CN114093663A - Room temperature magnetocaloric material and method for producing the same - Google Patents
Room temperature magnetocaloric material and method for producing the same Download PDFInfo
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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
- H01F41/14—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 applying magnetic films to substrates
- H01F41/18—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 applying magnetic films to substrates by cathode sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- H01F1/015—Metals or alloys
Abstract
The invention discloses a room temperature magnetocaloric material and a preparation method thereof. The preparation method of the room-temperature magnetocaloric material comprises the following steps: the method comprises the following steps: preparing Gd on a substrate by adopting a magnetron sputtering deposition technology5Si2Ge2An alloy thin film; step two: by magnetron sputtering deposition on Gd5Si2Ge2Preparation of Ni on alloy film50Mn37Sb13The alloy film is used for obtaining a first composite film material compounded by a GdSiGe/NiMnSb alloy film; step three: preparing Ni on the surface of the first composite film material by adopting a magnetron sputtering deposition technology50Mn37Sn13A film is obtained by compounding GdSiGe/NiMnSb/NiMnSn alloy filmA second composite film material of (a); step four: preparing Ni on the surface of the second composite film material by adopting a magnetron sputtering deposition technology50Mn35In15And (3) forming a film to obtain the room-temperature magnetocaloric material compounded by the GdSiGe/NiMnSb/NiMnSn/NiMnIn alloy film. The preparation method of the room-temperature magnetocaloric material provided by the invention is simple and easy to operate, has practical value, and the composite material is low in cost, environment-friendly and pollution-free.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a room-temperature magnetocaloric material and a preparation method thereof.
Background
With the increase of global economy, population increase and the continuous improvement of living standard of people, the demand of human beings on refrigeration technology and air conditioning is expected to be greatly increased in the next 30 years. In today's society, the power consumption of refrigeration and air conditioning accounts for 17% of the global power consumption, which is about 2000 TWh. If the energy efficiency for the refrigeration system is not improved or no new technology is developed for use, the power consumption will reach as much as 3 times the current consumption by 2050.
Currently, most residential, transportation, commercial refrigeration and air conditioning systems employ gas compression refrigeration technology. The refrigeration system is a relatively mature refrigeration technology and has the advantages of low production and maintenance cost, safe and reliable operation and the like. However, in the use of some small-sized household appliances, the refrigeration efficiency is often low, and the average efficiency of the Carnot cycle is 20%, and still there is considerable room for improvement. In addition, the main problem of the gas compression refrigeration technology is the adverse effect of the currently used refrigerants on the environment, which generate greenhouse gases accounting for 7.8% of the total amount of global greenhouse gas emissions. Although environmentally friendly refrigerants are very limited, the hydrofluorocarbons currently used are expected to be phased out globally in the next 30 to 40 years. Accordingly, there is a great deal of effort being devoted by humans to find alternative refrigerants to provide both everyday air conditioning and refrigeration uses.
In recent years, magnetic refrigeration technology based on the magnetocaloric effect has received much attention. The magnetic heat material has heat absorption and release phenomena in the magnetic phase change process, so the developed solid magnetic refrigeration technology has the advantages of environmental protection, high intrinsic efficiency, stability and reliability, can avoid the environmental problems of ozone layer destruction, greenhouse effect and the like brought by the traditional gas compression type refrigeration technology, is one of the most potential alternative technologies, and is also a hotspot of current scientific research. The magnetocaloric materials mainly include a first-stage phase-change magnetocaloric material and a second-stage phase-change magnetocaloric material. The first-order phase-change magnetocaloric material mainly comprises Gd-Si-Ge, La-Fe-Si, MnAs base compounds, manganese-based Heusler (Heusler) alloy, manganese-based anti-perovskite alloy, Mn-Co-Ge, Fe-Rh alloy, perovskite oxides and other series, and is widely concerned by domestic and foreign scholars because most of the materials have first-order magnetic phase change in a room temperature region and are accompanied by a large magnetocaloric effect. The two-stage phase change magnetocaloric material mainly comprises a binary rare earth-based intermetallic compound, a rare earth-transition metal-main group metal ternary compound, a quaternary compound and the like, the phase change is mostly in a low-temperature region, and the two-stage phase change magnetocaloric material has good thermal and magnetic reversibility and thermal conductivity. Theoretically, all magnetic materials have magnetocaloric effect, but there are not many materials with significant magnetocaloric effect, and only a very small number of magnetic materials can be used for magnetic refrigeration. Therefore, the exploration of the magnetic refrigeration material with excellent magnetocaloric effect has important practical significance for the development and application of the magnetic refrigeration technology. Through long-term research and development, magnetic refrigeration technology has been widely applied, for example, the magnetic refrigeration technology is used in the fields of liquid helium preparation, low-temperature superconducting technology, medical health, aerospace and the like. However, the application of the magnetic refrigeration technology is mainly focused on the low-temperature region (below 20K), and the magnetic refrigeration material in the near room temperature region needs further intensive research and exploration. The temperature range of the magnetic refrigeration material which can be applied at the present stage is small, and the requirement of production and life for the refrigeration effect cannot be met.
