CN115322442A - Electromagnetic shielding composite material with temperature response characteristic and preparation method and application thereof - Google Patents
Electromagnetic shielding composite material with temperature response characteristic and preparation method and application thereof Download PDFInfo
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- CN115322442A CN115322442A CN202211011976.XA CN202211011976A CN115322442A CN 115322442 A CN115322442 A CN 115322442A CN 202211011976 A CN202211011976 A CN 202211011976A CN 115322442 A CN115322442 A CN 115322442A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- H—ELECTRICITY
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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Abstract
The invention provides an electromagnetic shielding composite material with temperature response characteristics, and a preparation method and application thereof, and belongs to the technical field of electromagnetic shielding materials. The electromagnetic shielding composite material with the temperature response characteristic is prepared by compounding vanadium dioxide serving as a functional material and a base material. The invention also provides a preparation method and application of the electromagnetic shielding composite material with the temperature response characteristic. The material of the invention utilizes the fact that the vanadium dioxide is changed from an insulating state to a metal state when the temperature of the vanadium dioxide exceeds the phase transition temperature, realizes that the electromagnetic shielding performance of the composite material has the temperature response characteristic, and the material has the characteristics of capability of intrinsically performing tunable electromagnetic response to heat without structural deformation and recyclability, thereby greatly improving the reliability of the material, having wide application prospect and having great significance for being used as an intelligent temperature control electromagnetic shielding switch in devices.
Description
Technical Field
The invention belongs to the technical field of electromagnetic shielding materials, and relates to an electromagnetic shielding composite material with temperature response characteristics, and a preparation method and application thereof.
Background
With the rapid development of electronic communication technology, electronic devices develop towards high integration and multiple functions, and the traditional electromagnetic shielding composite material has single function and cannot make electromagnetic response to external stimulation. The intelligent electromagnetic shielding composite material means that the electromagnetic property of the composite material can be changed by external stimuli including force, electricity, magnetism, heat and the like. The existing intelligent electromagnetic shielding composite material is basically designed in a certain structure, and responds to electromagnetic waves through structural deformation. The existing intelligent shielding composite material cannot be based on the intrinsic characteristics of the material, and the composite material can deform when responding to external stimuli, which is a great challenge to the reliability of the material.
The heat is an important stimulus factor, and because the high-speed operation of the electronic device is inevitably accompanied with the generation of a large amount of heat, the heat is a problem that the chip cannot be avoided during working, and the development of the intrinsic composite material which can perform tunable electromagnetic response on the heat has wide application prospect.
Therefore, the electromagnetic shielding composite material with the thermal response and the recyclable characteristic is developed, and has great significance for being applied to devices as an intelligent temperature-controlled electromagnetic shielding switch.
Disclosure of Invention
In view of the above, the invention provides an electromagnetic shielding composite material with temperature response characteristic, and a preparation method and an application thereof.
In order to achieve the purpose, the invention provides an electromagnetic shielding composite material with temperature response characteristics, which is prepared by taking vanadium dioxide as a functional material and compounding the functional material and a base material.
Preferably, the vanadium dioxide is fibrous, or flake-like, or granular.
Preferably, the vanadium dioxide is doped before use, and the doping element is tungsten element or germanium element.
Preferably, the matrix material is a polymer, or cellulose fibers, or graphene material.
Preferably, the mass ratio of vanadium dioxide to the matrix material is 1.
The invention also provides a preparation method of the electromagnetic shielding composite material with the temperature response characteristic, which comprises the following steps:
ball-milling and uniformly blending vanadium dioxide and the gel or solution or dispersion liquid of the matrix material according to a certain proportion;
then freezing and molding, and then freeze-drying, and then mechanically pressing the film to form a film; or heating, curing and forming.
Preferably, the matrix material is cellulose fiber, and the preparation method comprises the following steps:
ball-milling vanadium dioxide and cellulose fiber gel according to a certain proportion, and uniformly blending;
then freezing and forming, and freeze-drying;
then mechanically pressing the film to obtain the vanadium dioxide/cellulose fiber film.
