CN115433549A - Composite microsphere with wave absorbing and heat management functions and preparation method and application thereof - Google Patents
Composite microsphere with wave absorbing and heat management functions and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 98
- 239000004005 microsphere Substances 0.000 title claims abstract description 91
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910017709 Ni Co Inorganic materials 0.000 claims abstract description 57
- 229910003267 Ni-Co Inorganic materials 0.000 claims abstract description 57
- 229910003262 Ni‐Co Inorganic materials 0.000 claims abstract description 57
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 51
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 51
- 239000002253 acid Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 23
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- 229940010698 activated attapulgite Drugs 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
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- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001694 spray drying Methods 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 10
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims abstract description 10
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 8
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims abstract description 8
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims abstract description 8
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- 239000007921 spray Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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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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Abstract
The invention discloses a composite microsphere with wave absorbing and heat management functions, a preparation method and application thereof. The preparation method comprises the following steps: s1: mixing and stirring the acid-activated attapulgite, the Ni-Co magnetic particles and the carbon nanotube slurry with sodium hexametaphosphate and water, and performing ultrasonic treatment to obtain an acid-activated attapulgite-Ni-Co magnetic particle-carbon nanotube suspension; s2: the suspension is subjected to spray drying to construct composite microspheres; s3: calcining the composite microspheres; s4: vacuum impregnation is carried out on the composite microspheres and the phase-change material to obtain composite microspheres with wave absorbing and heat management functions; wherein, the preparation steps of the Ni-Co magnetic particles are as follows; weighing hexadecyl trimethyl ammonium bromide, naOH, cobalt acetate tetrahydrate and nickel acetate tetrahydrate, adding the weighed materials into an ethylene glycol solution, stirring and carrying out ultrasonic treatment to obtain a mixed suspension, and carrying out hydrothermal synthesis; and collecting a black powder product after the reaction is finished, and washing and drying the black powder product. The material can simultaneously realize the dual functions of wave absorption and heat management.
Description
Technical Field
The invention relates to the technical field of chemical materials, in particular to a composite microsphere with wave absorbing and heat management functions, a preparation method and application thereof.
Background
Electromagnetic radiation pollution becomes an important pollution source which greatly influences the health of urban residents after waste water, waste gas, noise and solid waste are polluted, and great threat is generated to the health of human beings. With the development of wireless communications, highly integrated, high-speed, miniaturized wireless communication devices tend to suffer from undesirable electromagnetic interference effects and significant heat generation. Therefore, in modern wireless communication, autonomous cars, and portable devices, materials having both excellent thermal management properties and excellent electromagnetic interference shielding properties have received much attention. Phase change materials can store and release energy in the form of latent heat while maintaining a constant temperature, have been widely used in various fields such as thermal energy storage and thermal management of electronic devices due to their ultra-high volumetric energy density and narrow temperature distribution range during energy conversion and utilization, and are known as optimal temperature control materials for thermal protection and electronic cooling systems.
Most of the composite phase change materials and microwave absorbing materials for electronic devices reported at present are concentrated on a single-purpose project, and the problems of complex preparation method, poor mechanical strength, low economic benefit and the like generally exist. In smart devices with small size, light weight, and high energy density, it becomes very important to develop a protection system with dual functions of electromagnetic interference shielding and thermal management. However, designing a flexible, lightweight, and low volume integrated material with both efficient emi shielding and thermal management functions remains a significant challenge.
Disclosure of Invention
The invention aims to provide a composite microsphere with wave absorbing and heat management functions, a preparation method and application thereof, aiming at the defects in the prior art.
The invention relates to a preparation method of a composite microsphere with wave absorbing and heat management functions, which comprises the following steps:
s1: mixing and stirring the acid-activated attapulgite, the Ni-Co magnetic particles and the carbon nano tube slurry with sodium hexametaphosphate and water, and performing ultrasonic treatment to obtain an acid-activated attapulgite-Ni-Co magnetic particle-carbon nano tube suspension;
s2: the suspension is subjected to spray drying to construct acid-activated attapulgite-Ni-Co magnetic particle-carbon nano tube composite microspheres;
s3: calcining to obtain attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres;
s4: vacuum impregnation is carried out on the composite microspheres and the phase-change material to obtain composite microspheres with wave absorbing and heat management functions;
wherein, the preparation steps of the Ni-Co magnetic particles are as follows; weighing hexadecyl trimethyl ammonium bromide, naOH, cobalt acetate tetrahydrate and nickel acetate tetrahydrate, adding the weighed materials into an ethylene glycol solution, stirring and carrying out ultrasonic treatment to obtain a mixed suspension, and carrying out hydrothermal synthesis on the mixed suspension; and collecting a black powder product after the reaction is finished, washing the black powder product by using deionized water or absolute ethyl alcohol, and drying the black powder product.
