CN112582167A - Method for preparing nano-scale rare earth magnetic refrigeration material by laser ablation - Google Patents
Method for preparing nano-scale rare earth magnetic refrigeration material by laser ablation Download PDFInfo
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- CN112582167A CN112582167A CN202011614611.7A CN202011614611A CN112582167A CN 112582167 A CN112582167 A CN 112582167A CN 202011614611 A CN202011614611 A CN 202011614611A CN 112582167 A CN112582167 A CN 112582167A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
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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
- H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
- H01F1/017—Compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
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Abstract
The invention discloses a method for preparing a nano-scale rare earth magnetic refrigeration material by laser ablation. The chemical composition formula of the rare earth magnetic refrigeration material is LnxA1‑xMnO3In the compound, the element Ln is rare earth elements such as La, Pr, Sm and the like, the element A is monovalent and divalent metal elements such as Ca, Na, K, Sr and the like, and x is more than or equal to 0.1 and less than or equal to 0.9. Weighing raw material powder of the rare earth magnetic refrigeration material according to a certain stoichiometric ratio, fully grinding and mixing the raw material powder, pressing the raw material powder into blocks, presintering the pressed blocks at a certain temperature to form a precursor, preparing a mixed solution containing nano-scale particle precipitates by utilizing a laser ablation technology, filtering the precipitates of the mixed solution, and drying to obtain the nano-scale high-performance rare earth magnetic refrigeration material. The preparation method can obtain the rare earth magnetic refrigeration material with clean surface, good chemical activity and nano-scale size, and the refrigeration temperature range is obviously enlarged to prepare the rare earth magnetic refrigeration materialThe cold energy is enhanced, and the preparation method can effectively reduce the high-temperature sintering temperature and time, and has simple preparation process.
Description
Technical Field
The invention relates to a method for preparing a nano-scale rare earth magnetic refrigeration material by laser ablation, belonging to the field of high-performance magnetic materials.
Background
The liquid phase laser ablation technique is attracting attention as a new technique for preparing nanoparticles. Liquid phase Laser Ablation (LAL) is a simple, green nanomaterial preparation technique, and usually only needs to be performed in water or organic Liquid phase. In recent years, LAL has been used to prepare a series of nanomaterials with special morphology and microstructure, and to realize one-step preparation of functionalized nanomaterials in the fields of optics, display, detection, biology and the like, which are exploring new properties and applications. Laser ablation of various noble metals precipitated in a solvent has been shown to produce colloidal nanoparticles of these metals. And the result shows that the liquid laser ablation is also suitable for preparing the composite material nano particles. Compared with the traditional preparation method of the nano material, the liquid phase laser ablation method has the following advantages that (1) the method is a 'simple and clean' synthesis means, the preparation process is simple, the generation of byproducts is reduced, the use of precursors of the reaction is simplified, the high purity of the final product is ensured, and the surface activity is higher; (2) the liquid phase laser ablation method can prepare a high-temperature high-pressure metastable phase under mild conditions; (3) the preparation method has universality for almost all nano materials, and researchers can select required target materials and liquids to synthesize nano particles and structures according to the properties of the materials; and (4) the phase, size and shape of the nano structure can be synthesized by changing laser parameters and external conditions, and a plurality of reactions can be realized in one step, so that complicated post-treatment is avoided.
The magnetic refrigeration technology has wide application prospect in a plurality of fields in the future as a new technology with high efficiency, energy conservation and environmental protection. The key of the development lies in finding a magnet with wide working range near room temperature, easy preparation, low cost and generated by permanent magnet (<2T) a refrigerant material with large magnetic entropy change. Magnetic refrigeration materials of the type presently discovered, e.g. Gd5 (SixGe1-x)4、La( FeSi)13、RMnO3、MnFeP1-xAsxNi-Mn-X, etc., all have some application limitations. Gd (Si)xGen1-x)4The alloy must use high-purity Gd as raw material to maintain the giant magnetocaloric effect, and has high price,Strong magnetic field driving is required; la (Fe)xSi1-x)13The phase transition temperature of the alloy is low, and the chemical property is unstable after the solution treatment; the Curie temperature of the perovskite-like manganese oxide material is low; MnFeP1-xAsxThe compound has a complex preparation process, contains virulent As elements, and has increased thermal hysteresis and reduced efficiency if being replaced by nontoxic elements; since Mn element is easily volatile, the composition of Ni-Mn-X alloy is difficult to control, and a long-time high-temperature heat treatment is required to obtain a single-phase structure. Therefore, there are still many efforts to improve the practical use of magnetic refrigeration technology.