Preferably, the matrix material is a polymer, and the preparation method comprises the following steps:
ball-milling vanadium dioxide and polymer solution according to a certain proportion, and uniformly blending;
and then heating, curing and molding to obtain the vanadium dioxide/polymer composite material.
Preferably, the matrix material is graphene, and the preparation method comprises the following steps:
ball-milling vanadium dioxide and graphene dispersion liquid according to a certain proportion, and uniformly blending;
then freezing and forming, and freeze-drying;
and then mechanically pressing the film to obtain the vanadium dioxide/graphene film.
The invention also provides application of the electromagnetic shielding composite material with the temperature response characteristic, and the electromagnetic shielding composite material with the temperature response characteristic is used as an intelligent temperature-controlled electromagnetic shielding switch in a device.
The invention adopts the technical scheme that the method has the advantages that:
the electromagnetic shielding composite material with the temperature response characteristic is compounded with a base material by adopting a phase-change material vanadium dioxide as a functional material, and the electromagnetic shielding performance of the composite material has the temperature response characteristic by utilizing the transition of the vanadium dioxide from an insulating state to a metal state when the temperature of the vanadium dioxide exceeds the phase-change temperature; the electromagnetic shielding composite material with the temperature response characteristic is an intrinsic composite material capable of performing tunable electromagnetic response to heat, has a recyclable characteristic, avoids the problem that the traditional intelligent electromagnetic shielding composite material needs to respond to external stimulation through deformation on a design structure, and greatly improves the reliability of the material. The preparation method of the electromagnetic shielding composite material with the temperature response characteristic is simple and can be used for industrial production. The electromagnetic shielding composite material with the temperature response characteristic has wide application prospect and has important significance for being applied to devices as an intelligent temperature control electromagnetic shielding switch.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an XRD pattern of vanadium dioxide at different temperatures;
FIG. 2 is a cross-sectional microscopic view of a vanadium dioxide/nanocellulose fiber film in example 1 of the present invention;
FIG. 3 is a graph of the electrical conductivity of the vanadium dioxide/nanocellulose fibers of example 1 at different temperatures;
FIG. 4 is a graph of the electromagnetic shielding effectiveness of the vanadium dioxide/nanocellulose fibers of example 1 at different temperatures;
FIG. 5 shows the electromagnetic shielding effectiveness of vanadium dioxide/polyurethane of example 2 at different temperatures;
fig. 6 shows the electromagnetic shielding effectiveness of the vanadium dioxide/graphene of example 3 at different temperatures.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Vanadium dioxide (VO) 2 ) The crystal structure of monoclinic rutile at normal temperature has poor conductivity and presents an insulating state, and the XRD pattern of vanadium dioxide at different temperatures is shown in figure 1. Can be converted from an insulating state to gold when its temperature exceeds the phase transition temperatureThe "belongs" state. Before and after the phase change, the reflectivity, the absorptivity, the resistivity, the magnetic susceptibility and the like of the vanadium dioxide are greatly changed, particularly the change of the resistivity reaches 3 to 5 orders of magnitude, so that the vanadium dioxide can be used as an excellent filler with tunable thermal-electromagnetic response.
The invention provides an electromagnetic shielding composite material with temperature response characteristics, which is prepared by compounding vanadium dioxide serving as a functional material and a base material. Wherein, the vanadium dioxide can be in a fiber shape, a sheet shape or a particle shape. When the vanadium dioxide is in the form of particles, the particle size of the vanadium dioxide particles is in the range of 0.1 to 5 μm. When the vanadium dioxide is fibrous, a conductive network is easier to form mutually, the flaky shape is inferior, the particles are most difficult, the conductivity of the fibrous vanadium dioxide composite material is highest under the same filling ratio of the same base material, and the electromagnetic shielding performance of the material is in direct proportion to the conductivity. Before the vanadium dioxide is used, the vanadium dioxide can be doped, the doping element is tungsten element or germanium element, the phase transition temperature of the vanadium dioxide can be changed by common doping, and the conductivity of the vanadium dioxide can be reduced, so that the electromagnetic shielding performance of the vanadium dioxide is reduced. The matrix material may be a polymer, or cellulose fibers, or graphene materials, or the like. The mass ratio of the vanadium dioxide to the matrix material is 1-10, preferably 10:1, and the prepared composite material has a good electromagnetic shielding effect.