Further, in the preparation method of the Ni-Co magnetic particles, the cetyl trimethyl ammonium bromide, naOH, cobalt acetate tetrahydrate, nickel acetate tetrahydrate and ethylene glycol are calculated according to the following parts by weight:
cetyl trimethylammonium bromide: 2 to 6 portions of
NaOH:1 to 4 portions of
Cobalt acetate tetrahydrate: 0.2 to 0.5 portion
Nickel acetate tetrahydrate: 0.5 to 3 portions of
Ethylene glycol: 30 to 50 portions.
Furthermore, in the preparation method of the Ni-Co magnetic particles, the stirring speed is 500-1000r/min, and the stirring time is 30-60 min; the ultrasonic treatment time is 30-60 min; the hydrothermal synthesis temperature is 180-200 ℃, and the hydrothermal synthesis time is 6-12 h.
Further, the attapulgite raw ore is soaked in acid liquor to obtain the acid-activated attapulgite, and the acid activation process comprises the following steps: acid liquor leachingSoaking, solid-liquid separation, washing and drying; wherein the acid liquor is H + The inorganic strong acid aqueous solution with the concentration of 1-4 mol/L is soaked in the stirring, the stirring speed is 500-1000r/min, the soaking temperature is 60-90 ℃, and the soaking time is 40-120 min.
Further, in the step S1, the acid-activated attapulgite, the Ni-Co magnetic particles, the carbon nanotube slurry, sodium hexametaphosphate and water are calculated according to the following parts by weight:
acid-activated attapulgite: 0.5 to 2 portions of
Ni — Co magnetic particles: 1 to 5 portions of
Carbon nanotube slurry: 10 to 30 portions, the concentration of the carbon nano tube slurry is 10 percent
Sodium hexametaphosphate: 0.2 to 1 portion
Water: 30-80 parts.
Further, in the step S1, the stirring speed is 600-1000r/min, and the stirring time is 30-60 min; the ultrasonic treatment time is 40-80 min; in step S2, in the spray drying process: the through needle of the spray dryer is set to be 3.0, the frequency of the fan is set to be 35.00Hz, the air inlet temperature is set to be 150-180 ℃, and the peristaltic speed is 1-6 RPM.
Furthermore, in step S3, the calcining temperature is 300-400 ℃, the calcining time is 1-4 h, and the calcining atmosphere is inert gas.
Further, in step S4, the usage relationship between the composite microspheres and the phase change material is as follows: 40-60 wt.%: 40-60 wt.%; vacuum impregnation is firstly carried out for 10-50 min at room temperature, and then vacuum is carried out for 10-50 min at 40-90 ℃.
The composite microsphere with wave absorbing and heat management functions, which is prepared by the preparation method, is provided.
The composite microsphere with the wave absorbing and heat management functions is applied to electromagnetic interference shielding and heat energy regulation of high-end electronic equipment.
According to the invention, ni-Co magnetic particles with proper size are prepared through hydrothermal synthesis, attapulgite is bundled and purified through acid liquor soaking to obtain acid-activated attapulgite, attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres are constructed through spray drying and calcining, and phase change materials are packaged in a rigid structure of the composite microspheres to prevent leakage, so that the composite microsphere material with wave absorbing and heat management functions is obtained.
According to the invention, by utilizing the special properties of minerals in the heat storage field and the research of wave-absorbing materials, excellent heat management performance is realized through the phase-change material, and the microwave absorption performance is realized through the microsphere structure, the dielectric loss material and the magnetic loss material. Therefore, attapulgite is used as a base material to adjust the dielectric constant of the composite material, carbon nano tubes are used as a dielectric loss material, and magnetic metal alloy is used as a magnetic loss material, so that the composite microsphere is constructed to balance the intrinsic impedance and the free space impedance of the material as far as possible, the complex dielectric constant of the composite material can be adjusted to a proper range by introducing the attapulgite, the impedance matching characteristic balance of the material is ensured, the porous structure of the composite microsphere can enable incident electromagnetic waves to be reflected and lost for multiple times in a sphere, and the composite material has excellent wave absorbing performance by combining the strong magnetic loss capacity of magnetic metal particles and the synergistic effect of multiple loss mechanisms.