Therefore, the research and development of a magnetocaloric material which can be used for magnetic refrigeration in the room temperature region and has high and stable performance is a research subject worth of discussion and has great application potential.
Disclosure of Invention
The invention aims to provide a novel system for preparing a high-efficiency and stable room-temperature magnetocaloric material by utilizing a geometric structure gradient design and magnetocaloric effect matching.
The invention provides a preparation method of a room-temperature magnetocaloric material to achieve the purpose, which comprises the following steps:
the method comprises the following steps: preparing a GdSiGe alloy film;
preparing Gd on a substrate by adopting a magnetron sputtering deposition technology5Si2Ge2An alloy thin film;
step two: preparing a first composite film material;
using magnetron sputtering deposition technique to deposit Gd on the surface of the substrate5Si2Ge2Preparation of Ni on alloy film50Mn37Sb13The alloy film is used for obtaining a first composite film material compounded by a GdSiGe/NiMnSb alloy film;
step three: preparing a second composite film material;
preparing Ni on the surface of the first composite film material by adopting a magnetron sputtering deposition technology50Mn37Sn13A film, obtaining a second composite film material compounded by a GdSiGe/NiMnSb/NiMnSn alloy film;
step four: preparing a room-temperature magnetocaloric material;
preparing Ni on the surface of the second composite film material by adopting a magnetron sputtering deposition technology50Mn35In15And (3) forming a film to obtain the room-temperature magnetocaloric material compounded by the GdSiGe/NiMnSb/NiMnSn/NiMnIn alloy film.
In the room-temperature magnetocaloric material, the thickness of each alloy thin film layer is in the range of 0-100 μm, and the thickness of each alloy thin film layer is the same/different.
As a further improvement of the invention, the magnetic phase transition temperature of each alloy film in the room temperature magnetocaloric material is located in the room temperature region.
As a further improvement of the present invention, said Gd5Si2Ge2The magnetic phase transition temperature region of the alloy film is 270-285K, Ni50Mn37Sb13The magnetic phase transition temperature region of the alloy film is 280-294K, Ni50Mn37Sn13The magnetic phase transition temperature region of the alloy thin film layer is 295-305K, and Ni50Mn35In15The magnetic phase transition temperature of the alloy film layer is 301-310K.
As a further improvement of the invention, the steps of preparing each alloy film by adopting the magnetron sputtering deposition technology comprise:
s01, cleaning a magnetron sputtering system and a sample cavity, wherein the magnetron sputtering system is positioned in a cylindrical sample cavity with the diameter of 450mm and the height of 350 mm;
s02, selecting a cylindrical target with the diameter of 60mm and the thickness of 2-3 mm as an alloy target for sputtering, and adjusting the distance between the alloy target and a substrate to be 70 mm;
and S03, controlling the sputtering system to start working to sputter and deposit an alloy thin film matched with the alloy target.
As a further improvement of the present invention, in step S01, the background vacuum of the sample chamber is better than 9 × 10-5Pa。
As a further improvement of the present invention, in step S03, the rotation speed of the substrate is 5-10 rpm; the sputtering gas is high-purity argon with the purity of 99.99 percent, the working pressure during sputtering is 0.5-1.0 Pa, and the sputtering power is 100-150W.
As a further improvement of the invention, the substrate is a Si base made of silicon and has a thickness of about 1 mm.
In order to achieve the purpose, the invention further provides a room-temperature magnetocaloric material, and the room-temperature magnetocaloric material is prepared by the preparation method of the room-temperature magnetocaloric material.
