoacid.
3. the method for preparing Fe 3 O 4 magnetic material according to claim 1, it is characterised in that：Choosing in step (1)
Solution ph is adjusted with ammonia, carbamide or ammonium salt.
4. a kind of usage right requires the method that the method described in 1 prepares ferriferrous oxide composite material, it is characterised in that in step
Suddenly compounding ingredients source is added in the colloidal sol that (1) is formed, then according to prepared by the method for step (2)～(4), ferroso-ferric oxide is obtained final product
Composite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510658488.1A CN105271431B (en) | 2015-10-12 | 2015-10-12 | Method for preparing ferriferrous oxide magnetic material and composite material thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510658488.1A CN105271431B (en) | 2015-10-12 | 2015-10-12 | Method for preparing ferriferrous oxide magnetic material and composite material thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105271431A CN105271431A (en) | 2016-01-27 |
| CN105271431B true CN105271431B (en) | 2017-04-12 |
Family
ID=55141370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510658488.1A Expired - Fee Related CN105271431B (en) | 2015-10-12 | 2015-10-12 | Method for preparing ferriferrous oxide magnetic material and composite material thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105271431B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107128881B (en) * | 2017-06-22 | 2019-03-19 | 合肥学院 | A method of preparing sulphur micro-nano rice flour and ferriferrous oxide nano powder together |
| CN107282026A (en) * | 2017-06-26 | 2017-10-24 | 浙江大学宁波理工学院 | Chain nano magnetic material, preparation method and applications |
| CN107416909A (en) * | 2017-08-28 | 2017-12-01 | 哈尔滨工业大学 | A kind of preparation method of iron-based oxide silica aerogel |
| CN110548483A (en) * | 2019-05-25 | 2019-12-10 | 北京化工大学 | preparation method and application of biochar/nano ferroferric oxide composite material |
| CN110164703B (en) * | 2019-06-21 | 2021-07-09 | 江苏科技大学 | Porous Fe3O4/C polyhedral material and preparation method and application thereof |
| CN110404548B (en) * | 2019-08-21 | 2020-12-04 | 南京大学 | high-pH-adaptability carbon nanotube catalyst and application thereof |
| CN111348640B (en) * | 2019-12-14 | 2021-05-25 | 武汉瑞科美新能源有限责任公司 | Porous carbon-Fe3O4Nanomaterial, air positive electrode material and lithium-air battery |
| CN114452930A (en) * | 2022-01-26 | 2022-05-10 | 长春大学 | Preparation method and application of nanocrystalline material for removing formaldehyde |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0226834A (en) * | 1988-07-16 | 1990-01-29 | Nippon Steel Corp | Manufacture of spherical magnetic material |
| US5589097A (en) * | 1993-12-24 | 1996-12-31 | Tdk Corporation | Method for preparing magnetite magnetic powder |
| CN101229931B (en) * | 2008-01-25 | 2010-06-02 | 华中科技大学 | Method for preparing nano Fe3O4 |
| CN101381110B (en) * | 2008-10-24 | 2010-07-21 | 北京科技大学 | Method for preparing ferriferrous oxide nano powder by means of carbon thermal reduction |
-
2015
- 2015-10-12 CN CN201510658488.1A patent/CN105271431B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105271431A (en) | 2016-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105271431B (en) | Method for preparing ferriferrous oxide magnetic material and composite material thereof | |
| CN107086313B (en) | A kind of iron, cobalt, nitrogen co-doped Pd/carbon catalyst and its preparation method and application | |
| CN101299914B (en) | Nanocrystalline ultra-fine alloy powder electromagnetic wave absorbent and preparation method thereof | |
| CN108706637B (en) | A kind of preparation method of adjustable magnetic iron oxide mesomorphic material of uniform size | |
| CN101913854B (en) | Preparation method of nanometer strontium ferrite magnetic powder | |
| CN102515129A (en) | Preparation method for submicron battery-grade ferric phosphate | |
| CN102134470B (en) | Method for preparing porous carbon born nano ferrite wave-absorbing material | |
| CN103754954A (en) | Preparation method of iron molybdenum oxide (II) nanocube | |
| Masoudpanah et al. | The effect of the ethylene glycol to metal nitrate molar ratio on the phase evolution, morphology and magnetic properties of single phase BiFeO3 nanoparticles | |
| CN103466719B (en) | Preparation method of nanocomposite with controllable iron-loading state in ordered mesoporous carbon substrate | |
| CN103086706B (en) | Preparation method for Zr-Mn-Co multi-doped barium ferrite wave-absorbing material | |
| CN101229931B (en) | Method for preparing nano Fe3O4 | |
| CN112159219A (en) | Yttrium-doped nickel-zinc-cobalt ferrite and preparation method thereof | |
| CN104525962A (en) | Method for preparing nanoscale oxide dispersion strengthening iron-based composite powder | |
| CN102557151B (en) | Method for preparing nanometer ferroferric oxide powder by reducing at one step | |
| CN102744419B (en) | Morphology control method of magnetic nanometer particles | |
| CN105081338B (en) | Method for preparing mono-dispersed NdFeB nano particles | |
| CN102992377A (en) | Method for preparing nano rare earth oxide through microwave sol-gel technology | |
| CN104495947B (en) | A kind of method preparing receiving bore croci | |
| CN108373327B (en) | Nickel-zinc-cerium ferrite soft magnetic material and preparation method thereof | |
| CN106365205A (en) | Preparation method of manganese zinc ferrite nano-powder | |
| CN115947387A (en) | B-site five-element high-entropy double perovskite structure oxide electrode material and preparation method thereof | |
| CN101462774B (en) | Nano ferrous iron oxide colloid and preparation thereof | |
| CN103771536A (en) | Ferroferric oxide rhombic dodecahedron particles and preparation method thereof | |
| CN103274476B (en) | Method for preparing gamma-Fe2O3 nanosheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into 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: 20170412 Termination date: 20171012 |