The attapulgite-Ni-Co magnetic particle-carbon nano tube composite microsphere prepared by the invention has high specific surface area and porous structure, and can effectively package phase change materials through various interaction such as capillary force, surface tension, hydrogen bond, van der Waals force and the like. And the density of the attapulgite-Ni-Co magnetic particle-carbon nano tube composite microsphere prepared by the invention is smaller than that of the traditional wave-absorbing material, the wave-transmitting performance is good, and the unique structural characteristics of the attapulgite-Ni-Co magnetic particle-carbon nano tube composite microsphere are also beneficial to the loss of electromagnetic waves and other advantages. In addition, the attapulgite adopted by the invention also has special properties such as small size effect, quantum size effect, surface interface effect and the like, the special properties of the attapulgite are fully utilized, the characteristic advantages and functional designs of minerals, dielectric loss materials and magnetic loss materials are integrated, and the constructed composite microsphere material has double functions of wave absorption and heat management.
The attapulgite-Ni-Co magnetic particle-carbon nano tube composite microsphere constructed by the invention has the advantages that the effective wave-absorbing bandwidth can reach 5.54GHz when the thickness is only 1.7mm within the range of 2-18GHz, and the maximum reflection loss value is 21.81dB at 15.17GHz when the thickness is 1.6 mm.
The attapulgite-Ni-Co magnetic particle-carbon nano tube composite microsphere prepared by the invention is vacuum impregnated with loaded paraffin to prepare the microsphere-based composite phase change material, the loading capacity of the composite microsphere to the paraffin is about 47.8%, and the composite microsphere has excellent heat energy storage capacity. The material can simultaneously realize double functions of wave absorption and heat management, and has important significance for synchronously realizing electromagnetic interference shielding and heat energy regulation of high-end electronic equipment.
Drawings
FIG. 1 is a scanning electron micrograph of Ni-Co magnetic particles prepared in example 1;
FIG. 2 is a scanning electron microscope photograph of the composite microsphere prepared after the acid-activated attapulgite-Ni-Co magnetic particle-carbon nanotube suspension prepared in example 1 is spray-dried;
FIG. 3 is a scanning electron microscope photograph of the calcined attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres prepared in example 1;
FIG. 4 is a scanning electron microscope photograph of the composite microsphere material with wave absorbing and thermal management functions prepared in example 1;
FIG. 5 is a two-dimensional graph of the electromagnetic wave absorption characteristics of the calcined attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres prepared in example 1;
FIG. 6 is a three-dimensional graph of the electromagnetic wave absorption characteristics of the calcined attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres prepared in example 1;
FIG. 7 is a thermogravimetric analysis curve of the composite microsphere material with wave absorbing and heat management dual functions prepared in example 1;
FIG. 8 is a two-dimensional graph of the electromagnetic wave absorption characteristics of the calcined attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres prepared in example 2;
FIG. 9 is a two-dimensional graph of the electromagnetic wave absorption characteristics of the calcined attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres prepared in example 3.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
Example 1
Preparing Ni-Co magnetic particles:
weighing 4g of hexadecyl trimethyl ammonium bromide, 2.4g of NaOH, 0.32g of cobalt acetate tetrahydrate and 1.2g of nickel acetate tetrahydrate, adding the mixture into 40mL of glycol solution, stirring for 40min, performing ultrasonic treatment for 40min to obtain a mixed suspension, pouring the mixed suspension into a 100mL of polytetrafluoroethylene liner, transferring the mixed suspension into a stainless steel reaction kettle, and placing the stainless steel reaction kettle in an oven at 200 ℃ for 8h for hydrothermal synthesis. And collecting a black powder product after the reaction is finished, washing the black powder product by using deionized water or absolute ethyl alcohol, and drying the black powder product in an oven at the temperature of 60 ℃. Preparing acid-activated attapulgite:
weighing 20g of attapulgite raw ore, placing the attapulgite raw ore into a beaker filled with 200mL of hydrochloric acid solution with the mass fraction of 4wt.%, placing the beaker into a water bath kettle with the constant temperature of 80 ℃, stirring, carrying out ultrasonic treatment and water bath pickling for 60min, washing the attapulgite raw ore with deionized water by a suction filtration method to be neutral, drying, grinding and sieving with a 180-mesh sieve to obtain the acid-activated attapulgite.