The invention has the beneficial effects that:
(1) the room-temperature magnetocaloric material obtained by the invention is a multilayer magnetic film in a geometric structure gradient arrangement, and has a wider magnetic refrigeration working temperature area and good magnetic refrigeration performance;
(2) the preparation method of the room-temperature magnetocaloric material provided by the invention is simple and easy to operate, has the characteristics of low cost and no pollution in the processing process, can conveniently and quickly effectively regulate and control the preparation environment and the processing thickness of the room-temperature magnetocaloric material, and has higher feasibility and application prospect.
Drawings
Fig. 1 is a flowchart illustrating a method for preparing a room-temperature magnetocaloric material according to the present invention.
Fig. 2 is a scanning electron microscope image of the room temperature magnetocaloric material prepared by the method for preparing the room temperature magnetocaloric material according to the present invention.
FIG. 3 is a magnetic entropy change-temperature curve of the room temperature magnetocaloric material system according to the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the accompanying drawings and preferred embodiments.
Referring to fig. 1, a method for preparing a room temperature magnetocaloric material according to the present invention includes the following steps:
the method comprises the following steps: preparing a GdSiGe alloy film;
preparing Gd on a substrate by adopting a magnetron sputtering deposition technology5Si2Ge2An alloy thin film;
step two: preparing a first composite film material;
using magnetron sputtering deposition technique to deposit Gd on the surface of the substrate5Si2Ge2Preparation of Ni on alloy film50Mn37Sb13The alloy film is used for obtaining a first composite film material compounded by a GdSiGe/NiMnSb alloy film;
step three: preparing a second composite film material;
preparing Ni on the surface of the first composite film material by adopting a magnetron sputtering deposition technology50Mn37Sn13A film, obtaining a second composite film material compounded by a GdSiGe/NiMnSb/NiMnSn alloy film;
step four: preparing a room-temperature magnetocaloric material;
preparing Ni on the surface of the second composite film material by adopting a magnetron sputtering deposition technology50Mn35In15Alloying the film to obtain the room-temperature magnetocaloric material compounded by the GdSiGe/NiMnSb/NiMnSn/NiMnIn alloy film.
In the present invention, each of the alloy thin film layers includes Gd5Si2Ge2Alloy thin film, Ni50Mn37Sb13Alloy thin film, Ni50Mn37Sn13Thin film and Ni50Mn35In15The thickness of the alloy thin film is in the range of 0-100 mu m, and further, the thickness of each alloy thin film layer is the same/different, so that the prepared room-temperature magnetocaloric material has a wider magnetic refrigeration working temperature area and good magnetic refrigeration performance.
Optionally, the magnetic phase transition temperature of each alloy film in the room-temperature magnetocaloric material is located in the room-temperature region. In a preferred embodiment of the present invention, Gd5Si2Ge2The magnetic phase transition temperature region of the alloy film is 270-285K, Ni50Mn37Sb13The magnetic phase transition temperature region of the alloy film is 280-294K, Ni50Mn37Sn13The magnetic phase transition temperature region of the alloy thin film layer is 295-305K, and Ni50Mn35In15The magnetic phase transition temperature of the alloy film layer is 301-310K. By the arrangement, through the gradient design of the geometric structure and the preparation of the composite material, the effective expansion of the working temperature zone of the room-temperature magnetocaloric material is realized, the magnetic refrigeration capacity and the application value of a composite material system are improved, and the method is suitable for application and popularization in daily production and life.
In a preferred embodiment of the present invention, the substrate on which each alloy thin film layer is sputtered is a Si substrate made of silicon, and since the Si substrate has the advantages of low cost and good electrical and thermal conductivity, the preparation cost of the room temperature magnetocaloric material can be effectively reduced, and the practicability of the preparation method of the room temperature magnetocaloric material of the present application is further improved.
Furthermore, the preparation of each alloy film layer is obtained by adopting a magnetron sputtering deposition technology. In fact, the film structure prepared by the magnetron sputtering deposition technology has the advantages of high deposition speed, low substrate temperature rise and small damage to the film; the film obtained by sputtering is well combined with the substrate; the film has high purity, good density and good film forming uniformity; the thickness of the film layer can be accurately controlled, so that the magnetron sputtering deposition technology is preferably used for preparing each alloy film layer in the invention, and of course, in other embodiments of the invention, other film forming means can be adopted for preparing each alloy film layer, and the prepared alloy film layer is only required to be uniform in thickness and have good consistency.
