CN109898107A - Foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material and preparation method - Google Patents
Foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material and preparation method Download PDFInfo
- Publication number
- CN109898107A CN109898107A CN201910150840.9A CN201910150840A CN109898107A CN 109898107 A CN109898107 A CN 109898107A CN 201910150840 A CN201910150840 A CN 201910150840A CN 109898107 A CN109898107 A CN 109898107A
- Authority
- CN
- China
- Prior art keywords
- foam metal
- electromagnetic shielding
- preparation
- metal copper
- carbon nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 73
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 61
- 239000006260 foam Substances 0.000 title claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 58
- 239000002184 metal Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 41
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000005253 cladding Methods 0.000 title claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 41
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052709 silver Inorganic materials 0.000 claims abstract description 30
- 239000004332 silver Substances 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- 238000007747 plating Methods 0.000 claims abstract description 13
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 239000003638 chemical reducing agent Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000004033 plastic Substances 0.000 claims description 19
- 229920003023 plastic Polymers 0.000 claims description 19
- 229920000877 Melamine resin Polymers 0.000 claims description 18
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 18
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005352 clarification Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- TZEMBQSDIAYQEA-UHFFFAOYSA-N copper;1,3,5-triazine-2,4,6-triamine Chemical compound [Cu].NC1=NC(N)=NC(N)=N1 TZEMBQSDIAYQEA-UHFFFAOYSA-N 0.000 claims 1
- 238000009713 electroplating Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001652 electrophoretic deposition Methods 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000006250 one-dimensional material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Abstract
The present invention discloses a kind of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material and preparation method, belong to electromagnetic shielding field, the electromagnetic shielding material is using foam metal copper as basis material, carbon nanotube is inlaid with inside layers of copper, the preparation method is that first preparing silver ammino solution and reduction liquor, the electroplate liquid for having carbon nanotube for main salt dopping with cupric sulfate pentahydrate is prepared again, and foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material is prepared in such a way that chemical plating and plating combine；Carbon nanotube is embedded in layers of copper by the present invention by way of plating, and dispersibility is preferably, improves the electromagnetic shielding performance of foam metal copper, makes it have the field of being widely applied；Integrated artistic is simple, and device is simple, easy to operate, and the period is shorter, and repeatability is larger, can be realized volume production.
Description
Technical field
The invention belongs to be electromagnetically shielded field, and in particular to a kind of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material
And preparation method.
Background technique
The rapid development of modern electronic technology has brought very big convenience, but also brings serious electromagnetism simultaneously
Pollution.Electronic equipment not only endangers the health of people, also steady to the system of the information security of electronic equipment and surrounding devices
It is qualitative to constitute a threat to.So developing the hot spot that high performance electromagnetic shielding material is today's society research.Carbon nanotube is as one
Kind has the one-dimensional material of excellent magnetics and electric property, is widely used as reinforcement research, carbon nanotube itself has one
The improvement of fixed electromagnetic shielding performance, the electromagnetic shielding performance of foam metal copper preferable for electric conductivity has apparent mention
It is high.
Existing scholar prepares foamy carbon system metal using the method for electrophoretic deposition at present, but carbon nanotube is deposited on gold
The surface for belonging to coating has thickeied coating, and it is not apparent for being electromagnetically shielded improvement.Such as Chinese patent CN103434207 is public
A kind of foam metal-carbon nanotube composite material and preparation method thereof has been opened, has been deposited carbon nanotube using electrophoretic deposition technique
Onto foam metal skeleton, the composite material is made to have higher electromagnet shield effect by the synergistic effect at the two interface.
Accordingly, it is desirable to provide a kind of preparation method improves current foamy carbon system metal-plated thickness, electromagnetic shielding performance improves
Unconspicuous problem.
Summary of the invention
In order to overcome foamy carbon system metal-plated thickness in the prior art, electromagnetic shielding performance improves unconspicuous problem, this
Invention is designed to provide a kind of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material, and the material is with foam metal
Copper is basis material, is inlaid with carbon nanotube inside layers of copper.