Constructing the acid-activated attapulgite-Ni-Co magnetic particle-carbon nano tube composite microsphere:
(1) Weighing 1g of acid-activated attapulgite, 2g of Ni-Co magnetic particles, 20g of 10% carbon nanotube slurry, 0.4g of sodium hexametaphosphate and 50mL of deionized water, mixing and stirring for 40min, and performing ultrasonic treatment for 60min to obtain the acid-activated attapulgite-Ni-Co magnetic particle-carbon nanotube suspension.
(2) And (3) carrying out spray drying on the acid-activated attapulgite-Ni-Co magnetic particle-carbon nanotube suspension. The through needle of the spray dryer is set to be 3.0, the frequency of the fan is set to be 35.00Hz, the air inlet temperature is set to be 160 ℃, and the peristaltic speed is 2RPM. Collecting the dried material.
(3) Transferring the dried material collected by spray drying into a muffle furnace, and calcining for 2h at 350 ℃ in argon atmosphere to obtain the attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres. Preparing the composite microsphere material with wave absorbing and heat management functions.
Weighing 2g of attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres and 3g of paraffin (P), transferring the attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres and the paraffin (P) into a filter flask, vacuumizing the filter flask for 30min at room temperature, vacuumizing the filter flask for 30min under the condition of 90 ℃ water bath, and filtering the filter flask for 24h in a 60 ℃ oven to prepare the composite microsphere material with double functions of wave absorption and heat management.
Example 2
Constructing the acid-activated attapulgite-Ni-Co magnetic particle-carbon nano tube composite microsphere:
(1) Weighing 2g of acid-activated attapulgite, 4g of Ni-Co magnetic particles, 20g of 10% carbon nanotube slurry, 0.4g of sodium hexametaphosphate and 50mL of deionized water, mixing and stirring for 40min, and performing ultrasonic treatment for 60min to obtain the acid-activated attapulgite-Ni-Co magnetic particle-carbon nanotube suspension.
(2) And (3) carrying out spray drying on the acid-activated attapulgite-Ni-Co magnetic particle-carbon nano tube suspension. The through needle of the spray dryer is set to be 3.0, the frequency of a fan is set to be 35.00Hz, the air inlet temperature is set to be 160 ℃, and the peristaltic speed is 2RPM. And collecting the dried material.
(3) Transferring the dried material collected by spray drying into a muffle furnace, and calcining for 2h at 350 ℃ in argon atmosphere to obtain the attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres.
Example 3
Constructing the acid-activated attapulgite-Ni-Co magnetic particle-carbon nano tube composite microsphere:
(1) Weighing 1g of acid-activated attapulgite, 2g of Ni-Co magnetic particles, 15g of carbon nanotube slurry with the concentration of 10%, 0.4g of sodium hexametaphosphate and 50mL of deionized water, mixing and stirring for 40min, and performing ultrasonic treatment for 60min to obtain the acid-activated attapulgite-Ni-Co magnetic particle-carbon nanotube suspension.
(2) And (3) carrying out spray drying on the acid-activated attapulgite-Ni-Co magnetic particle-carbon nanotube suspension. The through needle of the spray dryer is set to be 3.0, the frequency of a fan is set to be 35.00Hz, the air inlet temperature is set to be 160 ℃, and the peristaltic speed is 2RPM. And collecting the dried material.
(3) Transferring the dried material collected by spray drying into a muffle furnace, and calcining for 2h at 350 ℃ in argon atmosphere to obtain the attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres. Preparing the composite microsphere material with wave absorbing and heat management functions.
Referring to fig. 1, it is a scanning electron micrograph of the Ni — Co magnetic particles prepared in example 1. It can be seen that the size of the prepared Ni — Co magnetic particles is about 0.5 to 1.0 μm. The magnetic particles with the size are beneficial to the subsequent construction of the composite microsphere, and meanwhile, the Ni-Co magnetic metal alloy is a better magnetic loss material, which is beneficial to improving the microwave absorption performance of the composite microsphere.
