CN109898107B - Foam metal copper-doped carbon nanotube electromagnetic shielding material and preparation method thereof - Google Patents
Foam metal copper-doped carbon nanotube electromagnetic shielding material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a foam metal copper-doped carbon nanotube electromagnetic shielding material and a preparation method thereof, belonging to the field of electromagnetic shielding, wherein the electromagnetic shielding material takes foam metal copper as a base material, and carbon nanotubes are embedded in a copper layer; according to the invention, the carbon nano tube is embedded in the copper layer in an electroplating manner, and the dispersibility is good, so that the electromagnetic shielding performance of the foam metal copper is improved, and the foam metal copper has a wide application field; the whole process is simple, the device is simple, the operation is convenient, the period is short, the repeatability is high, and the mass production can be realized.
Description
Technical Field
The invention belongs to the field of electromagnetic shielding, and particularly relates to a foam metal copper-doped carbon nanotube electromagnetic shielding material and a preparation method thereof.
Background
The rapid development of modern electronic technology brings great convenience to people, but also brings serious electromagnetic pollution. The electronic equipment not only harms the health of people, but also threatens the information safety of the electronic equipment and the system stability of surrounding equipment. Therefore, the development of high-performance electromagnetic shielding materials is a hot spot of research in the present society. The carbon nano tube is widely used as a one-dimensional material with excellent magnetic and electrical properties and researched as a reinforcement, and the carbon nano tube has certain electromagnetic shielding property and obviously improves the electromagnetic shielding property of the foam metal copper with better conductivity.
At present, the scholars adopt an electrophoretic deposition method to prepare the foam carbon series metal, but the carbon nano tube is deposited on the surface of a metal coating, the coating is thickened, and the electromagnetic shielding improvement is not obvious. For example, chinese patent CN103434207 discloses a foam metal-carbon nanotube composite material and a method for preparing the same, in which an electrophoretic deposition technique is used to deposit carbon nanotubes on a foam metal skeleton, and the composite material has a higher electromagnetic shielding performance due to the synergistic effect of the two interfaces.
Therefore, it is necessary to provide a preparation method to improve the thickness of the existing carbon foam metal plating layer, and the electromagnetic shielding performance is not obviously improved.
Disclosure of Invention
In order to overcome the problems that the foam carbon metal plating layer is thick and the electromagnetic shielding performance is not obviously improved in the prior art, the invention aims to provide the foam metal copper-doped carbon nanotube electromagnetic shielding material, wherein the material takes foam metal copper as a base material, and carbon nanotubes are embedded in a copper layer.
The invention also aims to provide a preparation method of the foam metal copper-doped carbon nanotube electromagnetic shielding material, which comprises the following steps:
(1) preparation of silver ammonia solution
Adding silver nitrate into deionized water to enable the concentration of the silver nitrate to be 10g/L-15g/L, and dropwise adding ammonia water with the mass fraction of 25% until a silver nitrate solution is clear to obtain a silver ammonia solution A;
(2) preparation of reducing agent solution
Dissolving glucose into deionized water to obtain a reducing agent solution B, wherein the concentration of the reducing agent solution B is 100-120 g/L;
(3) preparation of electroplating solution
Respectively dissolving copper sulfate pentahydrate, concentrated sulfuric acid, a carbon nano tube, a dispersing agent and a complexing agent in deionized water to form solutions, wherein the concentrations of the solutions are respectively 150-200g/L, 40-60g/L, 1-10g/L, 0.01-0.04g/L and 0.2-0.6g/L, and then mixing and stirring the five solutions to prepare an electroplating solution C;
(4) preparation of foam metal copper-doped carbon nanotube electromagnetic shielding material
Soaking melamine foam in a silver-ammonia solution A at the temperature of 20-30 ℃ for 8-10min, then dropwise adding a reducing agent solution B into the silver-ammonia solution A, stirring in a water bath for a certain time, fully washing the melamine foam, drying at the temperature of 50-70 ℃ for 4-6h, placing into an electroplating solution C at the temperature of 25-30 ℃, electroplating for a period of time, fully washing, drying, removing the melamine foam at the temperature of 600-700 ℃, cooling to room temperature, and then carrying out reduction and heat treatment to obtain the foamed metal copper-doped carbon nanotube electromagnetic shielding material.
Further, the silver ammonia solution A in the step (1) is prepared in a water bath kettle at the temperature of 20-30 ℃;
further, the carbon nanotubes in the step (3) are carbon nanotube dispersion liquid with a mass fraction of 10%.
Further, ultrasonic dispersion is adopted for 30min when the carbon nano tube solution is prepared in the step (3).
Further, after the electroplating solution C is prepared in the step (3), the electroplating solution C is subjected to ultrasonic dispersion for 30 min.
Further, the water bath stirring in the step (4) is carried out for a certain time of 10-15 min.
Further, the electroplating period in the step (4) is 6-8 h.
Further, in the step (4), the reduction step is as follows: heating to 450 ℃ at the heating rate of 5-10 ℃/min, preserving the heat for 200min, and cooling along with the furnace.
Further, the heat treatment step in the step (4) is: heating to 750-800 deg.C at a temperature rising rate of 5-10 deg.C/min, maintaining for 60-120min, and cooling with the furnace.
The invention has the following technical effects:
(1) the preparation method is simple, the instruments and equipment are simple, and the safety and the reliability are realized;
(2) the preparation method disclosed by the invention comprises a chemical plating and electroplating method, wherein a layer of silver is plated on melamine foam in a chemical plating mode to make the melamine foam conductive, the melamine foam is dried after being fully washed and then placed in an electroplating solution for deposition for a certain time, and the dispersibility of the carbon nano tube in the solution is improved due to the modification of the organic micromolecule surfactant, so that the deposition uniformity of the carbon nano tube on the surface of a coating is improved, the coating is thickened along with the extension of the deposition time, the carbon nano tube is uniformly dispersed in a metal matrix in the three-dimensional direction, and the foam metal copper-doped carbon nano tube electromagnetic shielding material is obtained after full washing and drying heat treatment;
(3) the carbon nano tube of the foam metal copper-doped carbon nano tube electromagnetic shielding material is not deposited on the surface of a copper layer and is embedded in the copper layer instead of a thickened coating, so that the uniformity is good, and the agglomeration phenomenon is avoided. When the thickness of the plating layer is 3um, the shielding performance reaches 40dB, compared with the plating layer thickness of the foam metal-carbon nanotube composite material disclosed in patent CN103434207, which is 6.67um, the shielding performance is 31.68 dB. The result shows that the foam metal copper-doped carbon nanotube electromagnetic shielding material prepared by the method has good electromagnetic shielding performance, reaches 45dB under the frequency of 8-12GHz, and can be used as a base material to be applied to contact materials, friction and wear materials and the like;
(6) the invention adopts nickel sulfate hexahydrate as a raw material, and the foamed metal nickel-doped carbon nanotube electromagnetic shielding material prepared by the same method is also used for researching the electromagnetic shielding performance;
(4) the foam metal copper-doped carbon nanotube electromagnetic shielding material prepared by the method has good electromagnetic shielding performance, reaches 45dB under the frequency of 8-12GHz, and can be used as a base material to be applied to contact materials, friction and wear materials and the like;
(5) the invention adopts nickel sulfate hexahydrate as a raw material, and the foamed metal nickel-doped carbon nanotube electromagnetic shielding material prepared by the same method can also be used for researching the electromagnetic shielding performance, and experimental results prove that the method can be applied to foamed carbon series metals such as nickel, cobalt and the like, and can be used for enlarging the application range.
Drawings
FIG. 1 is a graph showing the electromagnetic shielding performance of the copper foam doped carbon nanotube electromagnetic shielding material of the present invention;
FIG. 2 is a scanning electron microscope image of the foamed copper-doped carbon nanotube electromagnetic shielding material of example 1 of the present invention before heat treatment;
FIG. 3 is a scanning electron microscope image of the foamed copper-doped carbon nanotube electromagnetic shielding material of example 1 after heat treatment;
fig. 4 is a scanning electron microscope image of carbon nanotubes of the copper foam-doped carbon nanotube electromagnetic shielding material in embodiment 5 of the present invention.
Detailed Description
The following will clearly and completely describe the technical solutions 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 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.
Example 1
The preparation method of the foam metal copper-doped carbon nanotube electromagnetic shielding material comprises the following steps of:
(1) preparation of silver ammonia solution
Dissolving silver nitrate in deionized water to form a silver nitrate solution with the concentration of 10g/L, and dropwise adding ammonia water with the mass fraction of 25% until the silver nitrate solution is clear to prepare a silver ammonia solution A;
(2) preparation of reducing agent solution
Dissolving 99.9% glucose into deionized water to obtain a reducing agent solution B with the concentration of 100 g/L;
(3) preparation of electroplating solution
Preparing copper sulfate pentahydrate into a solution with the concentration of 150g/L by using deionized water, diluting concentrated sulfuric acid into a solution with the concentration of 40g/L by using the deionized water, respectively dissolving a dispersing agent and a complexing agent into a solution with the concentrations of 0.01g/L and 0.2g/L by using the deionized water, dissolving 10% by mass of carbon nano tubes into water to form a 1g/L carbon nano tube solution, ultrasonically dispersing the formed carbon nano tube solution for 30min, mixing the five solutions, stirring to prepare a plating solution C, and ultrasonically dispersing the plating solution C for 30 min.
(4) Preparation of foam metal copper-doped carbon nanotube electromagnetic shielding material
Soaking melamine foam in a silver-ammonia solution A at the temperature of 20 ℃ for 8min, dropwise adding a reducing agent solution B into the solution A, stirring in a water bath for 10min, fully washing with deionized water, drying at 50 ℃ for 4h, placing into an electroplating solution C at the temperature of 25 ℃, electroplating for 6h, fully washing, drying, preserving heat at 600 ℃ in a tubular furnace for 150min to remove the melamine foam, cooling to room temperature, then heating to 400 ℃ in the tubular furnace at the heating rate of 5 ℃/min, preserving heat for 150min, and furnace-cooling; and then heating to 750 ℃ at the heating rate of 5 ℃/min, preserving the heat for 60min, and then cooling along with the furnace to obtain the foam metal copper-doped carbon nanotube electromagnetic shielding material.
FIGS. 2 and 3 are comparative graphs before and after the heat treatment of the copper foam doped carbon nanotube electromagnetic shielding material according to example 1 of the present invention, in which it can be seen that the copper layer particles before the heat treatment are relatively large and less dense; after the heat treatment, the copper layer is smooth and compact, which shows that the densification of the plating layer after the heat treatment is beneficial to improving the strength of the foam metal.
Example 2
(1) Preparation of silver ammonia solution
Adding 99.8% by mass of silver nitrate into ionic water to form a silver nitrate solution with the concentration of 11g/L, and dropwise adding 25% by mass of ammonia water until the silver nitrate solution is clear to obtain a silver ammonia solution A;
(2) preparation of reducing agent solution
Dissolving a certain amount of glucose in deionized water to obtain a reducing agent solution B, wherein the concentration of the reducing agent solution B is 110 g/L;
(3) preparation of electroplating solution
Copper sulfate pentahydrate is dissolved in a 500ml beaker, and the concentration of the copper sulfate pentahydrate is 160 g/L; diluting 98.6 mass percent concentrated sulfuric acid with deionized water to 45g/L, respectively dissolving a dispersing agent and a complexing agent with the deionized water to 0.02g/L and 0.3g/L, respectively dissolving a carbon nano tube solution with the concentration of 3g/L for 30min, mixing the solutions, stirring to prepare a plating solution C, and ultrasonically dispersing the plating solution C for 30 min.
(4) Preparation of foam metal copper-doped carbon nanotube electromagnetic shielding material
Soaking melamine foam in a silver-ammonia solution A at the temperature of 23 ℃ for 9min, dropwise adding a reducing agent solution B into the solution A, stirring in a water bath for 12min, fully washing with deionized water, drying at the temperature of 55 ℃ for 5h, placing into an electroplating solution C at the temperature of 27 ℃, electroplating for 7h, fully washing, drying, removing the melamine foam through a tubular furnace at the temperature of 650 ℃, cooling to room temperature, heating to 420 ℃ at the heating rate of 8 ℃/min in the tubular furnace, preserving heat for 180min, and cooling along with the furnace; heating to 780 ℃ at the heating rate of 8 ℃/min, preserving the heat for 80min, and cooling along with the furnace to obtain the foam metal copper-doped carbon nanotube electromagnetic shielding material.
Example 3
(1) Preparation of silver ammonia solution
And (3) dissolving silver nitrate in 100ml, and dropwise adding ammonia water with the mass fraction of 25% until a silver nitrate solution is clear to obtain a silver-ammonia solution A with the concentration of 12 g/L.
(2) Preparation of reducing agent solution
Glucose was dissolved in deionized water to obtain a reducing agent solution B having a concentration of 120 g/L.
(3) Preparation of electroplating solution
Preparing a blue vitriol solution with the concentration of 170g/L by using deionized water, diluting concentrated sulfuric acid into 50g/L by using the deionized water, respectively dissolving a dispersing agent and a complexing agent into the blue vitriol solution with the concentrations of 0.03g/L and 0.4g/L by using the deionized water, and the concentration of a carbon nano tube solution of 8g/L, carrying out ultrasonic dispersion on the carbon nano tube solution for 30min, mixing the five solutions, stirring to prepare a plating solution C, and carrying out ultrasonic dispersion on the plating solution C for 30 min.
(4) Preparation of foam metal copper-doped carbon nanotube electromagnetic shielding material
Soaking the melamine foam in a silver-ammonia solution A at the temperature of 23 ℃ for 10min, and dropwise adding a reducing agent solution B into the solution A, stirring in a water bath for 15 min. Repeatedly washing with deionized water, drying at 60 deg.C for 6 hr, placing into electroplating solution C at 28 deg.C, electroplating for 8 hr, washing thoroughly, and drying. Removing melamine foam through a tubular furnace at 700 ℃, cooling to room temperature, heating to 450 ℃ in the tubular furnace at a heating rate of 10 ℃/min, preserving heat for 200min, and cooling with the furnace; heating to 800 ℃ at the heating rate of 10 ℃/min, preserving the heat for 120min, and then cooling along with the furnace to obtain the foam metal copper-doped carbon nanotube electromagnetic shielding material.
Example 4
(1) Preparation of silver ammonia solution
And (3) dropwise adding ammonia water with the mass fraction of 25% into the silver nitrate solution with the concentration of 13g/L until the silver nitrate solution is clear, so as to obtain a silver-ammonia solution A.
(2) Preparation of reducing agent solution
Dissolving a certain amount of glucose into deionized water to obtain a reducing agent solution B, wherein the concentration of the reducing agent solution B is 130 g/L.
(3) Preparation of electroplating solution
Dissolving copper sulfate pentahydrate, concentrated sulfuric acid, a dispersing agent (polyethylene glycol) and a complexing agent into deionized water to form 180g/L, 55g/L, 0.04g/L and 0.5g/L respectively, dissolving a carbon nano tube into the deionized water to form a solution of 5g/L, fixing the volume in a 10ml beaker, mixing the five solutions, stirring to prepare an electroplating solution C, and performing ultrasonic dispersion on the electroplating solution C for 30 min.
(4) Preparation of foam metal copper-doped carbon nanotube electromagnetic shielding material
Soaking melamine foam in a silver-ammonia solution A at the temperature of 28 ℃ for 8min, dropwise adding a reducing agent solution B into the solution A, stirring in a water bath for 15min, fully washing with deionized water, drying at 60 ℃ for 6h, placing into an electroplating solution C at the temperature of 28 ℃, electroplating for 8h, fully washing, and drying. Removing melamine foam through a tubular furnace at 600 ℃, cooling to room temperature, heating to 450 ℃ at a heating rate of 10 ℃/min in the tubular furnace, preserving heat for 200min, and cooling with the furnace; heating to 800 ℃ at the heating rate of 10 ℃/min, preserving the heat for 120min, and then cooling along with the furnace to obtain the foam metal copper-doped carbon nanotube electromagnetic shielding material.
Example 5
(1) Preparation of silver ammonia solution
Adding a certain amount of silver nitrate into deionized water, and dropwise adding ammonia water with the mass fraction of 25% until a silver nitrate solution is clear to obtain a silver-ammonia solution A, wherein the concentration of the silver-ammonia solution A is 13 g/L;
(2) preparation of reducing agent solution
Dissolving glucose into deionized water to obtain a reducing agent solution B, wherein the concentration of the reducing agent solution B is 115 g/L;
(3) preparation of electroplating solution
Preparing a copper sulfate pentahydrate solution with the concentration of 170g/L by using deionized water, diluting concentrated sulfuric acid into 60g/L by using the deionized water, respectively dissolving a dispersing agent and a complexing agent into solutions with the concentrations of 0.04g/L and 0.5g/L by using the deionized water, dissolving a carbon nano tube into a solution with the concentration of 8g/L, mixing and stirring to prepare a plating solution C, and performing ultrasonic dispersion on the plating solution C for 30 min;
(4) preparation of foam metal copper-doped carbon nanotube electromagnetic shielding material
Soaking melamine foam in a silver-ammonia solution A at the temperature of 29 ℃ for 8min, dropwise adding a reducing agent solution B into the solution A, stirring in a water bath for 15min, fully washing with deionized water, drying at 65 ℃ for 4h, placing into an electroplating solution C at the temperature of 28 ℃, electroplating for 8h, fully washing, drying, removing the melamine foam through a tubular furnace at the temperature of 650 ℃, cooling to room temperature, heating to 450 ℃ at the heating rate of 10 ℃/min in the tubular furnace, preserving heat for 200min, and cooling along with the furnace; heating to 800 ℃ at the heating rate of 10 ℃/min, preserving the heat for 120min, and then cooling along with the furnace to obtain the foam metal copper-doped carbon nanotube electromagnetic shielding material.
Fig. 4 is a scanning electron microscope image of the copper foam-doped carbon nanotube electromagnetic shielding material of embodiment 5, from which it can be seen that the carbon nanotubes have good dispersion uniformity and are in a damascene state in the copper layer, which is beneficial to improving the electromagnetic shielding performance of the copper foam.
Example 6
(1) Preparation of silver ammonia solution
Adding silver nitrate into deionized water, and dropwise adding ammonia water with the mass fraction of 25% until a silver nitrate solution is clear to obtain a silver-ammonia solution A with the concentration of 10 g/L.
(2) Preparation of reducing agent solution
Glucose was dissolved in deionized water to obtain a reducing agent solution B having a concentration of 100 g/L.
(3) Preparation of electroplating solution
Respectively dissolving nickel sulfate hexahydrate, nickel chloride, boric acid, formaldehyde, a surfactant and a carbon nano tube in deionized water, respectively adjusting the concentrations to be 400g/L, 30g/L, 20g/L, 0.15g/L, 0.2g/L and 1.5g/L, adjusting the pH to be 3.8-4.2 by using hydrochloric acid, and mixing the solutions to obtain the electroplating solution C.
(4) Preparation of electromagnetic shielding material of foam metal nickel doped carbon nano tube
Soaking melamine foam in a silver-ammonia solution A at the temperature of 25 ℃ for 8min, dropwise adding a reducing agent solution B into the solution A, stirring in a water bath for 15min, fully washing with deionized water, drying at 65 ℃ for 4h, placing into an electroplating solution C at the temperature of 28 ℃, electroplating for 8h, fully washing, and drying. Removing melamine foam through a tubular furnace at 650 ℃, cooling to room temperature, heating to 450 ℃ at a heating rate of 10 ℃/min in the tubular furnace, preserving heat for 200min, and cooling along with the furnace; heating to 800 ℃ at the heating rate of 10 ℃/min, preserving the heat for 120min, and then cooling along with the furnace to obtain the electromagnetic shielding material of the foam metal nickel doped carbon nano tube.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (9)
1. The foam metal copper-doped carbon nanotube electromagnetic shielding material is characterized in that foam metal copper is used as a base material, and carbon nanotubes are embedded in a foam metal copper layer;
the preparation method of the foam metal copper-doped carbon nanotube electromagnetic shielding material comprises the following steps:
(1) preparation of silver ammonia solution
Adding silver nitrate into deionized water to enable the concentration of the silver nitrate to be 10g/L-15g/L, and dropwise adding ammonia water with the mass fraction of 25% until a silver nitrate solution is clear to obtain a silver ammonia solution A;
(2) preparation of reducing agent solution
Dissolving glucose into deionized water to obtain a reducing agent solution B, wherein the concentration of the reducing agent solution B is 100-120 g/L;
(3) preparation of electroplating solution
Respectively dispersing copper sulfate pentahydrate, concentrated sulfuric acid, a carbon nano tube, a dispersing agent and a complexing agent in deionized water to form dispersing solutions, wherein the concentrations of the dispersing solutions are respectively 150-200g/L, 40-60g/L, 1-10g/L, 0.01-0.04g/L and 0.2-0.6g/L, and then mixing and stirring the five dispersing solutions to prepare an electroplating solution C;
(4) preparation of foamed metallic copper
Soaking melamine foam in a silver-ammonia solution A at the temperature of 20-30 ℃ for 8-10min, then dropwise adding a reducing agent solution B into the silver-ammonia solution A, stirring in a water bath, fully washing the melamine foam, drying at the temperature of 50-70 ℃ for 4-6h, placing into an electroplating solution C at the temperature of 25-30 ℃, after electroplating, fully washing, drying, removing the melamine foam at the temperature of 600-700 ℃, cooling to room temperature, and then carrying out reduction and heat treatment to obtain the foam metal copper doped carbon nanotube electromagnetic shielding material.
2. The metallic copper foam-doped carbon nanotube electromagnetic shielding material of claim 1, wherein the silver ammonia solution A in step (1) is prepared in a water bath at a temperature of 20-30 ℃.
3. The metallic copper foam-doped carbon nanotube electromagnetic shielding material of claim 1, wherein the carbon nanotubes in step (3) are a carbon nanotube dispersion with a mass fraction of 10%.
4. The metallic copper foam-doped carbon nanotube electromagnetic shielding material of claim 3, wherein the carbon nanotube solution prepared in step (3) is dispersed by ultrasonic wave for 30 min.
5. The metallic copper foam-doped carbon nanotube electromagnetic shielding material as claimed in claim 1, wherein the plating solution C is prepared in step (3), and then the plating solution C is subjected to ultrasonic dispersion for 30 min.
6. The metallic copper foam-doped carbon nanotube electromagnetic shielding material of claim 1, wherein the stirring time of the water bath in step (4) is 10-15 min.
7. The metallic copper foam-doped carbon nanotube electromagnetic shielding material of claim 1, wherein the electroplating time in step (4) is 6-8 h.
8. The metallic copper foam-doped carbon nanotube electromagnetic shielding material of claim 1, wherein the reducing step in step (4) is: heating to 450 ℃ at the heating rate of 5-10 ℃/min, preserving the heat for 200min, and cooling along with the furnace.
9. The method for preparing the metallic copper foam-doped carbon nanotube electromagnetic shielding material of claim 1, wherein the heat treatment step in the step (4) is: heating to 750-800 deg.C at a temperature rising rate of 5-10 deg.C/min, maintaining for 60-120min, and cooling with the furnace.
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| CN110218377B (en) * | 2019-06-20 | 2021-05-04 | 中原工学院 | Preparation method of multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film |
| CN111378998B (en) * | 2020-04-09 | 2022-03-01 | 烟台东方新程科技有限公司 | Foam metal processing technology |
| CN112281019B (en) * | 2020-10-13 | 2022-05-24 | 昆明理工大学 | Preparation method of copper alloy composite material for electronic packaging and product thereof |
| CN112853409B (en) * | 2020-12-29 | 2022-07-22 | 哈尔滨工业大学（深圳） | Silver-containing plating solution and preparation method of foam metal material |
| CN115869967B (en) * | 2022-11-21 | 2023-09-08 | 昆明理工大学 | Foam copper catalyst with trans-scale pore diameter structure and preparation method thereof |
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| CN101314837A (en) * | 2007-05-29 | 2008-12-03 | 孙桂平 | Ultra-thick foam iron, nickel alloy material, producing method and uses thereof |
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| KR100425630B1 (en) * | 2001-06-14 | 2004-04-03 | 오원춘 | Electromagnetic wave-shielding composition comprising metal treated carbon nanotube |
| CN1656574A (en) * | 2002-04-01 | 2005-08-17 | 环球产权公司 | Electrically conductive polymeric foams and elastomers and methods of manufacture thereof |
| CN100425653C (en) * | 2006-06-28 | 2008-10-15 | 四川大学 | Preparation of low density(0.03-0.2g/cm3)conductive polyurethane foam material containing carbon nanometer tube |
| CN103434207A (en) * | 2013-08-19 | 2013-12-11 | 南京航空航天大学 | Foam metal-carbon nanotube composite material and preparation method thereof |
| CN105525145A (en) * | 2014-10-23 | 2016-04-27 | 常德力元新材料有限责任公司 | Preparation method of carbon nanotube-coated foam nickel |
| CN104868134B (en) * | 2015-04-17 | 2017-04-19 | 华南理工大学 | Foam metal-carbon nanotube composite material, and preparation method and application thereof |
| CN106757282A (en) * | 2015-11-25 | 2017-05-31 | 常德力元新材料有限责任公司 | Foam metal-carbon nanotube composite material and preparation method thereof |
| CN106750284B (en) * | 2017-01-19 | 2020-05-19 | 北京工商大学 | Foamed metal doped polyaniline electromagnetic shielding material and preparation method thereof |
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| CN101314837A (en) * | 2007-05-29 | 2008-12-03 | 孙桂平 | Ultra-thick foam iron, nickel alloy material, producing method and uses thereof |
| CN105779806A (en) * | 2016-04-14 | 2016-07-20 | 河北工业大学 | Preparing method for foam metal composite material |
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