CN1651524A - Carbon nano-pipe composite coating layer type wave absorption material and its preparation method - Google Patents
Carbon nano-pipe composite coating layer type wave absorption material and its preparation method Download PDFInfo
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- CN1651524A CN1651524A CN 200510011177 CN200510011177A CN1651524A CN 1651524 A CN1651524 A CN 1651524A CN 200510011177 CN200510011177 CN 200510011177 CN 200510011177 A CN200510011177 A CN 200510011177A CN 1651524 A CN1651524 A CN 1651524A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 title claims description 63
- 239000011247 coating layer Substances 0.000 title claims description 14
- 238000010521 absorption reaction Methods 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title claims description 12
- 229910052799 carbon Inorganic materials 0.000 title claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 21
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 21
- 229920001971 elastomer Polymers 0.000 claims abstract description 12
- 239000005060 rubber Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 239000004033 plastic Substances 0.000 claims abstract description 6
- 229920003023 plastic Polymers 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims description 45
- 238000000576 coating method Methods 0.000 claims description 45
- 239000000126 substance Substances 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000002048 multi walled nanotube Substances 0.000 claims description 10
- 239000002966 varnish Substances 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920003987 resole Polymers 0.000 claims description 3
- 239000002109 single walled nanotube Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 19
- 239000011358 absorbing material Substances 0.000 abstract description 13
- 239000011787 zinc oxide Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 238000002310 reflectometry Methods 0.000 description 20
- 239000006185 dispersion Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000635 Spelter Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000007903 penetration ability Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A coated layer type composite wave absorbing material containing carbon nanotubes is composed of the basic substrate consisting of the polymer chosen from rubber, resin and plastics and carbon nanotubes, and the coated layer consisting of paint and nano-zinc oxide. Its advantages are high effect to absorb radar waves and adjustable frequency range of wave-absorbing peak.
Description
Technical field
The present invention relates to a kind of composite wave absorption material and preparation method thereof, particularly a kind of polymkeric substance that contains carbon nanotube and its coating (polymkeric substance that contains nano zine oxide) and preparation method thereof.Belong to the absorbing material technical field.
Background technology
Absorbing material is to absorb the electromagnetic wave energy that projects its surface, and changes a class material of heat energy into by the loss of material.On using,, still require material to have in light weight, heatproof, moisture-proof, performance such as anticorrosive except that requiring absorbing material in broad frequency band, hertzian wave to be had the high specific absorption.Advanced absorbing material is the basic substance of hi-tech and superior weapon, and material is absolutely necessary in the application of important war industrys such as space flight, aviation, weapons, naval vessels; Development to hi-tech and high-performance weapons system of new generation has very important influence.Absorbing material is a kind of epochmaking material of modern weapons equipment, and existence and the penetration ability that improves weaponry had decisive significance, is the critical material of modern weaponss such as guided missile, aircraft, naval vessels, tank.For example, the stealthy fighter-bomber of the F-117 of the U.S., the stealthy strategic bomber of B2 and the stealthy air fighter of developing of state-of-the-art the 4th generation air fighter F-22, strategic cruise missiles etc. have all adopted extraordinary absorbing material.
Carbon nanotube is hollow tubular fiber structure, and its diameter is generally a few nanometer to tens nanometers, and length can reach several microns even several millimeters.It has very strong surface effects, quantum size effect, local fields effect and special a lot of unusual physics and chemical propertys such as interface region.It has the conduction intensity of metalloid; Its theoretical strength is 100 times of steel, but weight only is 1/7 of steel.In addition, physics and electrology characteristics such as the specific surface area that carbon nanotube has is moderate, charging and discharging capabilities is strong, can be used for the ultracapacitor manufacturing in fields such as automobile, machinery, electronics, military affairs, and can with electro-conductive material, high strength composite, shielding material and the stealth material etc. of various metals, the nonmetal and compound composition excellent combination property of macromolecular material.