It is a further object of the present invention to provide a kind of preparation sides of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material
Method, comprising the following steps:
(1) preparation of silver ammino solution
Silver nitrate is add to deionized water, its concentration 10g/L-15g/L is made, the ammonia that mass fraction is 25% is added dropwise
Water to silver nitrate solution is clarified, and silver ammino solution A is obtained；
(2) preparation of reducing agent solution
Glucose is dissolved into deionized water and obtains reducing agent solution B, concentration 100-120g/L；
(3) preparation of electroplate liquid
Cupric sulfate pentahydrate, the concentrated sulfuric acid, carbon nanotube, dispersing agent and complexing agent are dissolved in deionized water respectively formed it is molten
Liquid, solution concentration are respectively 150-200g/L, 40-60g/L, 1-10g/L, 0.01-0.04g/L, 0.2-0.6g/L, then by five kinds
Solution mixing, stirring are configured to electroplate liquid C；
(4) preparation of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material
Melamine foamed plastic is impregnated into 8-10min in the silver ammino solution A that temperature is 20-30 DEG C, then into silver ammino solution A
Reducing agent solution B stirring in water bath certain time is added dropwise, dries 4- at a temperature of 50-70 DEG C after sufficiently washing melamine foamed plastic
6h is put into electroplate liquid C, and temperature is 25-30 DEG C, is electroplated after a period of time, dry after sufficiently washing, at 600-700 DEG C
Lower removing melamine foamed plastic, is cooled to room temperature, obtains foam metal Copper-cladding Aluminum Bar carbon nanotube electricity using reduction and heat treatment
Magnetic shielding material.
Further, it is carried out in water-bath when step (1) silver ammino solution A is prepared, temperature is 20-30 DEG C；
Further, carbon nanotube described in step (3) is the carbon nano tube dispersion liquid that mass fraction is 10%.
Further, ultrasonic disperse 30min is used when preparing carbon nano-tube solution in step (3).
Further, after being configured to electroplate liquid C in step (3), electroplate liquid C is subjected to ultrasonic disperse, jitter time is
30min。
Further, stirring in water bath certain time described in step (4) is 10-15min.
Further, plating a period of time described in step (4) is 6-8h.
Further, reduction step described in step (4) are as follows: 400-450 is warming up to the heating rate of 5-10 DEG C/min
DEG C, keep the temperature 150-200min, furnace cooling.
Further, heat treatment step described in step (4) are as follows: 750- is warming up to the heating rate of 5-10 DEG C/min
800 DEG C, keep the temperature 60-120min, furnace cooling.
Technical effect of the invention is as follows:
(1) preparation method of the present invention is simple, and instrument and equipment are simple, securely and reliably；
(2) preparation method disclosed by the invention includes chemical plating and electric plating method, first on melamine foamed plastic
One layer of silver is plated by way of chemical plating, makes its conduction, it is sufficiently dry after washing, then put into electroplate liquid, carry out a timing
Between deposition improve carbon nanotube dispersibility in the solution and then change due to the modification of small organic molecule surfactant
It has been apt to it in the uniformity of coating surface deposition, with the extension of sedimentation time, coating is thickened, and carbon nanotube is equal on three-dimensional
It is even to be scattered in metallic matrix, foam metal Copper-cladding Aluminum Bar carbon nanotube electromagnetism is obtained after being heat-treated using abundant washing and drying
Shielding material, the method simple process avoid foam and carry out cumbersome pretreated technique before plating, eliminate and pre-processing
The negative effect generated in step；
(3) carbon nanotube of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material of the invention is not deposited on copper
Layer surface thickeies coating, but is embedded in inside layers of copper, and uniformity is preferable, agglomeration does not occur.When thickness of coating is
When 3um, shielding properties reaches 40dB, compared to the plating of foam metal-carbon nanotube composite material disclosed in patent CN103434207
Layer is with a thickness of 6.67um, shielding properties 31.68dB.As a result the foam metal Copper-cladding Aluminum Bar carbon that method of the invention is prepared is indicated
The electromagnetic shielding performance of nanotube electromagnetic shielding material is preferable, reaches 45dB in the case where wave frequency is 8-12GHz frequency, can be with
Basis material is used as applied to contact material, fretting wear material etc.；
(6) present invention uses six hydration nickel sulfate for raw material, the foam metal nickel doping prepared in the same way
Carbon nano tube electromagnetic shielding material, also can be carried out research to electromagnetic wave shielding, and the results show method of the invention can answer
Used in foamy carbon system nickel, the metals such as cobalt can expand that application range coating is lighter, and electromagnetic shielding performance is better；
(4) electromagnetic wave shielding for the foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material that method of the invention is prepared
45dB preferably can be reached in the case where wave frequency is 8-12GHz frequency, basis material can be used as and be applied to contact material
Material, fretting wear material etc.；
(5) present invention uses six hydration nickel sulfate for raw material, the foam metal nickel doping prepared in the same way
Carbon nano tube electromagnetic shielding material, also can be carried out research to electromagnetic wave shielding, and the results show method of the invention can answer
Used in foamy carbon system nickel, the metals such as cobalt can expand application range.
