CN113200572A - Process method for preparing cobalt ferrite powder at low temperature in dry state - Google Patents
Process method for preparing cobalt ferrite powder at low temperature in dry state Download PDFInfo
- Publication number
- CN113200572A CN113200572A CN202110494793.7A CN202110494793A CN113200572A CN 113200572 A CN113200572 A CN 113200572A CN 202110494793 A CN202110494793 A CN 202110494793A CN 113200572 A CN113200572 A CN 113200572A
- Authority
- CN
- China
- Prior art keywords
- cobalt ferrite
- ferrite powder
- cobalt
- powder
- process method
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
Abstract
The invention discloses a process method for preparing magnetic cobalt ferrite powder at low temperature in a dry state, which comprises the steps of adding a cobalt source and an iron source into a solvent for dissolving, stirring and mixing to obtain a uniform solution, and drying to obtain mixed powder; and then, standing the mixed powder in an alkali steam environment at 100-200 ℃ for crystallization reaction, and performing magnetic adsorption separation, washing and drying on the obtained reaction product to obtain crystallized cobalt ferrite powder. The invention realizes the preparation of the low-temperature dry-state synthesized cobalt ferrite powder, effectively reduces the synthesis temperature of the highly crystallized cobalt ferrite powder, and avoids the problem of nonuniform crystal size caused by high-temperature synthesis; meanwhile, the problem of low crystallinity or difficulty in eliminating impurity phase (ferric oxide) caused by adopting liquid phase synthesis is avoided, thereby providing a new preparation way for preparing pure cobalt ferrite nano particles. The invention has simple operation and control and few concerned variables, and is beneficial to large-scale synthesis and use.
Description
Technical Field
The invention relates to the technical field of cobalt ferrite powder, in particular to a preparation method of cobalt ferrite powder.
Background
Cobalt ferrite has good catalytic, magnetic, magneto-optical and wave-absorbing properties, so that the cobalt ferrite has wide application in the fields of catalytic synthesis, communication, aerospace science and technology, biological radiography and the like, particularly as a novel non-metallic magnetic material, has a unique position in the fields of high frequency and low frequency, and is increasingly valued by countries in the world.
Cobalt ferrite is traditionally synthesized by a high-temperature solid phase: according to the process, after metal precursors are mixed, the metal precursors are synthesized in a solid-phase reaction through high-temperature calcination (more than 600 ℃), and the obtained product has high crystallinity, but has different particle sizes and high energy consumption. The emerging mechanical alloying method mainly utilizes high-energy ball milling, and monodisperse magnetic nanocrystals are difficult to form although the synthesis temperature is low; the sol-gel method can obtain nanocrystals with narrow particle size distribution, but the hydrolysis rate needs to be precisely controlled to avoid the generation of impurities, so that the industrial production is difficult to realize; hydrothermal method/solvothermal method is favorable for obtaining highly crystallized monodisperse nanocrystals, but the reaction time is longer and the safety is poorer; the microemulsion method is beneficial to controlling the crystal morphology, but the aftertreatment is difficult, and a pure product is difficult to obtain. The coprecipitation method has simple process, but the obtained powder is easy to agglomerate to cause uneven particle size. In addition, these new methods, except for high energy ball milling, require high temperature decomposition of organic substances therein, thereby causing environmental pollution.
Therefore, a new simple, feasible and environment-friendly method is searched, which is beneficial to enriching the preparation technology of the cobalt ferrite and provides a practical and feasible operation means for the industrial preparation of the cobalt ferrite material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a dry-state low-temperature preparation method of cobalt ferrite powder, which has the advantages of simple process, wide raw material source, stable reaction process and simple and convenient operation, so as to overcome the defects that the particle size is difficult to control through high-temperature calcination synthesis in the synthesis of cobalt ferrite in the prior art, or the crystallinity is low or an impurity phase exists under the liquid phase condition, and thus, the cobalt ferrite powder is prepared simply, safely and environmentally friendly.
The purpose of the invention is realized by the following technical scheme:
the invention provides a process method for preparing cobalt ferrite powder at low temperature in a dry state, which comprises the following steps:
(1) adding a cobalt source and an iron source into a solvent according to a molar ratio of 0.6-2.5: 1, dissolving, stirring and mixing to obtain a uniform solution, and drying to obtain a mixed powder;
(2) and standing the mixed powder in an alkali steam environment at 100-200 ℃ for crystallization reaction for 16-72 hours, and performing centrifugal separation, water washing, alcohol washing and drying on a reaction product to obtain crystallized cobalt ferrite powder.
