CN110615482A - Method for preparing epsilon-phase iron oxide by ball milling method - Google Patents
Method for preparing epsilon-phase iron oxide by ball milling method Download PDFInfo
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- CN110615482A CN110615482A CN201910948081.0A CN201910948081A CN110615482A CN 110615482 A CN110615482 A CN 110615482A CN 201910948081 A CN201910948081 A CN 201910948081A CN 110615482 A CN110615482 A CN 110615482A
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- iron oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/10—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
- H01F1/11—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles
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- 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 method for preparing epsilon-phase iron oxide by a ball milling method, belonging to the technical field of preparation of novel magnetic materials. The method mainly comprises the following steps: adding grinding balls into a ball milling tank as a grinding medium, adding ferric nitrate nonahydrate, hydrophilic gas-phase nano silicon dioxide and ethanol, sealing the ball milling tank, grinding for several hours, taking out a ground product, drying, and annealing to obtain a final sample. The method has the advantages of simple operation, high yield, less used instruments and equipment, low cost, no environmental pollution, capability of adjusting the coercivity of the product and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of novel magnetic materials, and particularly relates to a simple, novel and efficient method for preparing epsilon-phase iron oxide.
Background
Epsilon phase iron oxide (epsilon-Fe)2O3) Has higher coercive force and has wide application prospect in the fields of magnetic recording media, information storage, permanent magnets and the like. epsilon-Fe2O3Is a dark brown iron oxide magnetic phase which is known as alpha phase iron oxide (alpha-Fe)2O3) With gamma-phase iron oxide (gamma-Fe)2O3) The mesophase of (a). epsilon-Fe2O3The synthesis of (a) is very sensitive to the experimental conditions. Because of ε -Fe2O3A stable phase only appears in a certain nanometer size range. epsilon-Fe2O3A phase change occurs once a critical dimension is reached. And is easy to bealpha-Fe which is stable to thermodynamics2O3And (4) phase inversion. Therefore, the particle size is controlled and agglomeration among particles is prevented from occurring to epsilon-Fe2O3Is very important. At present,. epsilon. -Fe2O3The preparation method mainly comprises the following steps: sol-gel method using ferric nitrate nonahydrate and tetraethyl orthosilicate as raw materials, combination method of inverse micelle and sol-gel, impregnation method of mesoporous silica xerogel impregnated with ferric salt, and the like. However, these methods have disadvantages of long reaction time, complicated experimental operation, and high price of raw materials.
Disclosure of Invention
The invention aims to provide a method for preparing epsilon-Fe by a ball milling method aiming at the defects in the prior art2O3The method can obtain the epsilon-Fe with different coercive forces by changing the mixture ratio of the raw materials2O3And (3) sampling. The method has the advantages of simple operation, high yield, low cost, no environmental pollution and the like.
The technical scheme adopted by the invention is as follows:
a method for preparing epsilon-phase iron oxide by a ball milling method specifically comprises the following steps:
(1) firstly, 100g of grinding balls are put into a 100mL ball-milling tank to be used as a grinding medium;
(2) then adding ferric nitrate nonahydrate and hydrophilic gas-phase nano-silica in a mass ratio of 1: 1.5-10 into a ball milling tank, and adding 2mL of ethanol to reduce the grinding resistance;
(3) and sealing the ball milling tank, grinding for 6-8 hours at room temperature, taking out a sample in the tank when the temperature of the ball milling tank is reduced to the room temperature, drying, and annealing in the air to obtain the epsilon-phase iron oxide.
According to the invention, the coercive force of the prepared epsilon-phase iron oxide can be changed by changing the mass ratio of the ferric nitrate nonahydrate to the hydrophilic gas-phase nano silicon dioxide: when the mass ratio is 1:10, the coercive force of the prepared epsilon-phase iron oxide is 6.6 kOe; when the mass ratio is 1:6, the coercive force of the prepared epsilon-phase iron oxide is 11 kOe; when the mass ratio is 7:30, the coercive force of the prepared epsilon-phase iron oxide is 12.5 kOe; when the mass ratio is 1:3, the coercive force of the prepared epsilon-phase iron oxide is 13.7 kOe.
The mass ratio of the ferric nitrate nonahydrate to the hydrophilic gas-phase nano silicon dioxide in the step (2) is preferably 1: 6-10.
And (3) annealing in the step (3), wherein the temperature is preferably 1000 ℃, and the annealing time is preferably 4 hours.
The invention has the beneficial effects that the method for preparing the epsilon-Fe by using the ball milling method is provided for the first time2O3The method can obtain samples with different coercive forces by changing the mixture ratio of the raw materials. The obtained epsilon-Fe2O3The nano particles and the particles have uniform size and good dispersibility. Compared with the existing preparation method, the method has the advantages of high product yield, high purity, simple preparation method, no environmental pollution, good repeatability, low raw material cost and the like.
Drawings
FIG. 1 shows ε -Fe obtained in example 12O3XRD pattern of nanoparticles.
FIG. 2 shows ε -Fe obtained in example 12O3TEM images of nanoparticles.