Chinese patent 1513589 (publication number) discloses a kind of nano-scale carbon material dispersion liquid and preparation method thereof respectively.Said composition is made up of the dispersion medium of nano-scale carbon material, dispersion agent, stablizer, surplus; Its preparation method is that dispersion agent is added in the dispersion medium, adds nano-scale carbon material and stablizer again, with high speed dispersor or with ultrasonic dispersing 10-60 minute, makes nano-scale carbon material dispersion liquid.In addition, Chinese patent 1486927 (publication number) discloses carbon nanotube of a kind of grafted by super branched polymer and preparation method thereof.Carbon nanotube obtains the acidifying carbon nanotube after the acid with strong oxidizing property surface modification, evenly spread in plastics, rubber, the coating preparation nanometer high strength composite and absorbing material then as specialist additive.Though above-mentioned two patents are all declared to be applied to the absorbing material field, all there is not concrete absorbing property index parameter.
Shen Cengmin etc. studies show that (matrix material journal to the radar wave absorptive character of carbon nanotube/vinyl cyanide-butadiene-vinyl benzene composite material, the 20th volume, the 2nd phase, in April, 2003), the reflectivity of this material in 5.39GHz to 7.19GHz range of frequency is less than-5dB, absorbing property is arranged, and the reflectivity of material has reached-10dB when 5.83GHz.Shortcoming is that the crest of suction ripple is little, frequency is narrow.
Summary of the invention
The purpose of this invention is to provide a kind of absorbing material of inhaling the wave frequency broad.
The objective of the invention is to be achieved through the following technical solutions:
Absorbing material of the present invention contains two portions, i.e. body portion 1 and coating layer portion 2 (structrual description is shown in Figure 1).Body portion has following two kinds of components: polymkeric substance, carbon nanotube, its weight proportion is: polymkeric substance 30～99%, carbon nanotube 1～70%, coating layer portion have following two kinds of components: coating, nano zine oxide.Its weight proportion is: coating 40～99%, nano zine oxide 1～60%.Described polymkeric substance is at least a in rubber, resin, the plastics.
Described for rubber be terpolymer EP rubber, isoprene-isobutylene rubber, styrene-butadiene rubber(SBR) etc.
Described for resin be Resins, epoxy, resol, acrylic resin etc.
Described for plastics be polyethylene, polypropylene, polymeric amide etc.
Described coating is varnish, Polyurethane, Resins, epoxy etc.
It is 0.4～100nm that described carbon nanotube adopts external diameter, length be 10nm～1mm original Single Walled Carbon Nanotube,
At least a in the multi-walled carbon nano-tubes.
Described nano zine oxide adopts median size at 5nm～100nm, and coating of particles is bar-shaped, spherical, acicular at least a.
The invention provides a kind of preparation method of absorbing material, this method is carried out as follows:
A. the carbon nanotube (without chemistry and physical treatment) of getting original preparation in advance carries out vacuum-drying, according to the above ratio used polymkeric substance, carbon nanotube is joined in the mixer together then, it is mixed, then moulding;
The nano zine oxide that b. will contain aforementioned proportion is put into coating and is disperseed equably;
C. the coating that makes among the step b is coated in the surface that step a prepares material equably, the thickness of coating is 1 μ m-1mm.Bake out temperature is 25-80 ℃.
The present invention has following advantage: carbon nanotube has good electroconductibility, and its conduction intensity can reach more than 10000 times of copper, and it and polymkeric substance is compound, and its volume resistance is reduced significantly.Under the effect of electromagnetic field, carbon nanotube can produce polarized dissipation current as dipole, and under the matrix effect, dispersion current is attenuated around, thereby the radar wave energy transformation is the energy of other form.In addition, at the nano oxidized spelter coating of surface-coated one deck of matrix, change the dielectric parameter and the electromagnetic parameter of material, thereby adjust the frequency separation of wave absorbed crest value effectively, and the suction ripple curve shape of absorbing material is constant substantially.
Description of drawings
Fig. 1 is structure-coating type composite wave-suction material sketch.
Embodiment
Embodiment 1:
With external diameter after the vacuum-drying is 2～30nm, and length is the multi-walled carbon nano-tubes 1% of 1～20 μ m, and polypropylene 99% joins earlier in the high-speed mixer, extrudes in twin screw extruder again, prepares the thin slice that length is respectively 18mm * 18mm * 2mm.This material a peak value occurs at 17.03GHz, and reflectivity is-1.2dB.At 5nm particulate state zinc oxide 1%, varnish 99% is mixed with coating with median size, then coating is sprayed on the surface of above-mentioned materials, and thickness is 1 μ m.This material suction ripple curve shape of material after coating is constant substantially, is that the position that the peak changes, and a peak value occurs at 15.90GHz, and reflectivity is-1.1dB.