In the scheme, the cobalt source and the iron source are respectively cobalt chloride hexahydrate and ferric chloride hexahydrate or cobalt nitrate hexahydrate and ferric nitrate. The solvent in the step (1) is one or a combination of water, ethanol, acetone and benzene, and the molar ratio of the cobalt source to the solvent is 1: 50-600.
In the above scheme, the alkali solution adopted by the alkali vapor in the step (2) is one or a combination of an ammonia water solution, an ethylenediamine water solution, a triethylamine water solution, a tetrapropylammonium hydroxide water solution and a tetrabutylammonium hydroxide water solution; the concentration of the alkali solution is less than or equal to 5 mol/L. The volume mass ratio of the alkali solution to the mixed powder is 0.5-1.2 mL to 0.1-1.5 g.
Further, the reaction temperature of the step (2) is 120-180 ℃, and the reaction time is 24-48 h. The grain size of the crystallized cobalt ferrite powder is 10-120 nm.
The invention has the following beneficial effects:
(1) the invention separately carries out the preparation of the mixed powder of ferric chloride and cobalt chloride or the mixed powder of ferric nitrate and cobalt nitrate hexahydrate and the synthesis of cobalt ferrite crystals by alkali steam treatment. In the alkali steam treatment process, the alkali solution is not in direct contact with the mixed powder in a liquid state, but the gas phase formed by high-temperature evaporation is in contact with the dried mixed powder, so that the cobalt ferrite crystallization and the product purity are improved, the crystallization is carried out at a lower temperature, subsequent calcination treatment is not needed, and the high-crystallization pure cobalt ferrite material (the saturation magnetization is greater than 18emu/G, the residual magnetization is 2-40 emu/G, and the coercive force is 230-2250G) is obtained at a low temperature.
(2) The invention realizes the preparation of low-temperature solid-state synthesized cobalt ferrite powder, and discloses a preparation method for preparing the cobalt ferrite powder by a low-temperature dry method for the first time, thereby effectively reducing the synthesis temperature of the highly crystallized cobalt ferrite powder and avoiding the problem of excessive particle growth during high-temperature synthesis; meanwhile, the preparation of the cobalt ferrite is synthesized in a dry state, so that the problem of low crystallinity or difficult elimination of impurity phases caused by adopting liquid phase synthesis is solved, and a new preparation way is provided for preparing the cobalt ferrite nano material.
(3) The invention has simple operation and control and few concerned variables, and is beneficial to large-scale synthesis and use.
Drawings
The invention will now be described in further detail with reference to the following examples and the accompanying drawings:
FIG. 1 is an XRD spectrum and a magnetic adsorption optical photograph (a: XRD spectrum; b: magnetic adsorption photograph) of cobalt ferrite powder prepared in example one of the present invention;
FIG. 2 shows an XRD spectrum and a magnetic adsorption optical photograph (a: XRD spectrum; b: magnetic adsorption photograph) of cobalt ferrite powder prepared in example two of the present invention;
FIG. 3 is an XRD spectrum and SEM photograph (a: XRD spectrum; b: SEM photograph) of cobalt ferrite powder prepared in example three of the present invention;
FIG. 4 shows an XRD spectrum and an SEM photograph (a: XRD spectrum; b: SEM photograph) of cobalt ferrite powder prepared in example four of the present invention.
Detailed Description
The first embodiment is as follows:
the embodiment of the invention relates to a process method for preparing cobalt ferrite powder at low temperature in a dry state, which comprises the following steps:
(1) sequentially adding 0.0020mol of cobalt chloride hexahydrate, 0.0041mol of ferric chloride hexahydrate and 12mL of water into a reaction bottle for dissolving and mixing, stirring for 2 hours at room temperature to obtain a uniform solution, and then drying at 60 ℃ to obtain mixed powder;
(2) and (2) standing the mixed powder for crystallization reaction for 24 hours at 140 ℃ in an alkali steam environment, wherein an alkali solution adopted by alkali steam is an ammonia water solution with the concentration of 2mol/L, the volume mass ratio of the alkali solution to the mixed powder is 1.1mL to 0.2g, and the reaction product is subjected to centrifugal separation, water washing, alcohol washing and drying to obtain crystallized cobalt ferrite powder.