Referring to the attached figure 2, the scanning electron microscope photo of the composite microsphere prepared by spray drying the acid activated attapulgite-Ni-Co magnetic particle-carbon nanotube suspension in example 1 is shown. It can be seen that the size of the constructed composite microsphere is about 5-7 μm, and the composite microsphere has a plurality of staggered pore channels and a large specific surface, so that a large number of adsorption sites are provided for the phase change material, and the thermal energy storage capacity of the composite material is improved.
Referring to the attached figure 3, it is a scanning electron microscope photograph of the calcined attapulgite-Ni-Co magnetic particle-carbon nanotube composite microsphere of example 1. It can be seen that the constructed composite microspheres do not collapse after calcination and activation, and a large number of staggered pores and a large specific surface of the composite microspheres are still maintained, so that the subsequent encapsulation of the phase change material in a rigid structure of the composite microspheres is facilitated.
Referring to the attached figure 4, it is a scanning electron microscope photograph of the composite microsphere with wave absorbing and heat management functions prepared in example 1. It can be seen that after the constructed composite microspheres and the phase change material paraffin are compounded through vacuum impregnation, a layer of smooth paraffin is coated on the surfaces of the composite microspheres, and the paraffin is packaged in the pores of the composite microspheres, so that leakage is prevented.
Referring to the attached drawings 5 and 6, the electromagnetic wave absorption characteristics of the calcined attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres prepared in example 1 are shown, the reflection loss value of a sample is calculated in a simulation mode according to the relative complex dielectric constant and the magnetic permeability under different given absorber thicknesses and by combining a transmission line theory, and a corresponding two-dimensional curve graph and a corresponding three-dimensional curved surface graph are drawn. The composite microsphere is in the range of 2-18GHz, when the thickness is only 1.7mm, the effective wave-absorbing bandwidth can reach 5.54GHz, and when the thickness is 1.6mm, the maximum reflection loss value of 21.81dB is reached at 15.17 GHz. The introduction of the attapulgite can adjust the complex dielectric constant of the composite material to a proper range, ensure the impedance matching characteristic balance of the material, the porous structure of the composite microsphere can lead incident electromagnetic waves to be reflected for multiple times in the sphere to be lost, and the composite material has excellent wave-absorbing performance by combining the strong magnetic loss capacity of magnetic metal particles and the synergistic action of multiple loss mechanisms.
Referring to fig. 7, a thermogravimetric analysis curve of the composite microsphere material with wave absorbing and heat managing functions prepared in example 1 shows that the loading amount of the composite microsphere to paraffin is about 47.8%, which is mainly benefited by the porous structure and the large specific surface of the composite microsphere to provide a large number of adsorption sites for paraffin, and the paraffin is encapsulated in the structure of the composite microsphere, so that the composite material has excellent heat energy storage capacity.
Referring to the attached figure 8, the electromagnetic wave absorption characteristics of the calcined attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres prepared in example 2 are shown, the reflection loss values of the samples are calculated in a simulation manner according to the relative complex dielectric constants and magnetic conductivities under different given absorber thicknesses and in combination with the transmission line theory, and corresponding two-dimensional curve graphs are drawn. The composite microsphere is in a range of 2-18GHz, when the thickness is only 1.7mm, the effective wave-absorbing bandwidth can reach 5.02GHz, and when the thickness is 2.5mm, the maximum reflection loss value at 9.13GHz reaches 45.94dB.
Referring to the attached figure 9, the electromagnetic wave absorption characteristics of the calcined attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres prepared in example 3 are shown, the reflection loss values of the samples are calculated in a simulation manner according to the relative complex dielectric constants and magnetic conductivities under different given absorber thicknesses and in combination with the transmission line theory, and corresponding two-dimensional curve graphs are drawn. The composite microsphere is in a range of 2-18GHz, when the thickness is only 1.8mm, the effective wave-absorbing bandwidth can reach 5.44GHz, and when the thickness is 2.0mm, the maximum reflection loss value at 12.32GHz reaches 36.45dB.
The above is not mentioned, is suitable for the prior art.