Detailed description of the invention
Fig. 1 is the electromagnetic shielding performance curve graph of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material of the present invention；
Fig. 2 is the scanning before the foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material heat treatment of the embodiment of the present invention 1
Electron microscope；
Fig. 3 is the scanning after the foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material heat treatment of the embodiment of the present invention 1
Electron microscope；
Fig. 4 is that the carbon nanotube of 5 foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material of the embodiment of the present invention scans electricity
Mirror figure.
Specific embodiment
It is clearly and completely described below in conjunction with the technical solution in the embodiment of the present invention, it is clear that described reality
Applying example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff every other embodiment obtained without making creative work belongs to what the present invention protected
Range.
Embodiment 1
The preparation method of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material of the present invention, including following step
It is rapid:
(1) preparation of silver ammino solution
Silver nitrate is dissolved in deionized water, the silver nitrate solution that concentration is 10g/L is formed, quality point is added dropwise wherein
Number is clarified for 25% ammonium hydroxide to silver nitrate solution, and silver ammino solution A is made；
(2) preparation of reducing agent solution
The glucose that content is 99.9% is dissolved into deionized water and obtains reducing agent solution B, concentration 100g/L；
(3) preparation of electroplate liquid
Cupric sulfate pentahydrate is configured to the solution that concentration is 150g/L with deionized water, the concentrated sulfuric acid is diluted to deionized water
Concentration is 40g/L, and it is 0.01g/L and 0.2g/L, mass fraction that dispersing agent and complexing agent, which are dissolved into concentration with deionized water respectively,
It is dissolved in the carbon nano-tube solution of water formation 1g/L for 10% carbon nanotube, the carbon nano-tube solution of formation uses ultrasonic disperse
30min, then above-mentioned five kinds of solution is mixed, stirring is configured to electroplate liquid C, and electroplate liquid C is carried out ultrasonic disperse 30min.
(4) preparation of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material
Melamine foamed plastic is impregnated into 8min in the silver ammino solution A that temperature is 20 DEG C, it is molten that reducing agent is added dropwise in solution A
Liquid B, stirring in water bath 10min dry 4h at 50 DEG C, are put into electroplate liquid C, temperature 25 after sufficiently being washed with deionized water
DEG C, it is electroplated after 6h, it is dry after sufficiently washing, 150min is kept the temperature at 600 DEG C of tube furnace removes melamine foamed plastic, it is cooling
400 DEG C, warm 150min are warming up to the heating rate of 5 DEG C/min to after room temperature, then in tube furnace, furnace cooling；Again
It is warming up to 750 DEG C, warm 60min, then furnace cooling with the heating rate of 5 DEG C/min, foam metal Copper-cladding Aluminum Bar carbon is obtained and receives
Mitron electromagnetic shielding material.