As shown in FIG. 1a, the peak values corresponding to 2 θ of the cobalt ferrite powder prepared in this example are 35.3, 62.6 and 57.0 degrees, respectively, and are consistent with the cobalt ferrite crystal (pdf #03-0864), indicating that the obtained powder is cobalt ferrite powder. After the obtained powder was dispersed in water, magnetic adsorption was achieved by a magnetic bar, as shown in FIG. 1 b.
Example two:
the embodiment of the invention relates to a process method for preparing cobalt ferrite powder at low temperature in a dry state, which comprises the following steps:
(1) sequentially adding 0.0019mol of cobalt chloride hexahydrate, 0.0040mol of ferric chloride hexahydrate and 15mL of ethanol into a reaction bottle for dissolving and mixing, stirring for 2 hours at room temperature to obtain a uniform solution, naturally volatilizing the ethanol at room temperature, and drying at 60 ℃ to obtain mixed powder;
(2) and standing the mixed powder for crystallization reaction for 16h at 180 ℃ in an alkali steam environment, wherein an alkali solution adopted by the alkali steam is a mixed solution of ammonia water, urea and ethylenediamine (containing 1.5mol/L of ammonia, 1mol/L of urea and 0.6mol/L of ethylenediamine), the volume-mass ratio of the alkali solution to the mixed powder is 1mL to 0.1g, and the crystallized cobalt ferrite powder is obtained by centrifugally separating, washing with water, washing with alcohol and drying the reaction product.
As shown in FIG. 2a, the peak values corresponding to 2 θ of the cobalt ferrite powder prepared in this example are 35.2, 62.6 and 57.1 degrees, respectively, and are consistent with the cobalt ferrite crystal (pdf #03-0864), which indicates that the obtained powder is cobalt ferrite powder. After the obtained powder was dispersed in water, magnetic adsorption was achieved by a magnetic rod, as shown in FIG. 2 b.
Example three:
the embodiment of the invention relates to a process method for preparing cobalt ferrite powder at low temperature in a dry state, which comprises the following steps:
(1) sequentially adding 0.0021mol of cobalt chloride hexahydrate, 0.0037mol of ferric chloride hexahydrate and 10mL of water into a reaction bottle for dissolving and mixing, stirring for 2 hours at room temperature to obtain a uniform solution, and then drying at 60 ℃ to obtain mixed powder;
(2) and standing the mixed powder for crystallization reaction for 48 hours at 140 ℃ in an alkali steam environment, wherein the alkali solution adopted by the alkali steam is a mixed solution of ammonia water, ethylenediamine and tetrabutylammonium hydroxide (containing 3mol/L of ammonia, 0.2mol/L of ethylenediamine and 0.1mol/L of tetrabutylammonium hydroxide), the volume mass ratio of the alkali solution to the mixed powder is 1.2mL to 0.12g, and the reaction product is subjected to centrifugal separation, water washing, alcohol washing and drying to obtain crystallized cobalt ferrite powder.
As shown in FIG. 3a, the peak values corresponding to 2 θ of the cobalt ferrite powder prepared in this example are 35.3, 62.6 and 57.0 degrees, respectively, and are consistent with the cobalt ferrite crystal (pdf #03-0864), indicating that the obtained powder is cobalt ferrite powder. As shown in FIG. 3b, the obtained powder has uniform particle size of 100-110 nm.
Example four:
the embodiment of the invention relates to a process method for preparing cobalt ferrite powder at low temperature in a dry state, which comprises the following steps:
(1) sequentially adding 0.0019mol of cobalt chloride hexahydrate, 0.0038mol of ferric chloride hexahydrate and 8mL of ethanol into a reaction bottle for dissolving and mixing, stirring for 2 hours at room temperature to obtain a uniform solution, naturally volatilizing the ethanol at room temperature, and drying at 60 ℃ to obtain mixed powder;
(2) and standing the mixed powder for crystallization reaction for 30 hours at 160 ℃ in an alkali steam environment, wherein an alkali solution adopted by alkali steam is a mixed solution of ammonia water and urea (containing 3mol/L of ammonia and 0.1mol/L of urea), the volume mass ratio of the alkali solution to the mixed powder is 1.2mL to 0.3g, and the reaction product is subjected to centrifugal separation, water washing, alcohol washing and drying to obtain crystallized cobalt ferrite powder.
As shown in FIG. 4a, the peak values corresponding to 2 θ of the cobalt ferrite powder prepared in this example are 35.5, 62.7 and 57.2 degrees, respectively, and are consistent with the cobalt ferrite crystal (pdf #03-0864), which indicates that the obtained powder is cobalt ferrite powder. As shown in FIG. 3b, the obtained powder has uniform particle size of 90-100 nm.