FIG. 3 is the ε -Fe obtained in example 12O3Magnetic hysteresis loop of the nanoparticles.
FIG. 4 shows ε -Fe obtained in example 22O3XRD pattern of nanoparticles.
FIG. 5 shows ε -Fe obtained in example 22O3Magnetic hysteresis loop of the nanoparticles.
FIG. 6 is ε -Fe obtained in example 32O3XRD pattern of nanoparticles.
FIG. 7 shows ε -Fe obtained in example 32O3Magnetic hysteresis loop of the nanoparticles.
FIG. 8 shows ε -Fe obtained in example 42O3XRD pattern of nanoparticles.
FIG. 9 shows ε -Fe obtained in example 42O3Magnetic hysteresis loop of the nanoparticles.
Detailed Description
EXAMPLE 1 preparation of ε -F having a coercive force of 11kOee2O3Overall process of nanoparticles
With iron nitrate nonahydrate (Fe (NO)3)3·9H2O), gas phase nano silicon dioxide, ethanol (C)2H5OH) as a raw material. To prepare the nanoparticles, 100g of milling balls were first placed in a 100mL ball mill jar as the milling media. Then 0.5g Fe (NO) was added3)3·9H2O and 3g of hydrophilic gas phase nano silicon dioxide, and then a certain amount of ethanol solution (2mL) is added to reduce the grinding resistance. The jar was sealed and milled at room temperature for 8 h. After the reaction is finished, taking out the sample in the ball milling tank after the temperature of the ball milling tank is reduced to room temperature, drying for a plurality of hours, and annealing for 4 hours at 1000 ℃ in the air. The final sample was obtained.
FIG. 1 shows ε -Fe prepared under the above conditions2O3The XRD pattern of the nano-particles can show the diffraction peak of the sample and epsilon-Fe in PDF card2O3The positions of diffraction peaks of the standard spectrum are matched. Proves that the sample is epsilon-phase Fe2O3. FIG. 2 shows ε -Fe prepared under the above conditions2O3TEM image of the nanoparticles, from which it can be seen that ε -Fe2O3The nano particles have uniform size, the size is between 10nm and 35nm, and the nano particles are well dispersed in silicon dioxide.
FIG. 3 shows ε -Fe prepared under the above conditions2O3Magnetic hysteresis loop of the nanoparticles. It can be seen that the coercivity of the sample is 11kOe at room temperature.
Example 2 preparation of ε -Fe having a coercivity of 6.6kOe2O3Overall process of nanoparticles
Using ferric nitrate nonahydrate (Fe (NO)3)3·9H2O), gas phase nano silicon dioxide, ethanol (C)2H5OH) as a raw material. To prepare the nanoparticles, 100g of milling balls were first placed in a 100mL ball mill jar as the milling media. Then 0.3g Fe (NO) was added3)3·9H2O and 3g of hydrophilic gas phase nano silicon dioxide, and then a certain amount of ethanol solution (2mL) is added to reduce the grinding resistance. The jar was sealed and milled at room temperature for 8 h. After the reaction is finished, the temperature of the ball milling tank is keptThe temperature was lowered to room temperature and finally the sample in the pot was taken out and dried for several hours and then annealed at 1000 ℃ for 4 hours in air. The final sample was obtained.
FIG. 4 shows ε -Fe prepared under the above conditions2O3The XRD pattern of the nano-particles can show the diffraction peak of the sample and epsilon-Fe in PDF card2O3The positions of diffraction peaks of the standard spectrum are matched. Proves that the sample is epsilon-phase Fe2O3. FIG. 5 shows ε -Fe prepared under the above conditions2O3Magnetic hysteresis loop of the nanoparticles. It can be seen that the coercivity of the sample is 6.6kOe at room temperature.
Example 3 preparation of ε -Fe having a coercivity of 12.5kOe2O3Overall process of nanoparticles
Using ferric nitrate nonahydrate (Fe (NO)3)3·9H2O), gas phase nano silicon dioxide, ethanol (C)2H5OH) as a raw material. To prepare the nanoparticles, 100g of milling balls were first placed in a 100mL ball mill jar as the milling media. Then 0.7g Fe (NO) was added3)3·9H2O and 3g of hydrophilic gas phase nano silicon dioxide, and then a certain amount of ethanol solution (2mL) is added to reduce the grinding resistance. The jar was sealed and milled at room temperature for 8 h. After the reaction is finished, the temperature of the ball milling tank is reduced to room temperature, and finally the sample in the tank is taken out and dried for several hours, and then the annealing is carried out for 4 hours at 1000 ℃ in the air. The final sample was obtained.
FIG. 6 shows ε -Fe prepared under the above conditions2O3The XRD pattern of the nano-particles shows that epsilon-Fe is removed from the diffraction peak of the sample2O3A few alpha-Fe in addition to diffraction peaks2O3The diffraction peak of (1). Illustrating the removal of epsilon-Fe in the sample2O3The nano particles are also partially antiferromagnetic alpha-Fe2O3Nanoparticle heterogeneous phase. FIG. 7 shows ε -Fe prepared under the above conditions2O3Magnetic hysteresis loop of the nanoparticles. It can be seen that the coercivity of the sample is 12.5kOe at room temperature.