While certain specific embodiments of the present invention have been described in detail by way of illustration, it will be understood by those skilled in the art that the foregoing is illustrative only and is not limiting of the scope of the invention, as various modifications or additions may be made to the specific embodiments described and substituted in a similar manner by those skilled in the art without departing from the scope of the invention as defined in the appending claims. It should be understood by those skilled in the art that any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. A preparation method of composite microspheres with wave absorbing and heat management functions is characterized by comprising the following steps: the method comprises the following steps:
s1: mixing and stirring the acid-activated attapulgite, the Ni-Co magnetic particles and the carbon nanotube slurry with sodium hexametaphosphate and water, and performing ultrasonic treatment to obtain an acid-activated attapulgite-Ni-Co magnetic particle-carbon nanotube suspension;
s2: the suspension is subjected to spray drying to construct acid-activated attapulgite-Ni-Co magnetic particle-carbon nano tube composite microspheres;
s3: calcining to obtain attapulgite-Ni-Co magnetic particle-carbon nanotube composite microspheres;
s4: vacuum impregnation is carried out on the composite microspheres and the phase-change material to obtain composite microspheres with wave absorbing and heat management functions;
wherein, the preparation steps of the Ni-Co magnetic particles are as follows; weighing hexadecyl trimethyl ammonium bromide, naOH, cobalt acetate tetrahydrate and nickel acetate tetrahydrate, adding the weighed materials into an ethylene glycol solution, stirring and ultrasonically treating the mixture to obtain a mixed suspension, and carrying out hydrothermal synthesis on the mixed suspension; and collecting a black powder product after the reaction is finished, washing the black powder product by using deionized water or absolute ethyl alcohol, and drying the black powder product.
2. The preparation method of the composite microsphere with the wave absorbing and heat management functions of claim 1, which is characterized by comprising the following steps: in the preparation method of the Ni-Co magnetic particles, the cetyl trimethyl ammonium bromide, the NaOH, the cobalt acetate tetrahydrate, the nickel acetate tetrahydrate and the ethylene glycol are calculated according to the following parts by weight:
cetyl trimethylammonium bromide: 2 to 6 portions of
NaOH:1 to 4 portions of
Cobalt acetate tetrahydrate: 0.2 to 0.5 portion
Nickel acetate tetrahydrate: 0.5 to 3 portions of
Ethylene glycol: 30-50 parts.
3. The preparation method of the composite microsphere with the wave absorbing and heat management functions of claim 1, which is characterized by comprising the following steps: in the preparation method of the Ni-Co magnetic particles, the stirring speed is 500-1000r/min, and the stirring time is 30-60 min; the ultrasonic treatment time is 30-60 min; the hydrothermal synthesis temperature is 180-200 ℃, and the hydrothermal synthesis time is 6-12 h.
4. The preparation method of the composite microsphere with the wave absorbing and heat management functions of claim 1, which is characterized by comprising the following steps: soaking attapulgite raw ore in acid liquor to obtain acid-activated attapulgite, wherein the acid-activating process comprises the following steps: soaking in acid liquor, performing solid-liquid separation, washing and drying; wherein the acid liquor is H + Soaking inorganic strong acid water solution with the concentration of 1-4 mol/L in stirring at the stirring speed of 500-1000r/min at the soaking temperature of 60-90 ℃ for 40-120 min.
5. The preparation method of the composite microsphere with the wave absorbing and heat management functions of claim 1, which is characterized by comprising the following steps: in the step S1, the acid-activated attapulgite, the Ni-Co magnetic particles, the carbon nanotube slurry, sodium hexametaphosphate and water are calculated according to the following parts by weight:
acid-activated attapulgite: 0.5 to 2 portions of
Ni-Co magnetic particles: 1 to 5 portions of
Carbon nanotube slurry: 10 to 30 portions, the concentration of the carbon nano tube slurry is 10 percent
Sodium hexametaphosphate: 0.2 to 1 portion
Water: 30-80 parts.
6. The preparation method of the composite microsphere with the wave absorbing and heat management functions of claim 1, which is characterized by comprising the following steps: in the step S1, the stirring speed is 600-1000r/min, and the stirring time is 30-60 min; the ultrasonic treatment time is 40-80 min; in step S2, in the spray drying process: the through needle of the spray dryer is set to be 3.0, the frequency of the fan is set to be 35.00Hz, the air inlet temperature is set to be 150-180 ℃, and the peristaltic speed is 1-6 RPM.