The invention adopts the liquid phase laser ablation method, can generate extreme environments such as high temperature and high pressure at room temperature, can generate various reactions by particles from a target material and a solution medium in the extreme environments with high temperature and high pressure, has good cooling effect of liquid, can realize the rapid cooling of high-temperature plasma, has simple preparation process, effectively reduces the high time consumption of the traditional annealing process, ensures that the prepared rare earth magnetic refrigeration material has clean surface and good chemical activity, effectively inhibits structural deformity, widens the refrigeration temperature area, and improves the magnetic entropy and the magnetocaloric effect of the rare earth magnetic refrigeration material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing a nanoscale high-performance rare earth magnetic refrigeration material by using a liquid-phase laser ablation method, wherein the preparation process is simple, the energy consumption is low, the temperature coefficient is low, and the time consumption is low
The preparation method comprises the following steps:
(1) a burdening stage: weighing raw material powder of the rare earth magnetic refrigeration material according to a certain stoichiometric ratio, fully grinding and mixing, and then pressing the raw material powder into blocks;
(2) and (3) pre-burning stage: presintering the pressed blocks at a certain temperature to form a precursor;
(3) an ablation stage: cleaning the precursor for 15-30 min by using an ultrasonic cleaning agent, drying, placing on a target support of a beaker, filling an isopropyl acetone solution to submerge the precursor for 5-10 mm, placing the beaker on a rotating platform with the rotating speed of 30 r/min, adopting Nd, namely YAG laser third harmonic as an ablation laser light source, focusing a laser pulse light beam on the surface of the precursor to ablate for 30-60 min, and generating a mixed solution containing nano-scale particle precipitates;
(4) a separation stage: and filtering the precipitate of the mixed solution, repeatedly cleaning for 3-5 times, and drying to obtain the nanometer grade high-performance rare earth magnetic refrigeration material.
Specifically, the chemical composition formula of the rare earth magnetic refrigeration material in the step (1) is LnxA1-x MnO3Elements of compounds
Ln is rare earth elements such as La, Pr, Sm and the like, element A is monovalent and divalent metal elements such as Ca, Na, K, Sr and the like, x is more than or equal to 0.1 and less than or equal to 0.9, and raw material powder is La2O3、Sm2O3One or more kinds of rare earth oxides, CaO and Mn2O3One or more of monovalent and divalent A metal oxides or carbonates, wherein the size of the pressed block is 10-20 mm in diameter and 2-5 mm in thickness.
Specifically, the pre-sintering condition in the step (2) is 700-900 ℃oC, the time is 12-24 hours.
Specifically, the laser in the step (3) is a nanosecond solid laser, the laser frequency is 10 Hz, the wavelength is 1064nm, the pulse width is 1-7 ns, the laser pulse intensity is 100-350 mJ/pulse, the spot diameter is 1-3 mm, and the cleaning agent is chromatographic pure ethanol.
Specifically, the filtering method in the step (4) adopts a centrifugal machine for filtering, and the speed is 5000-15000 rpm.
Compared with the traditional solid-phase sintering method, the method has the following advantages:
(1) the novel preparation method of the laser liquid phase ablation rare earth magnetic refrigeration material is simpler, the environment is easier to control, the cooling effect of liquid is good, the high-temperature plasma can be rapidly cooled, the conventional time-consuming annealing stage is skipped, and the rare earth magnetic refrigeration material is protected;
(2) the nanometer rare earth magnetic refrigeration material with cleaner surface and higher chemical activity in the ablated magnet grain boundary phase widens the refrigeration temperature zone of the magnetic refrigeration material with magnetic entropy change, thereby improving the Refrigeration Capacity (RCP) of the rare earth magnetic material;
(3) the invention has the advantages of environment-friendly and simple process, easy operation, time saving and energy saving.
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FIG. 1: a schematic diagram of preparing a nanometer-level high-performance rare earth magnetic refrigeration material by a liquid-phase laser ablation method target.
Detailed Description
The present invention will be further described with reference to the following specific embodiments and comparative examples.
Example 1: preparing nano-scale (Pr) by liquid-phase laser ablation0.7Sm0.3)0.5(Sr0.8Ca0.2)0.5 MnO3The method comprises the following specific steps:
(1) a burdening stage: according to atomic ratio: weighing raw material powder Pr of rare earth magnetic refrigeration material, wherein Pr is Sm, Sr, Ca, Mn is =0.35:0.15:0.4:0.1:16O11，Sm2O3SrCO3, CaO and Mn2O3After fully grinding and mixing, pressing the raw material powder into blocks with the diameter of 12mm and the thickness of 5mm under the pressure of 15 Mpa;
(2) and (3) pre-burning stage: pressing the pressed block at 900oC, pre-burning for 12h to form a precursor;
(3) an ablation stage: cleaning the precursor for 30min by using an ultrasonic cleaning agent, drying, placing the precursor on a target support of a beaker, filling isopropyl alcohol to submerge the precursor for 10mm, placing the beaker on a rotating platform with the rotating speed of 30 r/min, adopting Nd, namely YAG laser third harmonic as an ablation laser light source, wherein the laser frequency is 10 Hz, the wavelength is 1064nm, the pulse width is 1ns, the laser pulse intensity is 100 mJ/pulse, the spot diameter is 3 mm, focusing a laser pulse light beam on the surface of the precursor for ablation for 60 min to generate a mixed solution containing nano-scale particle precipitates, and the sample preparation schematic diagram is shown in FIG. 1;
(4) a separation stage: the precipitate of the mixed solution was filtered by a centrifuge at 15000rpm and washed repeatedly 5 times, followed by 150oDrying under the condition of C to obtainObtaining the nanometer grade high-performance rare earth magnetic refrigeration material.