Example 4 preparation of ε -Fe having a coercivity of 13.7kOe2O3Overall process of nanoparticles
Using ferric nitrate nonahydrate (Fe (NO)3)3·9H2O), gas phase nano silicon dioxide, ethanol (C)2H5OH) as a raw material. To prepare the nanoparticles, 100g of milling balls were first placed in a 100mL ball mill jar as the milling media. Then 1g Fe (NO) is added3)3·9H2O and 3g of hydrophilic gas phase nano silicon dioxide, and then a certain amount of ethanol solution (2mL) is added to reduce the grinding resistance. The jar was sealed and milled at room temperature for 8 h. After the reaction is finished, the temperature of the ball milling tank is reduced to room temperature, then the sample in the tank is taken out and dried for a plurality of hours, and then the annealing is carried out for 4 hours at 1000 ℃ in the air. The final sample was obtained.
FIG. 8 shows ε -Fe prepared under the above conditions2O3The XRD pattern of the nano-particles shows that epsilon-Fe is removed from the diffraction peak of the sample2O3alpha-Fe in addition to diffraction peaks2O3The diffraction peak of (1). Illustrating the removal of epsilon-Fe in the sample2O3The nano particles are also provided with anti-ferromagnetic alpha-Fe2O3And (3) nanoparticles. FIG. 9 shows ε -Fe prepared under the above conditions2O3Magnetic hysteresis loop of the nanoparticles. It can be seen that the coercivity of the sample is 13.7kOe at room temperature.
Claims (4)
1. A method for preparing epsilon-phase iron oxide by a ball milling method specifically comprises the following steps:
(1) firstly, 100g of grinding balls are put into a 100mL ball-milling tank to be used as a grinding medium;
(2) then adding ferric nitrate nonahydrate and hydrophilic gas-phase nano-silica in a mass ratio of 1: 1.5-10 into a ball milling tank, and adding 2mL of ethanol to reduce the grinding resistance;
(3) and sealing the ball milling tank, grinding for 6-8 hours at room temperature, taking out a sample in the tank when the temperature of the ball milling tank is reduced to the room temperature, drying, and annealing in the air to obtain the epsilon-phase iron oxide.
2. The method for preparing epsilon-phase iron oxide by a ball milling method according to claim 1, characterized in that the coercive force of the prepared epsilon-phase iron oxide is adjusted by changing the mass ratio of ferric nitrate nonahydrate to hydrophilic fumed nano-silica: when the mass ratio is 1:10, the coercive force of the prepared epsilon-phase iron oxide is 6.6 kOe; when the mass ratio is 1:6, the coercive force of the prepared epsilon-phase iron oxide is 11 kOe; when the mass ratio is 7:30, the coercive force of the prepared epsilon-phase iron oxide is 12.5 kOe; when the mass ratio is 1:3, the coercive force of the prepared epsilon-phase iron oxide is 13.7 kOe.
3. The method for preparing epsilon-phase iron oxide by the ball milling method according to claim 1, wherein the mass ratio of the ferric nitrate nonahydrate to the hydrophilic fumed nano-silica in the step (2) is 1: 6-10.
4. The method for preparing epsilon-phase iron oxide by a ball milling method according to any one of claims 1 to 3, characterized in that the annealing in the step (3) is carried out at 1000 ℃ for 4 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4299635A (en) * | 1979-03-23 | 1981-11-10 | Theodore Dickerson | Flow characteristics of synthetic iron oxide |
| CN103274365A (en) * | 2013-06-13 | 2013-09-04 | 南京大学 | Preparation method for metallic oxide spherical cascade structure |
| CN106745305A (en) * | 2016-12-09 | 2017-05-31 | 江苏大学 | A kind of α Fe2O3The preparation method of magnetic nano powder material |
| JP2017201672A (en) * | 2016-05-08 | 2017-11-09 | 真平 山本 | Method for producing magnetic powder |
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2019
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4299635A (en) * | 1979-03-23 | 1981-11-10 | Theodore Dickerson | Flow characteristics of synthetic iron oxide |
| CN103274365A (en) * | 2013-06-13 | 2013-09-04 | 南京大学 | Preparation method for metallic oxide spherical cascade structure |
| JP2017201672A (en) * | 2016-05-08 | 2017-11-09 | 真平 山本 | Method for producing magnetic powder |
| CN106745305A (en) * | 2016-12-09 | 2017-05-31 | 江苏大学 | A kind of α Fe2O3The preparation method of magnetic nano powder material |
Non-Patent Citations (1)
| Title |
|---|
| YUNGUO WANG等: "Self-assemblinge-Fe2O3/SiO2nanoparticles to nanoflakes with paramagnetic-class properties via a milling-etching route", 《ADVANCED POWDER TECHNOLOGY》 * |
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