Fig. 2 and Fig. 3 is the foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material heat treatment front and back of the embodiment of the present invention 1
Comparison diagram, layers of copper particle is bigger before being as can be seen from the figure heat-treated, not so dense；After Overheating Treatment, layers of copper ratio
It is more smooth and fine and close, illustrate that after Overheating Treatment plated layer compact is conducive to the raising of foam metal intensity.
Embodiment 2
(1) preparation of silver ammino solution
The silver nitrate that mass fraction is 99.8% is added in ionized water, the silver nitrate solution that concentration is 11g/L is formed,
After the ammonium hydroxide to silver nitrate solution clarification that mass fraction is 25% is wherein added dropwise, silver ammino solution A is obtained；
(2) preparation of reducing agent solution
A certain amount of glucose is dissolved in deionized water and obtains reducing agent solution B, concentration 110g/L；
(3) preparation of electroplate liquid
By cupric sulfate pentahydrate constant volume in the beaker of 500ml, concentration 160g/L；Mass fraction is 98.6% concentrated sulfuric acid
Being diluted to concentration with deionized water is 45g/L, dispersing agent and complexing agent respectively with deionized water be dissolved into concentration be 0.02g/L and
0.3g/L, carbon nano-tube solution concentration are 3g/L, and carbon nano-tube solution uses ultrasonic disperse 30min, then above-mentioned solution is mixed,
Stirring is configured to electroplate liquid C, and electroplate liquid C is carried out ultrasonic disperse 30min.
(4) preparation of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material
Melamine foamed plastic is impregnated into 9min in the silver ammino solution A that temperature is 23 DEG C, it is molten that reducing agent is added dropwise in solution A
Liquid B stirring in water bath 12min dries 5h at 55 DEG C, is put into electroplate liquid C after sufficiently being washed with deionized water, temperature is 27 DEG C,
It is electroplated after 7h, it is dry after sufficiently washing, melamine foamed plastic is removed at 650 DEG C by tube furnace and is cooled to room temperature, then
420 DEG C, warm 180min are warming up to the heating rate of 8 DEG C/min in tube furnace, furnace cooling；With the liter of 8 DEG C/min
Warm rate is warming up to 780 DEG C, warm 80min, then furnace cooling, obtains foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material
Material.
Embodiment 3
(1) preparation of silver ammino solution
By silver nitrate constant volume in 100ml, ammonium hydroxide to the silver nitrate solution that mass fraction is 25% is added dropwise and clarifies, obtains silver-colored ammonia
Solution A, concentration 12g/L.
(2) preparation of reducing agent solution
Glucose is dissolved into deionized water and obtains reducing agent solution B, concentration 120g/L.
(3) preparation of electroplate liquid
Cupric sulfate pentahydrate is configured to the cupric sulfate pentahydrate solution that concentration is 170g/L with deionized water, the concentrated sulfuric acid spend from
Sub- water is diluted to 50g/L, and it is 0.03g/L and 0.4g/L that dispersing agent and complexing agent, which are dissolved into concentration with deionized water respectively, and carbon is received
Mitron solution concentration is 8g/L, carbon nano-tube solution is carried out ultrasonic disperse 30min, then above-mentioned five kinds of solution is mixed, stirring
It is configured to electroplate liquid C, electroplate liquid C is subjected to ultrasonic disperse 30min.
(4) preparation of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material
By melamine foamed plastic temperature be 23 DEG C of silver ammino solution A in impregnate 10min, in solution A be added dropwise reducing agent it is molten
Liquid B stirring in water bath 15min.6h to be dried after being washed repeatedly with deionized water at 60 DEG C, is put into electroplate liquid C, temperature is 28 DEG C,
It is electroplated after 8h, it is dry after sufficiently washing.Melamine foamed plastic is removed at 700 DEG C by tube furnace and is cooled to room temperature, then
450 DEG C, warm 200min are warming up to the heating rate of 10 DEG C/min in tube furnace, furnace cooling；With 10 DEG C/min's
Heating rate is warming up to 800 DEG C, warm 120min, then furnace cooling, obtains foam metal Copper-cladding Aluminum Bar carbon nanotube electromagnetic screen
Cover material.