Prepared by solid phase sintering method (Pr)0.7Sm0.3)0.5(Sr0.8Ca0.2)0.5 MnO3Compared with the rare earth magnetic refrigeration material, the maximum magnetic entropy change of the obtained nano refrigeration material is almost unchanged, but the refrigeration temperature area is widened by 23 percent, so that the refrigeration capacity of the magnetic refrigeration material is obviously improved.
Claims (5)
1. A method for preparing a nano-scale rare earth magnetic refrigeration material by laser ablation is characterized by comprising the following steps:
(1) a burdening stage: weighing raw material powder of the rare earth magnetic refrigeration material according to a certain stoichiometric ratio, fully grinding and mixing, and then pressing the raw material powder into blocks;
(2) and (3) pre-burning stage: presintering the pressed blocks at a certain temperature to form a precursor;
(3) an ablation stage: cleaning the precursor for 15-30 min by using an ultrasonic cleaning agent, drying, placing on a target support of a beaker, filling an isopropyl acetone solution to submerge the precursor for 5-10 mm, placing the beaker on a rotating platform with the rotating speed of 30 r/min, adopting Nd, namely YAG laser third harmonic as an ablation laser light source, focusing a laser pulse light beam on the surface of the precursor to ablate for 30-60 min, and generating a mixed solution containing nano-scale particle precipitates;
(4) a separation stage: and filtering the precipitate of the mixed solution, repeatedly cleaning for 3-5 times, and drying to obtain the nanometer grade high-performance rare earth magnetic refrigeration material.
2. The method according to claim 1, wherein the chemical composition formula of the rare earth magnetic refrigeration material in the step (1) is LnxA1-x MnO3In the compound, the element Ln is rare earth elements such as La, Pr, Sm and the like, the element A is monovalent and divalent metal elements such as Ca, Na, K, Sr and the like, x is more than or equal to 0.1 and less than or equal to 0.9, and the raw material powder is La2O3、Sm2O3One or more kinds of rare earth oxides, CaO and Mn2O3One or more of monovalent and divalent A metal oxides or carbonates are equal, the size of the pressed powder is 10-20 mm in diameter, and the thickness is 2-5 mm.
3. The method according to claim 1, wherein the pre-firing conditions in the step (2) are 700 to 900 ℃oC, the time is 12-24 hours.
4. The method according to claim 1, wherein the laser in step (3) is a nanosecond solid-state laser, the laser frequency is 10 Hz, the wavelength is 1064nm, the pulse width is 1-7 ns, the laser pulse intensity is 100-350 mJ/pulse, the spot diameter is 1-3 mm, and the cleaning agent is chromatographically pure ethanol.
5. The method according to claim 1, wherein the filtration in step (4) is performed by using a centrifuge at a speed of 5000-15000 rpm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113593878A (en) * | 2021-07-06 | 2021-11-02 | 中国计量大学 | Preparation of nano-grade high-performance Nd2Fe14Method for preparing B/MnBi composite magnet material |
| CN113593874A (en) * | 2021-06-30 | 2021-11-02 | 中国计量大学 | Preparation method of high-performance samarium cobalt/neodymium iron boron double-phase composite magnet material |
| CN113593881A (en) * | 2021-07-13 | 2021-11-02 | 东阳市顶峰磁材有限公司 | Method for preparing neodymium iron boron composite permanent magnet by liquid phase laser ablation method |
| CN113593877A (en) * | 2021-07-06 | 2021-11-02 | 中国计量大学 | Method for preparing nano-scale high-performance composite magnet material |
| CN113690042A (en) * | 2021-09-12 | 2021-11-23 | 杨杭福 | Device and method for continuously preparing alnico nanoparticles |
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2020
- 2020-12-31 CN CN202011614611.7A patent/CN112582167A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113593874A (en) * | 2021-06-30 | 2021-11-02 | 中国计量大学 | Preparation method of high-performance samarium cobalt/neodymium iron boron double-phase composite magnet material |
| CN113593878A (en) * | 2021-07-06 | 2021-11-02 | 中国计量大学 | Preparation of nano-grade high-performance Nd2Fe14Method for preparing B/MnBi composite magnet material |
| CN113593877A (en) * | 2021-07-06 | 2021-11-02 | 中国计量大学 | Method for preparing nano-scale high-performance composite magnet material |
| CN113593881A (en) * | 2021-07-13 | 2021-11-02 | 东阳市顶峰磁材有限公司 | Method for preparing neodymium iron boron composite permanent magnet by liquid phase laser ablation method |
| CN113690042A (en) * | 2021-09-12 | 2021-11-23 | 杨杭福 | Device and method for continuously preparing alnico nanoparticles |
| CN113690042B (en) * | 2021-09-12 | 2023-09-26 | 杨杭福 | Device and method for continuously preparing aluminum nickel cobalt nano particles |
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