The invention also provides a preparation method of the electromagnetic shielding composite material with the temperature response characteristic, which comprises the following steps:
ball-milling vanadium dioxide and the gel or solution or dispersion liquid of the matrix material according to a certain proportion, and uniformly blending;
then freezing and forming, freezing and drying, and then mechanically pressing the film into a film; or heating, curing and forming.
In some embodiments, the matrix material is cellulose fibers and the method of making comprises the steps of:
ball-milling and blending vanadium dioxide and cellulose fiber gel uniformly according to a certain proportion;
then freezing and molding, and then freezing and drying;
then mechanically pressing the film to obtain the vanadium dioxide/cellulose fiber film.
In some embodiments, the matrix material is a polymer and the method of preparation comprises the steps of:
ball-milling vanadium dioxide and polymer solution according to a certain proportion, and uniformly blending; wherein, the polymer can be thermoplastic polyurethane, preferably polyester type or polyether type, the Shore hardness range is 40-90A, and the molecular weight range is 30-20W;
and then heating, curing and molding to obtain the vanadium dioxide/polymer composite material.
In some embodiments, the matrix material is graphene, and the preparation method comprises the following steps:
ball-milling vanadium dioxide and graphene dispersion liquid according to a certain proportion, and uniformly blending; wherein the dispersing agent in the graphene dispersion liquid is water or an organic solvent, and the organic solvent mainly comprises methanol, ethanol, isopropanol, dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and the like;
then freezing and molding, and then freezing and drying;
and then mechanically pressing the film to obtain the vanadium dioxide/graphene film.
The invention also provides application of the electromagnetic shielding composite material with the temperature response characteristic, and the electromagnetic shielding composite material with the temperature response characteristic is used as an intelligent temperature-controlled electromagnetic shielding switch in a device.
Example 1
The preparation process of the vanadium dioxide/nano cellulose fiber film is as follows:
weighing 0.1mol of vanadium dioxide particles (the particle size is about 200 nm) and 0.01mol of nano cellulose fiber gel (the mass fraction of the nano cellulose fibers is one percent), ball-milling and blending at the rotating speed of 100-2000r/min for 1-60min;
pouring the uniformly stirred vanadium dioxide/nano cellulose fiber gel into a plastic culture dish, freezing for 4 hours at the temperature of minus 20 ℃ in a refrigerator, and then carrying out freeze drying on the frozen and molded vanadium dioxide/nano cellulose fiber gel for 24 hours;
and mechanically pressing the dried vanadium dioxide/nano cellulose fiber gel for 1 minute under the pressure of 50MPa to obtain a vanadium dioxide/nano cellulose fiber film with the thickness of about 0.6mm.
FIG. 2 is a cross-sectional microscopic view of the vanadium dioxide/nanocellulose fiber membrane, from which it can be seen that vanadium dioxide particles are confined within the nanocellulose fiber network, enhancing the mechanical stability of the composite.
Pressing the freeze-dried vanadium dioxide/nano cellulose fiber gel into a regular block of 20 × 10 × 2mm (l × w × h), then adhering copper foils coated with conductive silver paste to two sides of the block to serve as electrodes, finally measuring the resistance of the material by using a resistance meter, converting to obtain the conductivity, and measuring the conductivity of the vanadium dioxide/nano cellulose fiber at different temperatures as shown in figure 3, wherein the graph shows that the conductivity of the vanadium dioxide/nano cellulose fiber is sharply increased between 65 ℃ and 70 ℃, which indicates that the vanadium dioxide phase change starts to occur. When the temperature reaches 70 ℃, the conductivity of the vanadium dioxide/nano cellulose fiber composite material reaches a stable value, and then the temperature is raised, so that the conductivity cannot rise along with the temperature rise. The conductivity of the material is in direct proportion to the electromagnetic shielding effectiveness, so that the electromagnetic shielding effectiveness is proved not to be further improved after the phase change of the vanadium dioxide/nano cellulose fiber composite material occurs.