Embodiment 4
(1) preparation of silver ammino solution
Ammonium hydroxide to the silver nitrate solution that mass fraction is 25% is added dropwise in the silver nitrate solution that concentration is 13g/L to clarify,
Obtain silver ammino solution A.
(2) preparation of reducing agent solution
A certain amount of glucose is dissolved into deionized water and obtains reducing agent solution B, the concentration of reducing agent solution B is
130g/L。
(3) preparation of electroplate liquid
Cupric sulfate pentahydrate, the concentrated sulfuric acid, dispersing agent (polyethylene glycol) and complexing agent are dissolved into 180g/ with deionized water respectively
L, 55g/L, 0.04g/L and 0.5g/L, carbon nanotube are dissolved in the solution that 5g/L is formed in deionized water, burning of the constant volume in 10ml
In cup, then by the mixing of above-mentioned five kinds of solution, stirring is configured to electroplate liquid C, and electroplate liquid C is carried out ultrasonic disperse 30min.
(4) preparation of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material
By melamine foamed plastic temperature be 28 DEG C of silver ammino solution A in impregnate 8min, reducing agent solution is added dropwise in solution A
B stirring in water bath 15min dries 6h at 60 DEG C, is put into electroplate liquid C after sufficiently being washed with deionized water, temperature is 28 DEG C, electricity
It is dry after sufficiently washing after plating 8h.Melamine foamed plastic is removed at 600 DEG C by tube furnace and is cooled to room temperature, then
450 DEG C, warm 200min are warming up to the heating rate of 10 DEG C/min in tube furnace, furnace cooling；With the liter of 10 DEG C/min
Warm rate is warming up to 800 DEG C, warm 120min, then furnace cooling, obtains foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding
Material.
Embodiment 5
(1) preparation of silver ammino solution
A certain amount of silver nitrate is add to deionized water, the ammonium hydroxide that dropwise addition mass fraction is 25% to silver nitrate solution
Clarification, obtains silver ammino solution A, makes silver ammino solution A concentration 13g/L；
(2) preparation of reducing agent solution
Glucose is dissolved into deionized water and obtains reducing agent solution B, makes reducing agent solution B concentration 115g/L；
(3) preparation of electroplate liquid
Cupric sulfate pentahydrate is configured to the cupric sulfate pentahydrate solution that concentration is 170g/L with deionized water, the concentrated sulfuric acid spend from
Sub- water is diluted to 60g/L, and it is 0.04g/L and 0.5g/L that dispersing agent and complexing agent, which are dissolved into concentration with deionized water respectively, and carbon is received
Mitron is dissolved into the solution of 8g/L, remixes stirring and is configured to electroplate liquid C, and electroplate liquid C is carried out ultrasonic disperse 30min；
(4) preparation of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material
By melamine foamed plastic temperature be 29 DEG C of silver ammino solution A in impregnate 8min, reducing agent solution is added dropwise into solution A
B stirring in water bath 15min dries 4h at 65 DEG C, is put into electroplate liquid C after sufficiently being washed with deionized water, temperature is 28 DEG C, electricity
It is dry after sufficiently washing after plating 8h, melamine foamed plastic is removed at 650 DEG C by tube furnace and is cooled to room temperature, then
450 DEG C, warm 200min are warming up to the heating rate of 10 DEG C/min in tube furnace, furnace cooling；With the liter of 10 DEG C/min
Warm rate is warming up to 800 DEG C, warm 120min, then furnace cooling, obtains foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding
Material.
Fig. 4 is the scanning electron microscope (SEM) photograph of 5 foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material of embodiment, can be with from figure
Find out that the dispersing uniformity of carbon nanotube is preferable, and in state is inlayed in layers of copper, this is conducive to improve foam metal copper
Electromagnetic shielding performance.
Embodiment 6
(1) preparation of silver ammino solution
Silver nitrate is add to deionized water, ammonium hydroxide to the silver nitrate solution that mass fraction is 25% is added dropwise and clarifies, obtains
To silver ammino solution A, concentration 10g/L.