Embodiment 2:
With external diameter after the vacuum-drying is 2～30nm, length is the multi-walled carbon nano-tubes 4% of 1～50 μ m, and resol 96% joins in the high-speed mixer earlier, in twin screw extruder, extrude again, prepare the thin slice that length is respectively 18mm * 18mm * 2mm.This material a peak value occurs at 7.6GHz, and reflectivity is-17.6dB.At 30nm particulate state zinc oxide 50%, Resins, epoxy 50% is mixed with coating with median size, then coating is sprayed on the surface of above-mentioned materials, and thickness is 2 μ m.This material suction ripple curve shape of material after coating is constant substantially, is that the position that the peak changes, and a peak value occurs at 6.5GHz, and reflectivity is-14.6dB.
Embodiment 3:
With external diameter after the vacuum-drying is 1～20nm, length is the Single Walled Carbon Nanotube 10% of 1～100 μ m, and terpolymer EP rubber 90% joins in the high-speed mixer earlier, in twin screw extruder, extrude again, prepare the thin slice that length is respectively 18mm * 18mm * 2mm.This material a peak value occurs at 16.5GHz, and reflectivity is-10.2dB.At the bar-shaped zinc oxide 50% of 100nm, varnish 50% is mixed with coating with median size, then coating is sprayed on the surface of above-mentioned materials, and thickness is 50 μ m.This material suction ripple curve shape of material after coating is constant substantially, is that the position that the peak changes, and a peak value occurs at 15.5GHz, and reflectivity is-9.1dB.
Embodiment 4:
With external diameter after the vacuum-drying is 2～30nm, length is the multi-walled carbon nano-tubes 30% of 1～50 μ m, and Resins, epoxy 70% joins in the high-speed mixer earlier, in twin screw extruder, extrude again, prepare the thin slice that length is respectively 18mm * 18mm * 2mm.This material a peak value occurs at 15.2GHz, and reflectivity is-24.9dB.At 50nm particulate state zinc oxide 30%, Polyurethane 70% is mixed with coating with median size, then coating is sprayed on the surface of above-mentioned materials, and thickness is 5 μ m.This material suction ripple curve shape of material after coating is constant substantially, is that the position that the peak changes, and a peak value occurs at 13.3GHz, and reflectivity is-23.6dB.
Embodiment 5:
With external diameter after the vacuum-drying is 2～60nm, and length is the multi-walled carbon nano-tubes 40% of 1～100 μ m, and styrene-butadiene rubber(SBR) 60% joins uniform mixing in the mill, prepares the thin slice that length is respectively 18mm * 18mm * 2mm.This material a peak value occurs at 8.1GHz, and reflectivity is-17.5dB.At 30nm particulate state zinc oxide 60%, varnish 40% is mixed with coating with median size, then coating is sprayed on the surface of above-mentioned materials, and thickness is 1mm.This material suction ripple curve shape of material after coating is constant substantially, is that variation has taken place in the position that the peak, a peak value occurs at 9.5GHz, and reflectivity is-16.3dB.
Embodiment 6:
With external diameter after the vacuum-drying is 2～30nm, and length is the multi-walled carbon nano-tubes 70% of 1～50 μ m, and acrylic resin 30% joins uniform mixing in the high-speed mixer, prepares the thin slice that length is respectively 18mm * 18mm * 2mm.This material a peak value occurs at 13.5GHz, and reflectivity is-20.9dB.At 5nm～30nm particulate state zinc oxide 30%, Polyurethane 70% is mixed with coating with median size, then coating is sprayed on the surface of above-mentioned materials, and thickness is 5 μ m.This material suction ripple curve shape of material after coating is constant substantially, is that the position that the peak changes, and a peak value occurs at 11.2GHz, and reflectivity is-19.6dB.
Embodiment 7:
With external diameter after the vacuum-drying is 2～60nm, and length is the multi-walled carbon nano-tubes 40% of 1～100 μ m, and polyethylene 60% joins uniform mixing in the mill, prepares the thin slice that length is respectively 18mm * 18mm * 2mm.This material a peak value occurs at 6.1GHz, and reflectivity is-10.5dB.At 30nm particulate state zinc oxide 60%, varnish 40% is mixed with coating with median size, then coating is sprayed on the surface of above-mentioned materials, and thickness is 1mm.This material suction ripple curve shape of material after coating is constant substantially, is that variation has taken place in the position that the peak, a peak value occurs at 5.0GHz, and reflectivity is-16.3dB.