7. The preparation method of the composite microsphere with the wave absorbing and heat management functions of claim 1, which is characterized by comprising the following steps: in the step S3, the calcining temperature is 300-400 ℃, the calcining time is 1-4 h, and the calcining atmosphere is inert gas.
8. The preparation method of the composite microsphere with the wave absorbing and heat management functions of claim 1, which is characterized by comprising the following steps: in step S4, the dosage relationship between the composite microspheres and the phase change material is as follows: 40-60 wt.%: 40-60 wt.%; vacuum impregnation is firstly carried out for 10-50 min at room temperature, and then vacuum impregnation is carried out for 10-50 min at 40-90 ℃.
9. The composite microsphere with wave absorbing and heat management functions, which is prepared by the preparation method of any one of claims 1 to 8.
10. The application of the composite microsphere with the wave absorbing and heat management functions of claim 9, wherein the composite microsphere comprises the following components in percentage by weight: for emi shielding and thermal energy regulation of high-end electronic devices.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157430A (en) * | 2011-12-09 | 2013-06-19 | 中国科学院大连化学物理研究所 | Sea-urchin-shaped core-shell type Fe3O4@TiO2 magnetic microspheres, and preparation and application thereof |
| CN105295832A (en) * | 2014-07-25 | 2016-02-03 | 南京理工大学 | Preparation method for reduced graphene oxide/Ni-Co ternary composite wave-absorbing material |
| CN109536138A (en) * | 2018-12-29 | 2019-03-29 | 苏州铂韬新材料科技有限公司 | Waveguide hot material and preparation method thereof is inhaled in a kind of paste phase transformation |
| CN111534278A (en) * | 2019-12-25 | 2020-08-14 | 江西悦安新材料股份有限公司 | Preparation method of carbon nano tube composite wave-absorbing material |
| CN112087939A (en) * | 2020-09-10 | 2020-12-15 | 中山大学 | FeCoNi @ C/carbon nanotube magnetic composite wave-absorbing material and preparation method and application thereof |
| CN113451783A (en) * | 2021-06-18 | 2021-09-28 | 西安交通大学 | Phase-change controllable composite wave absorber and preparation and performance regulation and control method thereof |
| CN113637459A (en) * | 2021-07-13 | 2021-11-12 | 中南大学 | Preparation method of composite mineral microsphere-based phase-change heat storage material |
| CN113789609A (en) * | 2021-08-30 | 2021-12-14 | 武汉理工大学 | Film material with heat absorption/wave absorption double-effect function and preparation method thereof |
-
2022
- 2022-08-18 CN CN202210994488.9A patent/CN115433549B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157430A (en) * | 2011-12-09 | 2013-06-19 | 中国科学院大连化学物理研究所 | Sea-urchin-shaped core-shell type Fe3O4@TiO2 magnetic microspheres, and preparation and application thereof |
| CN105295832A (en) * | 2014-07-25 | 2016-02-03 | 南京理工大学 | Preparation method for reduced graphene oxide/Ni-Co ternary composite wave-absorbing material |
| CN109536138A (en) * | 2018-12-29 | 2019-03-29 | 苏州铂韬新材料科技有限公司 | Waveguide hot material and preparation method thereof is inhaled in a kind of paste phase transformation |
| CN111534278A (en) * | 2019-12-25 | 2020-08-14 | 江西悦安新材料股份有限公司 | Preparation method of carbon nano tube composite wave-absorbing material |
| CN112087939A (en) * | 2020-09-10 | 2020-12-15 | 中山大学 | FeCoNi @ C/carbon nanotube magnetic composite wave-absorbing material and preparation method and application thereof |
| CN113451783A (en) * | 2021-06-18 | 2021-09-28 | 西安交通大学 | Phase-change controllable composite wave absorber and preparation and performance regulation and control method thereof |
| CN113637459A (en) * | 2021-07-13 | 2021-11-12 | 中南大学 | Preparation method of composite mineral microsphere-based phase-change heat storage material |
| CN113789609A (en) * | 2021-08-30 | 2021-12-14 | 武汉理工大学 | Film material with heat absorption/wave absorption double-effect function and preparation method thereof |
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