The VSM results of the cobalt ferrite powder prepared in the examples of the present invention are shown in Table 1.
TABLE 1 VSM results of cobalt ferrite powders prepared in the examples of the present invention
Claims (7)
1. A process method for preparing cobalt ferrite powder at low temperature in a dry state is characterized by comprising the following steps:
(1) adding a cobalt source and an iron source into a solvent according to a molar ratio of 0.6-2.5: 1, dissolving, stirring and mixing to obtain a uniform solution, and drying to obtain a mixed powder;
(2) and standing the mixed powder in an alkali steam environment at 100-200 ℃ for crystallization reaction for 16-72 hours, and performing centrifugal separation, water washing, alcohol washing and drying on a reaction product to obtain crystallized cobalt ferrite powder.
2. The process method for preparing cobalt ferrite powder at low temperature in a dry state according to claim 1, which is characterized in that: the cobalt source and the iron source are respectively cobalt chloride hexahydrate and ferric chloride hexahydrate or cobalt nitrate hexahydrate and ferric nitrate.
3. The process method for preparing cobalt ferrite powder at low temperature in a dry state according to claim 1, which is characterized in that: the solvent in the step (1) is one or a combination of water, ethanol, acetone and benzene, and the molar ratio of the cobalt source to the solvent is 1: 50-600.
4. The process method for preparing cobalt ferrite powder at low temperature in a dry state according to claim 1, which is characterized in that: the alkali solution adopted by the alkali steam in the step (2) is one or a combination of an ammonia water solution, an ethylenediamine water solution, a triethylamine water solution, a tetrapropylammonium hydroxide water solution and a tetrabutylammonium hydroxide water solution; the concentration of the alkali solution is less than or equal to 5 mol/L.
5. The dry low-temperature preparation process method of cobalt ferrite powder according to claim 4, characterized in that: the volume mass ratio of the alkali solution to the mixed powder is 0.5-1.2 mL to 0.1-1.5 g.
6. The process method for preparing cobalt ferrite powder at low temperature in a dry state according to claim 1, which is characterized in that: the reaction temperature of the step (2) is 120-180 ℃, and the reaction time is 24-48 h.
7. The process method for preparing cobalt ferrite powder at low temperature in a dry state according to claim 1, which is characterized in that: the grain size of the crystallized cobalt ferrite powder is 10-120 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110494793.7A CN113200572A (en) | 2021-05-07 | 2021-05-07 | Process method for preparing cobalt ferrite powder at low temperature in dry state |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110494793.7A CN113200572A (en) | 2021-05-07 | 2021-05-07 | Process method for preparing cobalt ferrite powder at low temperature in dry state |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113200572A true CN113200572A (en) | 2021-08-03 |
Family
ID=77029075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110494793.7A Pending CN113200572A (en) | 2021-05-07 | 2021-05-07 | Process method for preparing cobalt ferrite powder at low temperature in dry state |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113200572A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6395120A (en) * | 1986-10-13 | 1988-04-26 | Matsushita Electric Ind Co Ltd | Production of complex type ferrite powder |
| CN101555042A (en) * | 2009-05-19 | 2009-10-14 | 李峰 | Method for preparing spinel type iron-containing oxide nano-materials by low heat solid state reaction |
| CN101804968A (en) * | 2010-03-19 | 2010-08-18 | 清华大学 | Direct synthesis method of nanometer oxide powder |
| CN101870475A (en) * | 2010-06-09 | 2010-10-27 | 景德镇陶瓷学院 | Method for low-temperature synthesis of zirconium silicate powder through non-hydrolytic sol-gel reaction by using zirconium acetate as zirconium source |
| CN101891483A (en) * | 2010-07-09 | 2010-11-24 | 东华大学 | Method for preparing Co1-xNixFe2O4 magnetic nano-powder by solvothermal method |
| CN103058284A (en) * | 2011-10-18 | 2013-04-24 | 成都快典科技有限公司 | Preparation method of spinel-type cobalt |
| CN103204546A (en) * | 2013-04-17 | 2013-07-17 | 兰州大学 | Method for preparing nano cobalt ferrite |