(2) preparation of reducing agent solution
Glucose is dissolved into deionized water and obtains reducing agent solution B, concentration 100g/L.
(3) preparation of electroplate liquid
By six hydration nickel sulfate, nickel chloride, boric acid, formaldehyde, surfactant, carbon nanotube is dissolved separately in deionized water
In, concentration is respectively that 400g/L, 30g/L, 20g/L, 0.15g/L, 0.2g/L, 1.5g/L will with hydrochloric acid tune pH to 3.8-4.2
Above-mentioned several solns are mixed to get electroplate liquid C.
(4) preparation of the electromagnetic shielding material of foam metal nickel doped carbon nanometer pipe
By melamine foamed plastic temperature be 25 DEG C of silver ammino solution A in impregnate 8min, reducing agent solution is added dropwise into solution A
B stirring in water bath 15min dries 4h at 65 DEG C, is put into electroplate liquid C after sufficiently being washed with deionized water, temperature is 28 DEG C, electricity
It is dry after sufficiently washing after plating 8h.Melamine foamed plastic is removed at 650 DEG C by tube furnace and is cooled to room temperature, then
450 DEG C are warming up to the heating rate of 10 DEG C/min in tube furnace, keeps the temperature 200min, furnace cooling；With the heating of 10 DEG C/min
Rate is warming up to 800 DEG C, keeps the temperature 120min, then furnace cooling, obtains the electromagnetic shielding material of foam metal nickel doped carbon nanometer pipe
Material.
Embodiment described above is only that preferred embodiment of the invention is described, and is not carried out to the scope of the present invention
It limits, without departing from the spirit of the design of the present invention, those of ordinary skill in the art make technical solution of the present invention
Various changes and improvements, should all fall into claims of the present invention determine protection scope in.
Claims (10)
1. a kind of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material, which is characterized in that the material is with foam metal
Copper is basis material, is inlaid with carbon nanotube inside foam metal layers of copper.
2. the preparation method of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material described in claim 1, which is characterized in that
The following steps are included:
(1) preparation of silver ammino solution
Silver nitrate is add to deionized water, its concentration 10g/L-15g/L is made, the ammonium hydroxide that mass fraction is 25% is added dropwise extremely
Silver nitrate solution clarification, obtains silver ammino solution A；
(2) preparation of reducing agent solution
Glucose is dissolved into deionized water and obtains reducing agent solution B, concentration 100-120g/L；
(3) preparation of electroplate liquid
Cupric sulfate pentahydrate, the concentrated sulfuric acid, carbon nanotube, dispersing agent and complexing agent are dissolved in deionized water respectively and form solution,
Solution concentration is respectively 150-200g/L, 40-60g/L, 1-10g/L, 0.01-0.04g/L, 0.2-0.6g/L, then by above-mentioned five
Kind solution mixing, stirring are configured to electroplate liquid C；
(4) preparation of foam metal copper
Melamine foamed plastic is impregnated into 8-10min in the silver ammino solution A that temperature is 20-30 DEG C, then is added dropwise into silver ammino solution A
Reducing agent solution B, stirring in water bath dry 4-6h after sufficiently washing melamine foamed plastic at a temperature of 50-70 DEG C, are put into electroplate liquid
In C, temperature is 25-30 DEG C, after plating, dry after sufficiently washing, and melamine foamed plastic is removed at 600-700 DEG C, cold
But room temperature is arrived, obtains foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material using reduction and heat treatment.
3. the preparation method of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material, feature exist according to claim 2
In step (1) silver ammino solution A is carried out in water-bath when preparing, and temperature is 20-30 DEG C.
4. the preparation method of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material, feature exist according to claim 2
In carbon nanotube described in step (3) is the carbon nano tube dispersion liquid that mass fraction is 10%.
5. the preparation method of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material, feature exist according to claim 4
In using ultrasonic disperse 30min when preparing carbon nano-tube solution in step (3).
6. the preparation method of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material, feature exist according to claim 2
In after being configured to electroplate liquid C in step (3), by electroplate liquid C progress ultrasonic disperse, jitter time 30min.