The vanadium dioxide/nanocellulose fiber thin film was made into a 22.86mm by 10.16mm (l w) block sample (the size corresponds to the size of the 8.2-12.4GHz band test fixture), and then the sample was placed in a high temperature waveguide test apparatus for testing, the model of the vector network analyzer was N5227B. During testing, the heating rate is 1 ℃ per minute, the electromagnetic shielding performance of the material is tested after the material is heated to the target testing temperature and is kept for 20 minutes. The electromagnetic shielding effectiveness of the vanadium dioxide/nanocellulose fiber at different temperatures is shown in fig. 4, and it can be seen from the graph that the vanadium dioxide/nanocellulose fiber film is still an insulator when the phase transition temperature of the vanadium dioxide is not reached, and the electromagnetic shielding effectiveness is hardly improved. When the temperature is 70 ℃, the vanadium dioxide is subjected to phase transition and is converted into a metal conductor, the electromagnetic shielding effectiveness of the vanadium dioxide/nano cellulose fiber film is rapidly improved, but when the temperature is increased after the phase transition temperature is reached, the electromagnetic shielding effectiveness of response is not further improved.
Example 2
The preparation process of the vanadium dioxide/polyurethane composite material is as follows:
weighing 0.1mol of vanadium dioxide particles (the particle size is about 200 nm) and 0.01mol of thermoplastic polyurethane (polyester type, the Shore hardness range is 50A, and the molecular weight range is 20W), carrying out ball milling and blending, wherein the rotating speed is 100-2000r/min, and the ball milling is 1-60min;
and pouring the uniformly stirred vanadium dioxide/polyurethane into a mold, and putting the mold into an oven to heat for 3 hours at the temperature of 80 ℃ to finally obtain the vanadium dioxide/polyurethane composite material.
The vanadium dioxide/polyurethane composite material is made into a 22.86mm 10.16mm (l w) block sample (the size corresponds to the size of a test fixture of 8.2-12.4GHz wave band), and then the sample is put into a high-temperature waveguide test device for testing, wherein the model of a vector network analyzer is N5227B. In the test, the heating rate is 1 ℃ per minute, the electromagnetic shielding performance of the material is obtained by testing after heating to the target test temperature and keeping the temperature for 20 minutes, as shown in fig. 5, it can be seen from the figure that the electromagnetic shielding performance of the vanadium dioxide/polyurethane composite material is increased along with the increase of the temperature, when the temperature is 70 ℃, the vanadium dioxide is subjected to phase change and is completely converted into a metal conductor, and the electromagnetic shielding performance of the vanadium dioxide/polyurethane composite material is stable.
Example 3
The preparation process of the vanadium dioxide/graphene composite material is as follows:
weighing 0.1mol of vanadium dioxide particles (the particle size is about 200 nm) and 0.01mol of graphene dispersion liquid (water is used as a dispersing agent), and carrying out ball milling and blending at the rotating speed of 100-2000r/min for 1-60min;
pouring the uniformly stirred vanadium dioxide/graphene solution into a plastic culture dish, freezing for 4 hours in a refrigerator at the temperature of-20 ℃, and then freeze-drying the frozen and molded vanadium dioxide/graphene gel for 24 hours;
and mechanically pressing the dried vanadium dioxide/graphene gel for 1 minute under the pressure of 50MPa to finally obtain the vanadium dioxide/graphene film with the thickness of about 0.6mm.