Embodiment 8:
With external diameter after the vacuum-drying is 2～60nm, and length is the multi-walled carbon nano-tubes 20% of 1～100 μ m, and polymeric amide 80% joins uniform mixing in the mill, prepares the thin slice that length is respectively 18mm * 18mm * 2mm.This material a peak value occurs at 10.2GHz, and reflectivity is-20.5dB.At 30nm particulate state zinc oxide 60%, varnish 40% is mixed with coating with median size, then coating is sprayed on the surface of above-mentioned materials, and thickness is 1mm.This material suction ripple curve shape of material after coating is constant substantially, is that variation has taken place in the position that the peak, a peak value occurs at 8.2GHz, and reflectivity is-19.3dB.
Embodiment 9:
With external diameter after the vacuum-drying is 2～60nm, and length is the multi-walled carbon nano-tubes 40% of 1～100 μ m, and isoprene-isobutylene rubber 60% joins uniform mixing in the mill, prepares the thin slice that length is respectively 18mm * 18mm * 2mm.This material a peak value occurs at 8.2GHz, and reflectivity is-13.5dB.At 30nm particulate state zinc oxide 60%, varnish 40% is mixed with coating with median size, then coating is sprayed on the surface of above-mentioned materials, and thickness is 1mm.This material suction ripple curve shape of material after coating is constant substantially, is that variation has taken place in the position that the peak, a peak value occurs at 7.3GHz, and reflectivity is-11.8dB.
Claims (8)
1. carbon nano-pipe composite coating layer type wave absorption material, it is characterized in that this material contains two portions, be that body portion and coating layer portion, body portion contain following two kinds of components: polymkeric substance, carbon nanotube, its weight proportion is: polymkeric substance 30～99%, carbon nanotube 1～70%, coating layer portion contains following two kinds of components: coating, nano zine oxide, its weight proportion is: coating 40～99%, nano zine oxide 1～60%, described polymkeric substance are at least a in rubber, resin, the plastics.
2. a kind of carbon nano-pipe composite coating layer type wave absorption material according to claim 1 is characterized in that described rubber is any in terpolymer EP rubber, isoprene-isobutylene rubber, the styrene-butadiene rubber(SBR) etc.
3. a kind of carbon nano-pipe composite coating layer type wave absorption material according to claim 1 is characterized in that described resin is any in Resins, epoxy, resol, the acrylic resin etc.
4. a kind of carbon nano-pipe composite coating layer type wave absorption material according to claim 1 is characterized in that described plastics are any in polyethylene, polypropylene, the polymeric amide etc.
5. a kind of carbon nano-pipe composite coating layer type wave absorption material according to claim 1 is characterized in that it is 0.4～100nm that described carbon nanotube adopts external diameter, and length is at least a in the original Single Walled Carbon Nanotube, multi-walled carbon nano-tubes of 10nm～1mm.
6. a kind of carbon nano-pipe composite coating layer type wave absorption material according to claim 1 is characterized in that described nano zine oxide adopts median size at 5nm～100nm, and coating of particles is bar-shaped, and is spherical or acicular at least a.
7. a kind of carbon nano-pipe composite coating layer type wave absorption material according to claim 1 is characterized in that described coating is any in varnish, Polyurethane, the Resins, epoxy etc.
8. the preparation method of a carbon nano-pipe composite coating layer type wave absorption material is characterized in that this method carries out as follows:
A. the carbon nanotube of getting original preparation in advance carries out vacuum-drying, by the described proportioning of claim 1 used polymkeric substance, carbon nanotube is joined in the mixer together then, it is mixed, then moulding;
B. by the described proportioning of claim 1 nano zine oxide being put into coating disperses equably;
C. the coating that makes among the step b is coated in the surface that step a prepares material equably, the thickness of coating is 1 μ m-1mm.Bake out temperature is 25-80 ℃.
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| CNB2005100111772A CN1304497C (en) | 2005-01-14 | 2005-01-14 | Carbon nano-pipe composite coating layer type wave absorption material and its preparation method |
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| CN1304497C CN1304497C (en) | 2007-03-14 |
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