| CN104150544A (en) * | 2014-08-06 | 2014-11-19 | 厦门理工学院 | Method for acetate-assisted synthesis of monodisperse ferric acid cobalt nano powder material |
-
2021
- 2021-05-07 CN CN202110494793.7A patent/CN113200572A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6395120A (en) * | 1986-10-13 | 1988-04-26 | Matsushita Electric Ind Co Ltd | Production of complex type ferrite powder |
| CN101555042A (en) * | 2009-05-19 | 2009-10-14 | 李峰 | Method for preparing spinel type iron-containing oxide nano-materials by low heat solid state reaction |
| CN101804968A (en) * | 2010-03-19 | 2010-08-18 | 清华大学 | Direct synthesis method of nanometer oxide powder |
| CN101870475A (en) * | 2010-06-09 | 2010-10-27 | 景德镇陶瓷学院 | Method for low-temperature synthesis of zirconium silicate powder through non-hydrolytic sol-gel reaction by using zirconium acetate as zirconium source |
| CN101891483A (en) * | 2010-07-09 | 2010-11-24 | 东华大学 | Method for preparing Co1-xNixFe2O4 magnetic nano-powder by solvothermal method |
| CN103058284A (en) * | 2011-10-18 | 2013-04-24 | 成都快典科技有限公司 | Preparation method of spinel-type cobalt |
| CN103204546A (en) * | 2013-04-17 | 2013-07-17 | 兰州大学 | Method for preparing nano cobalt ferrite |
| CN104150544A (en) * | 2014-08-06 | 2014-11-19 | 厦门理工学院 | Method for acetate-assisted synthesis of monodisperse ferric acid cobalt nano powder material |
Non-Patent Citations (2)
| Title |
|---|
| MANG LU ET AL: "Preparation of TiO2/Silicalite-2@CoFe2O4 Magnetic Composites and Evaluation of their Photocatalytic Activity in Cr(VI) Removal", 《WATER AIR SOIL POLLUTION》 * |
| 张梅梅等: "混合碱媒介法制备磁性铁酸钴纳米粉体", 《人工晶体学报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20200148548A1 (en) | Method for prepareing copper-nickel cobaltate nanowire and application thereof | |
| CN110975795A (en) | Synthesis method of lithium extraction adsorbent | |
| Gao et al. | Preparation of samarium oxide nanoparticles and its catalytic activity on the esterification | |
| CN101293674A (en) | Method for preparing spindle shaped alpha-Fe2O3 powder | |
| CN104310458B (en) | A kind of method preparing zinc oxide nano rod | |
| CN104475078B (en) | Preparation method of nano rare-earth metal oxide/ carbon nano pipe composite catalyst | |
| CN104538145A (en) | Multi-scale uniform and single-dispersion magnetic microsphere and preparation method thereof | |
| CN100532270C (en) | Nano crystal constructed porous copper oxide aggregate and its preparing method | |
| CN109734056A (en) | Metal oxide/preparation method of fold rGO composite nano materials and the preparation method of fold nano-metal-oxide | |
| CN101293675B (en) | Method for preparing hexagonal disc shaped alpha-Fe2O3 powder | |
| CN110255598B (en) | Preparation method of flower-like microsphere cerium carbonate and cerium dioxide | |
| CN108395542B (en) | MOFs nanocrystalline material regulated and controlled by porous membrane substrate and preparation method thereof | |
| CN102850056A (en) | Preparation method of spherical ferrite | |
| CN102718262A (en) | Preparation of nanowire assembled calcium tungstate spherical structure | |
| CN103436958A (en) | Preparation method of bismuth nanocrystalline | |
| CN103318954A (en) | Method for preparing sodium trititanate nanorods through solid-phase chemical reaction | |
| CN102557151A (en) | Method for preparing nanometer ferroferric oxide powder by reducing at one step | |
| CN113200572A (en) | Process method for preparing cobalt ferrite powder at low temperature in dry state | |
| CN100534904C (en) | Method for preparing nano Al2O3 adopting salt-melting calcination process | |
| CN113479897B (en) | Method for preparing two-dimensional nano sheet silicate by using attapulgite and application thereof | |
| Zeng et al. | Chemical synthesis of nanosized BaCO3 with a pillar-like morphology | |
| CN108640158A (en) | A kind of preparation method of high-purity hexagonal sheet-like barium ferrite | |
| Wang et al. | Synthesis and magnetic properties of lanthanum orthovanadate nanorods | |
| CN111569879B (en) | Method for preparing silicate/carbon composite material by using attapulgite and application thereof | |
| CN109019694B (en) | Micro-nano structure spherical MnCO3Preparation method of (1) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210803 |
|
| RJ01 | Rejection of invention patent application after publication |