In a preferred embodiment of the present invention, the step of preparing each alloy thin film by using a magnetron sputtering deposition technique comprises:
s01, cleaning a magnetron sputtering system and a sample cavity, wherein the sputtering system is positioned in a cylindrical sample cavity with the diameter of 450mm and the height of 350 mm;
s02, selecting a cylindrical target with the diameter of 60mm and the thickness of 2-3 mm as an alloy target for sputtering, and adjusting the distance between the alloy target and a substrate to be 70 mm;
and S03, controlling the sputtering system to start working to sputter and deposit an alloy thin film matched with the alloy target.
In this example, the background vacuum of the sample chamber in step S01 is better than 9X 10-5Pa. Further, in step S03, the rotation speed of the substrate is 5-10 rpm; the sputtering gas is high-purity argon with the purity of 99.99 percent, the working pressure during sputtering is 0.5-1.0 Pa, and the sputtering power is 100-150W.
The following description will describe in detail a method for preparing a room temperature magnetocaloric material according to the present invention with specific examples.
Example 1:
the method comprises the following steps: preparation of GdSiGe alloy film
With Gd5Si2Ge2Preparing Gd on a silicon substrate by taking the alloy as a target material and adopting a magnetron sputtering deposition method5Si2Ge2Alloy film, the background vacuum of sample cavity before sputtering is less than 9X 10-5Pa; in the sputtering process, the silicon substrate rotates at the speed of 10rpm, the used sputtering gas is high-purity argon with the purity of 99.99 percent, the working pressure is 0.5Pa, the sputtering power is 150W, the sputtering temperature is 25 ℃, and the sputtering thickness is 100 mu m.
Step two: preparing a first composite film material;
with Ni50Mn37Sb13The Gd prepared in the step one by adopting a magnetron sputtering deposition method with the alloy as the target material5Si2Ge2Preparing Ni on the alloy film50Mn37Sb13An alloy thin film in which a sample substrate was rotated at a speed of 5rpm, a sputtering gas was high-purity argon gas having a purity of 99.99%, an operating gas pressure was 0.5Pa, a sputtering power was 100W, a sputtering temperature was 30 ℃, and a sputtering thickness was 50 μm.
Step three: preparing a second composite film material;
with Ni50Mn37Sn13The alloy is taken as a target material, and the Gd prepared in the step two by adopting a magnetron sputtering deposition method5Si2Ge2/Ni50Mn37Sb13Preparing Ni on the alloy film50Mn37Sn13An alloy thin film in which a sample substrate was rotated at a speed of 10rpm, a sputtering gas was high-purity argon gas having a purity of 99.99%, an operating gas pressure was 1Pa, a sputtering power was 100W, a sputtering temperature was 25 ℃, and a sputtering thickness was 25 μm.
Step four: preparing a room-temperature magnetocaloric material;
with Ni50Mn35In15Gd prepared in the third step by using the alloy as a target material and adopting a magnetron sputtering deposition method5Si2Ge2/Ni50Mn37Sb13/Ni50Mn37Sn13Preparing Ni on the alloy film50Mn35In15An alloy thin film in which a sample substrate was rotated at a speed of 10rpm, a sputtering gas was high-purity argon gas having a purity of 99.99%, an operating gas pressure was 0.5Pa, a sputtering power was 100W, a sputtering temperature was 30 ℃, and a sputtering thickness was 15 μm.
Example 2
The method comprises the following steps: preparing a GdSiGe alloy film;
with Gd5Si2Ge2Preparing Gd on a silicon substrate by taking the alloy as a target material and adopting a magnetron sputtering deposition method5Si2Ge2Alloy film, the background vacuum of sample cavity before sputtering is less than 9X 10-5Pa; in the sputtering process, the silicon substrate rotates at the speed of 5rpm, the used sputtering gas is high-purity argon with the purity of 99.99 percent, the working pressure is 1.0Pa, the sputtering power is 100W, the sputtering temperature is 25 ℃, and the sputtering thickness is 80 mu m.
Step two: preparing a first composite film material;
with Ni50Mn37Sb13The Gd prepared in the step one by adopting a magnetron sputtering deposition method with the alloy as the target material5Si2Ge2Preparing Ni on the alloy film50Mn37Sb13An alloy thin film in which a sample substrate was rotated at a speed of 10rpm, a sputtering gas was high-purity argon gas having a purity of 99.99%, an operating gas pressure was 0.5Pa, a sputtering power was 150W, a sputtering temperature was 30 ℃, and a sputtering thickness was 60 μm.
Step three: preparing a second composite film material;
with Ni50Mn37Sn13The alloy is taken as a target material, and the Gd prepared in the step two by adopting a magnetron sputtering deposition method5Si2Ge2/Ni50Mn37Sb13Preparing Ni on the alloy film50Mn37Sn13An alloy thin film in which a sample substrate was rotated at a speed of 10rpm, a sputtering gas was high-purity argon gas having a purity of 99.99%, an operating gas pressure was 0.5Pa, a sputtering power was 100W, a sputtering temperature was 30 ℃, and a sputtering thickness was 40 μm.
Step four: preparing a room-temperature magnetocaloric material;
with Ni50Mn35In15Gd prepared in the third step by using the alloy as a target material and adopting a magnetron sputtering deposition method5Si2Ge2/Ni50Mn37Sb13/Ni50Mn37Sn13Preparing Ni on the alloy film50Mn35In15An alloy thin film in which a sample substrate was rotated at a speed of 5rpm, a sputtering gas was high-purity argon gas having a purity of 99.99%, an operating gas pressure was 0.8Pa, a sputtering power was 120W, a sputtering temperature was 30 ℃, and a sputtering thickness was 20 μm.
Example 3
The method comprises the following steps: preparing a GdSiGe alloy film;
with Gd5Si2Ge2Preparing Gd on a silicon substrate by taking the alloy as a target material and adopting a magnetron sputtering deposition method5Si2Ge2Alloy film, the background vacuum of sample cavity before sputtering is less than 9X 10-5Pa; in the sputtering process, the silicon substrate rotates at the speed of 8rpm, the used sputtering gas is high-purity argon with the purity of 99.99 percent, the working pressure is 0.8Pa, the sputtering power is 140W, the sputtering temperature is 25 ℃, and the sputtering thickness is 50 mu m.
Step two: preparing a first composite film material;
with Ni50Mn37Sb13The Gd prepared in the step one by adopting a magnetron sputtering deposition method with the alloy as the target material5Si2Ge2Preparing Ni on the alloy film50Mn37Sb13An alloy thin film in which a sample substrate was rotated at a speed of 10rpm, a sputtering gas was high-purity argon gas having a purity of 99.99%, an operating gas pressure was 0.8Pa, a sputtering power was 140W, a sputtering temperature was 28 ℃, and a sputtering thickness was 100 μm.
Step three: preparing a second composite film material;
with Ni50Mn37Sn13The alloy is taken as a target material, and the Gd prepared in the step two by adopting a magnetron sputtering deposition method5Si2Ge2/Ni50Mn37Sb13Preparing Ni on the alloy film50Mn37Sn13An alloy thin film in which a sample substrate was rotated at a speed of 10rpm, a sputtering gas was high-purity argon gas having a purity of 99.99%, an operating gas pressure was 0.5Pa, a sputtering power was 130W, a sputtering temperature was 30 ℃, and a sputtering thickness was 50 μm.
Step four: preparing a room-temperature magnetocaloric material;
with Ni50Mn35In15Gd prepared in the third step by using the alloy as a target material and adopting a magnetron sputtering deposition method5Si2Ge2/Ni50Mn37Sb13/Ni50Mn37Sn13Preparing Ni on the alloy film50Mn35In15An alloy thin film in which a sample substrate was rotated at a speed of 5rpm, a sputtering gas was high-purity argon gas having a purity of 99.99%, an operating gas pressure was 1.0Pa, a sputtering power was 130W, a sputtering temperature was 26 ℃, and a sputtering thickness was 100 μm.
The action mechanism of the invention is as follows: the material with excellent magnetic refrigeration performance in the near room temperature area is selected, a gradient multilayer film material system is constructed through the geometric structure design, and the magnetic refrigeration working temperature area of the system can be greatly expanded through regulating and controlling the thickness and quality relation of different components, so that the magnetic entropy change and the magnetic refrigeration efficiency of the system are improved. Therefore, the GdSiGe/NiMnSb/NiMnSn/NiMnIn composite film material with the gradient change of the geometric structure is a high-efficiency and stable magnetic refrigeration material which can be applied to the room temperature environment.
Referring to fig. 3, it can be seen that, compared to the composite magnetocaloric material prepared in the prior art, the working temperature range and the magnetocaloric performance of the room temperature magnetocaloric material system prepared and obtained in the embodiment of the present application are both significantly improved, which is beneficial to popularization and use.
In conclusion, the room-temperature magnetocaloric material obtained by the invention is a multilayer magnetic film with a geometric structure gradient arrangement, and has a wider magnetic refrigeration working temperature area and good magnetic refrigeration performance. Meanwhile, the preparation method of the room-temperature magnetocaloric material provided by the invention is simple and easy to operate, has the characteristics of low cost and no pollution in the processing process, can conveniently and quickly effectively regulate and control the preparation environment and the processing thickness of the room-temperature magnetocaloric material, and has higher feasibility and application prospects.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (9)
1. A preparation method of a room-temperature magnetocaloric material comprises the following steps:
the method comprises the following steps: preparing a GdSiGe alloy film;
preparing Gd on a substrate by adopting a magnetron sputtering deposition technology5Si2Ge2An alloy thin film;
step two: preparing a first composite film material;
using magnetron sputtering deposition technique to deposit Gd on the surface of the substrate5Si2Ge2Preparation of Ni on alloy film50Mn37Sb13The alloy film is used for obtaining a first composite film material compounded by a GdSiGe/NiMnSb alloy film;
step three: preparing a second composite film material;
preparing Ni on the surface of the first composite film material by adopting a magnetron sputtering deposition technology50Mn37Sn13A film, obtaining a second composite film material compounded by a GdSiGe/NiMnSb/NiMnSn alloy film;
step four: preparing a room-temperature magnetocaloric material;
preparing Ni on the surface of the second composite film material by adopting a magnetron sputtering deposition technology50Mn35In15And (3) forming a film to obtain the room-temperature magnetocaloric material compounded by the GdSiGe/NiMnSb/NiMnSn/NiMnIn alloy film.
2. A method for preparing a magnetocaloric material at room temperature according to claim 1, characterized in that: in the room-temperature magnetocaloric material, the thickness of each alloy thin film layer is within the range of 0-100 μm, and the thickness of each alloy thin film layer is the same or different.
3. The method of preparing a room temperature magnetocaloric material according to claim 1, wherein the magnetic phase transition temperature of each alloy thin film in the room temperature magnetocaloric material is in a room temperature region.
4. A method for preparing a magnetocaloric material at room temperature according to claim 2, characterized in that: the Gd5Si2Ge2The magnetic phase transition temperature region of the alloy film is 270-285K, Ni50Mn37Sb13The magnetic phase transition temperature region of the alloy film is 280-294K, Ni50Mn37Sn13The magnetic phase transition temperature region of the alloy thin film layer is 295-305K, and Ni50Mn35In15The magnetic phase transition temperature of the alloy film layer is 301-310K.
5. A method for preparing a magnetocaloric material at room temperature according to claim 1, wherein the step of preparing each alloy thin film by magnetron sputtering deposition technique comprises:
s01, cleaning a magnetron sputtering system and a sample cavity, wherein the magnetron sputtering system is positioned in a cylindrical sample cavity with the diameter of 450mm and the height of 350 mm;
s02, selecting a cylindrical target with the diameter of 60mm and the thickness of 2-3 mm as an alloy target for sputtering, and adjusting the distance between the alloy target and a substrate to be 70 mm;
and S03, controlling the sputtering system to start working to sputter and deposit an alloy thin film matched with the alloy target.
6. A method for preparing a magnetocaloric material at room temperature according to claim 4, characterized in that: in step S01, the background vacuum of the sample chamber is better than 9 × 10-5Pa。
7. A method for preparing a magnetocaloric material at room temperature according to claim 4, characterized in that: in step S03, the rotation speed of the substrate is 5-10 rpm; the sputtering gas is high-purity argon with the purity of 99.99 percent, the working pressure during sputtering is 0.5-1.0 Pa, and the sputtering power is 100-150W.
8. A method for preparing a magnetocaloric material at room temperature according to claim 1, characterized in that: the substrate is a Si base made of silicon and is about 1mm thick.
9. A room temperature magnetocaloric material, characterized in that: the room-temperature magnetocaloric material is prepared by the method for preparing the room-temperature magnetocaloric material according to any one of claims 1 to 8.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003277926A (en) * | 2001-12-07 | 2003-10-02 | Samsung Electronics Co Ltd | Method of vapor deposition of heusler alloy by co- sputtering method |
| US20040261420A1 (en) * | 2003-06-30 | 2004-12-30 | Lewis Laura J. Henderson | Enhanced magnetocaloric effect material |
| CN1670241A (en) * | 2005-03-03 | 2005-09-21 | 西华大学 | Method and device for producing membrane on magnetic refrigeration material surface |
| JP2006161120A (en) * | 2004-12-09 | 2006-06-22 | Ulvac Japan Ltd | Deposition method of heusler's alloy film, and tunnelling magnetoresistive element |
| CN101532752A (en) * | 2009-04-09 | 2009-09-16 | 浙江科技学院 | Room temperature magnetic fluid refrigerating device |
| CN105755346A (en) * | 2016-04-15 | 2016-07-13 | 西安交通大学 | Ni-Mn-In room-temperature magnetic refrigeration material and preparation method thereof |
| CN106554006A (en) * | 2015-09-25 | 2017-04-05 | 国家纳米科学中心 | A kind of material with carbon element, preparation method and applications |
| CN108511142A (en) * | 2018-04-28 | 2018-09-07 | 中国科学院物理研究所 | A kind of more iron composite materials and its preparation method and application based on the hot La-Fe-Co-Si of huge magnetic |
| CN109913816A (en) * | 2019-04-29 | 2019-06-21 | 天津城建大学 | Temperature gradient magneto-caloric material and preparation method thereof |
| US20190352747A1 (en) * | 2017-01-09 | 2019-11-21 | General Engineering & Research, L.L.C. | Magnetocaloric alloys useful for magnetic refrigeration applications |
| US20200294697A1 (en) * | 2017-12-01 | 2020-09-17 | Virginia Commonwealth University | Perovskite manganese oxides with strong magnetocaloric effect and uses thereof |
| CN112251721A (en) * | 2020-10-20 | 2021-01-22 | 广州市豪越新能源设备有限公司 | Double-layer Hastelloy magnetic refrigeration coating and preparation method thereof |
-
2021
- 2021-12-03 CN CN202111462601.0A patent/CN114093663A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003277926A (en) * | 2001-12-07 | 2003-10-02 | Samsung Electronics Co Ltd | Method of vapor deposition of heusler alloy by co- sputtering method |
| US20040261420A1 (en) * | 2003-06-30 | 2004-12-30 | Lewis Laura J. Henderson | Enhanced magnetocaloric effect material |
| JP2006161120A (en) * | 2004-12-09 | 2006-06-22 | Ulvac Japan Ltd | Deposition method of heusler's alloy film, and tunnelling magnetoresistive element |
| CN1670241A (en) * | 2005-03-03 | 2005-09-21 | 西华大学 | Method and device for producing membrane on magnetic refrigeration material surface |
| CN101532752A (en) * | 2009-04-09 | 2009-09-16 | 浙江科技学院 | Room temperature magnetic fluid refrigerating device |
| CN106554006A (en) * | 2015-09-25 | 2017-04-05 | 国家纳米科学中心 | A kind of material with carbon element, preparation method and applications |
| CN105755346A (en) * | 2016-04-15 | 2016-07-13 | 西安交通大学 | Ni-Mn-In room-temperature magnetic refrigeration material and preparation method thereof |
| US20190352747A1 (en) * | 2017-01-09 | 2019-11-21 | General Engineering & Research, L.L.C. | Magnetocaloric alloys useful for magnetic refrigeration applications |
| US20200294697A1 (en) * | 2017-12-01 | 2020-09-17 | Virginia Commonwealth University | Perovskite manganese oxides with strong magnetocaloric effect and uses thereof |
| CN108511142A (en) * | 2018-04-28 | 2018-09-07 | 中国科学院物理研究所 | A kind of more iron composite materials and its preparation method and application based on the hot La-Fe-Co-Si of huge magnetic |
| CN109913816A (en) * | 2019-04-29 | 2019-06-21 | 天津城建大学 | Temperature gradient magneto-caloric material and preparation method thereof |
| CN112251721A (en) * | 2020-10-20 | 2021-01-22 | 广州市豪越新能源设备有限公司 | Double-layer Hastelloy magnetic refrigeration coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 董晓冬: ""室温磁制冷技术研究进展"", 河南科技能源与化学 * |
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