7. the preparation method of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material, feature exist according to claim 2
In the stirring in water bath time described in step (4) is 10-15min.
8. the preparation method of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material, feature exist according to claim 2
In electroplating time described in step (4) is 6-8h.
9. the preparation method of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material, feature exist according to claim 2
In reduction step described in step (4) are as follows: be warming up to 400-450 DEG C with the heating rate of 5-10 DEG C/min, keep the temperature 150-
200min, furnace cooling.
10. the preparation method of foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material, feature exist according to claim 2
In heat treatment step described in step (4) are as follows: be warming up to 750-800 DEG C with the heating rate of 5-10 DEG C/min, keep the temperature 60-
120min, furnace cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910150840.9A CN109898107B (en) | 2019-02-28 | 2019-02-28 | Foam metal copper-doped carbon nanotube electromagnetic shielding material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910150840.9A CN109898107B (en) | 2019-02-28 | 2019-02-28 | Foam metal copper-doped carbon nanotube electromagnetic shielding material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109898107A true CN109898107A (en) | 2019-06-18 |
| CN109898107B CN109898107B (en) | 2021-02-19 |
Family
ID=66945748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910150840.9A Active CN109898107B (en) | 2019-02-28 | 2019-02-28 | Foam metal copper-doped carbon nanotube electromagnetic shielding material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109898107B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218377A (en) * | 2019-06-20 | 2019-09-10 | 中原工学院 | A kind of preparation method of multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film |
| CN111378998A (en) * | 2020-04-09 | 2020-07-07 | 烟台东方新程科技有限公司 | Foam metal processing technology |
| CN112281019A (en) * | 2020-10-13 | 2021-01-29 | 昆明理工大学 | Preparation method of copper alloy composite material for electronic packaging and product thereof |
| CN112853409A (en) * | 2020-12-29 | 2021-05-28 | 哈尔滨工业大学（深圳） | Silver-containing plating solution and preparation method of foam metal material |
| CN115869967A (en) * | 2022-11-21 | 2023-03-31 | 昆明理工大学 | Foam copper catalyst with cross-scale pore-size structure and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020096068A (en) * | 2001-06-14 | 2002-12-31 | 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 |
| CN1884373A (en) * | 2006-06-28 | 2006-12-27 | 四川大学 | Preparation of low density(0.03-0.2g/cm3)conductive polyurethane foam material containing carbon nanometer tube |
| CN101314837A (en) * | 2007-05-29 | 2008-12-03 | 孙桂平 | Ultra-thick foam iron, nickel alloy material, producing method and uses thereof |
| 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 |
| CN104868134A (en) * | 2015-04-17 | 2015-08-26 | 华南理工大学 | Foam metal-carbon nanotube composite material, and preparation method and application 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 |
| CN105779806A (en) * | 2016-04-14 | 2016-07-20 | 河北工业大学 | Preparing method for foam metal composite material |
| CN106750284A (en) * | 2017-01-19 | 2017-05-31 | 北京工商大学 | A kind of foam metal doped polyaniline electromagnetic shielding material and preparation method 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 |
-
2019
- 2019-02-28 CN CN201910150840.9A patent/CN109898107B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020096068A (en) * | 2001-06-14 | 2002-12-31 | 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 |
| CN1884373A (en) * | 2006-06-28 | 2006-12-27 | 四川大学 | Preparation of low density(0.03-0.2g/cm3)conductive polyurethane foam material containing carbon nanometer tube |
| CN101314837A (en) * | 2007-05-29 | 2008-12-03 | 孙桂平 | Ultra-thick foam iron, nickel alloy material, producing method and uses thereof |
| 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 |
| CN104868134A (en) * | 2015-04-17 | 2015-08-26 | 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 |
| CN105779806A (en) * | 2016-04-14 | 2016-07-20 | 河北工业大学 | Preparing method for foam metal composite material |