The vanadium dioxide/graphene film is made into a 22.86mm 10.16mm (l w) block sample (the size corresponds to the size of a test fixture of 8.2-12.4GHz waveband), and then the sample is put into a high-temperature waveguide test device for testing, wherein the model of a vector network analyzer is N5227B. During testing, the heating rate is 1 ℃ per minute, the electromagnetic shielding performance of the material is tested after heating to the target testing temperature and keeping the temperature for 20 minutes, and the electromagnetic shielding performance is shown in fig. 6. It can be seen from the figure that the electromagnetic shielding effectiveness of the vanadium dioxide/graphene film increases with the increase of the temperature, when the temperature is 70 ℃, the vanadium dioxide is subjected to phase change and is completely converted into a metal conductor, and the electromagnetic shielding effectiveness of the vanadium dioxide/graphene film is stable.
The invention adopts the technical scheme that the advantages are as follows:
the electromagnetic shielding composite material with the temperature response characteristic is compounded with a base material by adopting a phase-change material vanadium dioxide as a functional material, and the electromagnetic shielding performance of the composite material is realized to have the temperature response characteristic by utilizing the fact that the vanadium dioxide is converted into a metal state from an insulating state when the temperature of the vanadium dioxide exceeds the phase-change temperature; the electromagnetic shielding composite material with the temperature response characteristic is an intrinsic composite material capable of performing tunable electromagnetic response to heat, has a recyclable characteristic, avoids the problem that the traditional intelligent electromagnetic shielding composite material needs to respond to external stimulation through deformation on a design structure, and greatly improves the reliability of the material. The preparation method of the electromagnetic shielding composite material with the temperature response characteristic is simple and can be used for industrial production. The electromagnetic shielding composite material with the temperature response characteristic has wide application prospect and has important significance for being applied to devices as an intelligent temperature control electromagnetic shielding switch.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The electromagnetic shielding composite material with the temperature response characteristic is characterized in that vanadium dioxide is used as a functional material, and the functional material is prepared by compounding with a base material.
2. The composite material for electromagnetic shielding with temperature response characteristic of claim 1, wherein the vanadium dioxide is fibrous, or flaky, or granular.
3. The electromagnetically shielding composite material as claimed in claim 1, wherein the vanadium dioxide is doped before use, and the doping element is tungsten element or germanium element.
4. The electromagnetically shielding composite material as claimed in claim 1, wherein the matrix material is a polymer, or a cellulose fiber, or a graphene material.
5. The electromagnetic shielding composite material with temperature response characteristic as claimed in claim 1, wherein the ratio of the amount of vanadium dioxide to the substance of the base material is 1.
6. The method for preparing an electromagnetic shielding composite material with temperature response characteristic according to any one of claims 1 to 5, comprising the steps of:
ball-milling vanadium dioxide and the gel or solution or dispersion liquid of the matrix material according to a certain proportion, and uniformly blending;
then freezing and forming, freezing and drying, and then mechanically pressing the film into a film; or heating, curing and forming.
7. The method for preparing an electromagnetic shielding composite material with temperature response characteristics as claimed in claim 6, wherein the base material is cellulose fiber, and the preparation method comprises the following steps:
ball-milling and blending vanadium dioxide and cellulose fiber gel uniformly according to a certain proportion;
then freezing and forming, and freeze-drying;
then mechanically pressing the film to obtain the vanadium dioxide/cellulose fiber film.
8. The method for preparing an electromagnetic shielding composite material with temperature response characteristic according to claim 6, wherein the matrix material is a polymer, and the preparation method comprises the following steps:
ball-milling vanadium dioxide and polymer solution according to a certain proportion, and uniformly blending;
and then heating, curing and molding to obtain the vanadium dioxide/polymer composite material.
9. The method for preparing an electromagnetic shielding composite material with temperature response characteristic according to claim 6, wherein the matrix material is graphene, and the preparation method comprises the following steps:
ball-milling and blending vanadium dioxide and graphene dispersion liquid according to a certain proportion uniformly;
then freezing and molding, and then freezing and drying;
and then mechanically pressing the film to obtain the vanadium dioxide/graphene film.
10. Use of the electromagnetically shielding composite material with temperature response characteristic as claimed in any one of claims 1 to 5, wherein the electromagnetically shielding composite material with temperature response characteristic is used as an intelligent temperature-controlled electromagnetically shielding switch in a device.
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