| CN106750284A (en) * | 2017-01-19 | 2017-05-31 | 北京工商大学 | A kind of foam metal doped polyaniline electromagnetic shielding material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| KEJU JI等: "Fabrication and electromagnetic interference shielding performance of open-cell foam of a Cu–Ni alloy integrated with CNTs", 《APPLIED SURFACE SCIENCE》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218377A (en) * | 2019-06-20 | 2019-09-10 | 中原工学院 | A kind of preparation method of multi-walled carbon nanotube/copper sulfide composite electromagnetic shielding film |
| 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 |
| CN111378998A (en) * | 2020-04-09 | 2020-07-07 | 烟台东方新程科技有限公司 | Foam metal processing technology |
| CN111378998B (en) * | 2020-04-09 | 2022-03-01 | 烟台东方新程科技有限公司 | Foam metal processing technology |
| CN112281019A (en) * | 2020-10-13 | 2021-01-29 | 昆明理工大学 | Preparation method of copper alloy composite material for electronic packaging and product thereof |
| 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 |
| CN112853409A (en) * | 2020-12-29 | 2021-05-28 | 哈尔滨工业大学（深圳） | Silver-containing plating solution and preparation method of foam metal material |
| 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 |
| CN115869967A (en) * | 2022-11-21 | 2023-03-31 | 昆明理工大学 | Foam copper catalyst with cross-scale pore-size structure and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109898107B (en) | 2021-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109898107A (en) | Foam metal Copper-cladding Aluminum Bar carbon nano tube electromagnetic shielding material and preparation method | |
| CN106366409B (en) | A kind of ultra-high molecular weight polyethylene/graphite alkene/nickel composite material and preparation method | |
| CN110283570B (en) | FeCo @ MXene core-shell structure composite wave-absorbing material and preparation method thereof | |
| CN109423637B (en) | Preparation method of high-conductivity material | |
| CN103130421B (en) | Nickel plating silvered glass bead and preparation method thereof | |
| CN109957144B (en) | Preparation method of conductive filler with silver-plated surface | |
| CN102381844A (en) | Method for modifying hollow glass microspheres by chemical precipitation process | |
| CN107557769A (en) | A kind of preparation method of complex metal layer coating carbon nanotubes electromagnetic shielding material | |
| Wang et al. | Enhanced microwave absorbing properties and heat resistance of carbonyl iron by electroless plating Co | |
| CN106028768A (en) | Iron-plated graphene and preparation method | |
| CN105063580A (en) | Preparation method of nickel-coated graphite powder for electroconductive rubber of electromagnetic shielding material | |
| CN103981513A (en) | Chemical nickel plating method on carbon fiber surface | |
| CN110666157A (en) | Core-shell structure C @ CoNi composite material and preparation method and application thereof | |
| CN108633242A (en) | A kind of titanium carbon/nickle composite powder radio-radar absorber and preparation method | |
| CN108486555A (en) | A kind of preparation method of conduction and Electromagnetically shielding fabrics based on chemical plating tungsten nickel | |
| CN104043826B (en) | Aluminum powder surface hydration processing method and application of aluminum powder in preparing Al@Ag nuclear shell composite particle conductive and electromagnetic shielding filler | |
| CN103866364B (en) | The magnetospheric preparation method of stainless steel fibre Surface Fe nickel alloy | |
| CN105671529A (en) | Preparation method for continuous fiber copper pipe | |
| CN107779851A (en) | A kind of carbon fiber/non-crystaline amorphous metal composite electromagnetic absorption material and preparation method thereof | |
| CN101353790B (en) | Ni-Fe-Ce-P plating bath and its preparation method, glass fibre Ni-Fe-Ce-P alloy preparation method | |
| CN104195532A (en) | Preparation method of graphite sheet surface chemical plating iron-nickel alloy layer | |
| CN111360281A (en) | Excellent conductive silver powder and preparation method thereof | |
| Guo et al. | Nickel-catalyzed deposition of Cu film on PET fabric with supercritical fluid | |
| CN102757670B (en) | Preparation method of conductive filler | |
| CN108103506A (en) | A kind of preparation method of foam metal shielding material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |