CN103408899A - Tree-like structure micro-nano wave absorption agent/epoxy resin composite wave absorption material preparation method - Google Patents
Tree-like structure micro-nano wave absorption agent/epoxy resin composite wave absorption material preparation method Download PDFInfo
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Abstract
The present invention relates to a tree-like structure micro-nano wave absorption agent/epoxy resin composite wave absorption material preparation method, which specifically comprises: adopting polymer base hollow porous fibers as a raw material to obtain nano-scale stem hollow porous carbon fibers, adopting a vapor deposition method in a tubular furnace to grow nano-scale branch carbon nano-tubes on the surface of the stem structure and inside the stem structure to obtain a stem-branch composite carbon material, soaking the composite carbon material in a metal solution, drying, introducing hydrogen to reduce so as to load metal particle fruits on the stem-branch structure in an in situ manner to obtain a tree-like structure micro-nano wave absorption agent, and adding the wave absorption agent to an epoxy resin to cure to obtain the wave absorption stealth composite material. The tree-like structure micro-nano wave absorption agent/epoxy resin composite wave absorption material has the following characteristics that: characteristics of microporous structure, high specific surface area, high dielectric constant, and high magnetic permeability are provided, respective effects and synergistic coupling effects of hollow porous carbon fibers, carbon nano-tubes and metal particles can be provided, an excellent wave absorption performance is provided, and the composite wave absorption material has an excellent radar X-wave band wave absorption performance.
Description
Technical field
The invention belongs to the interleaving techniques field of porous carbon materials and nano material, be specifically related to a kind of take hollow carbon fibers as the matrix adopting vapour deposition process prepare porous carbon fiber carbon nano-tube and loaded with nano metal particles " class tree construction " wave absorbing agent and with the preparation method of the composite wave-suction material of epoxy resin.
Background technology
For take hollow carbon fibers, prepare the preparation method of " class tree construction " wave absorbing agent of porous carbon fiber carbon nano-tube and loaded with nano metal particles thereof as the matrix adopting vapour deposition process, yet there are no corresponding report at home and abroad, under regard to the research background that the present invention is correlated with and be introduced explanation.
Along with improving constantly of countries in the world military technique, the wave-absorbing and camouflage technology is as a kind of effective means that can improve weapons system existence, breakthrough and deep strike ability, with laser, cruise missile and be called the three great revolutionary movements of modern military technology.Wherein radar invisible is the emphasis of stealthy technique, accounts for more than 60% of stealthy technique.And development radar stealth technology main path is the efficient radar absorbings of research and development, the development of radar absorbing and use have extremely important meaning to following military development.Traditional absorption agent ferrite, metal fine powder, silicon carbide and graphite isodensity are larger, and mechanical property is bad; Its main absorption peak of primary carbon nanotube is in C frequency range (4 ~ 8GHz), and the look-in frequency of short range tracking radar, marine radar or missile-guidance radar is positioned at X frequency range (8 ~ 12GHz), therefore, with the little hollow carbon fibers of the density primary carbon nanotube of growth and loaded with nano metal particles, at X-band, has good assimilation effect as the epoxy resin composite material of absorbent preparation.
Hollow carbon fibers is a kind of porous carbon fiber with hollow structure, is a kind of new carbon of developing in recent years.Hollow carbon fibers inside has hollow structure, and internal diameter is generally between 20-100 μ m, and wall thickness is 1/4-1/10 of internal diameter.Its surfaces externally and internally respectively has the microporous layers that one deck is very thin, and the following atomic hole rich content of 1nm, adds in upper wall abundant micropore is also arranged, make hertzian wave between hole, can occur repeatedly reflection, refraction and loss.Simultaneously, hollow carbon fibers is a kind of good dielectric materials, has fine electroconductibility, preferably the absorption of electromagnetic wave ability.
Carbon nanotube is a kind of important new carbon, the length-to-diameter ratio that it is large and stratiform hollow structure, and high specific inductivity is given its very large specific surface area and good wave-sucking performance.In addition, carbon nanotube also has strong mechanical performance, stablizes the characteristics such as physicochemical property and high reaction activity, in numerous wave absorbing agents, has obvious superiority, in invisbile plane and Stealth weapon, is used widely.Nano-metal particle has high magnetic permeability and very excellent magnetic loss characteristic, is a kind of good absorbing material.
The present invention propose a kind of take hollow carbon fibers as the matrix adopting vapour deposition process prepare porous carbon fiber carbon nano-tube and loaded with nano metal particles " class tree construction " wave absorbing agent and with the preparation method of the composite wave-suction material of epoxy resin.Propose three kinds of wave absorbing agents of different nature---the new system that-hollow carbon fibers, carbon nanotube and nano-metal particle organically combine, realize that by dielectric loss and magnetic loss effect composite wave-suction material has good assimilation effect at X-band.This is the preparation method of the novel wave-absorbing material of a kind of low cost, easy to operate, high yield, and design and the preparation science of absorbing material enriched in research, and research and development have important directive significance to novel wave-absorbing material.
Summary of the invention
The object of the present invention is to provide a kind of take hollow carbon fibers as the matrix adopting vapour deposition process prepare porous carbon fiber carbon nano-tube and loaded with nano metal particles " class tree construction " wave absorbing agent and with the preparation method of the composite wave-suction material of epoxy resin.By carbon nano-tube on hollow carbon fibers and loaded with nano metal particles, make " class tree construction " wave absorbing agent/epoxy resin composite wave-absorbing material in X-band, have good assimilation effect.
The preparation method of class tree construction micro-nano wave absorbing agent/epoxy resin composite wave-absorbing material that the present invention proposes, described absorbing material is the class tree construction, comprise the micron order hollow carbon fibers that is positioned at " doing " section, be positioned at the nano-scale carbon nanotube of " branch " section, be positioned at the nanometer grade gold metal particles of " really " section; Concrete steps are as follows:
(1) " do "---the preparation of-micron order hollow carbon fibers: using the polymer-based carbon hollow porous fiber of purifying as raw material, after it is cut into to the staple fibre of 3 ~ 5cm, at 200 ~ 300 ℃ of lower preoxidation 1 ~ 3h; The sample of gained is at 600 ~ 950 ℃, carbonization in rare gas element, and carbonization time is 30 ~ 120min, then utilizes CO
2Gas activates, and activation temperature is 600 ~ 950 ℃, and soak time is 20 ~ 120 min, obtains hollow carbon fibers;
(2) " dry-branch " structure---preparation of-hollow carbon fibers/carbon nanotube: the hollow carbon fibers that step (1) is obtained is immersed in the metallic solution with katalysis, magnetic agitation 5 ~ 48h, carry out suction filtration, dry, apply again vapour deposition process, in tube furnace, pass through successively rare gas element, hydrogen and carbon-source gas, thereby obtain all growing " dry-branch " of carbon nanotube structure being arranged at the surfaces externally and internally of hollow carbon fibers, wherein, logical hydrogen reducing metallic solution 30 ~ 120min at 400 ~ 700 ℃ of temperature, logical carbon-source gas carbon nano-tube 30 ~ 120min at 500 ~ 900 ℃ of temperature,
(3) preparation of " class tree construction " micro-nano wave absorbing agent: the hollow carbon fibers that obtains in step (2)/carbon nanotube sample is immersed in to 5 ~ 48h in metallic solution, after carrying out suction filtration and drying, in tube furnace, the applied chemistry vapour deposition process is logical rare gas element the temperature to 400 ℃ that raises gradually first, then in temperature, be 400 ~ 700 ℃ of logical hydrogen 30 ~ 120min reducing metal solution, what in quartz boat, obtain is " class tree construction " micro-nano wave absorbing agent;
(4) preparation of wave-absorbing and camouflage composite material: " class tree construction " the micro-nano wave absorbing agent in step (3) is mixed in proportion with epoxy resin and solidifying agent, the curing reaction aftershaping, its working method is: take 50 ~ 100g epoxy resin, be positioned over 1-2h in 80 ℃ of baking ovens, during this period, taking mass ratio is that 1-5% " class tree construction " micro-nano wave absorbing agent is placed in acetone soln, constant temperature water bath 80-100 ℃, the epoxy resin that adds preheating under high-speed stirring, treat that acetone volatilizees fully, add solidifying agent (mass ratio of solidifying agent and epoxy resin is 1:10), after high-speed stirring 5-10min, pour in mould, de-bubble, solidify, finally had to " class tree construction " micro-nano wave absorbing agent/epoxy resin composite wave-absorbing material.
In the present invention, the polymer-based carbon hollow porous fiber described in step (1) is any in polyacrylonitrile-radical hollow porous fiber, polypropylene-base hollow porous fiber, polyvinylidene fluoride hollow porous fiber, PVA-based hollow porous fiber or polytetrafluoroethylene (PTFE) base hollow porous fiber etc.
In the present invention, the metallic solution with katalysis described in step (2) is any or the many group combination in nickelous nitrate, nickel oxide, nickelous chloride, single nickel salt, iron nitrate, ferrocene, ferric oxide, iron(ic) chloride, ferric sulfate, cobalt oxide, cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol or Vanadium Pentoxide in FLAKES etc.Wherein take nickelous nitrate, iron nitrate or ferrocene metallic solution as preferred.
In the present invention, the carbon-source gas described in step (2) is any in ethanol, methyl alcohol, ethane, methane, ethene, benzene, toluene or dimethylbenzene etc.Wherein take the dehydrated alcohol carbon-source gas as preferred.
In the present invention, the metallic solution described in step (3) is any or the many group combination in nickelous nitrate, nickel oxide, nickelous chloride, single nickel salt, iron nitrate, ferrocene, ferric oxide, iron(ic) chloride, ferric sulfate, cobalt oxide, cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol or Vanadium Pentoxide in FLAKES etc.Wherein take iron nitrate or ferrocene metallic solution as preferred.
In the present invention, the epoxy resin described in step (4) is a kind of in bisphenol A-type E-51, E-44, E-42 or E-54 type epoxy resin.
In the present invention, the solidifying agent described in step (4) is a kind of in aromatic series agent solidifying agent phenylenediamine, two amido ditans, two amido sulfobenzides, diethylenetriamine, tetraethylene pentamine or triethylene tetramine.
Superiority of the present invention:
(1) to adopt a kind of superpolymer base hollow porous fiber be that raw material prepares hollow carbon fibers in the present invention, and thereby load carbon nanotube and nano-metal particle prepare the method for " class tree construction " wave absorbing agent on hollow carbon fibers, technique is simple, easy to operate, processing and manufacturing is with low cost, has great practical value.
(2) the present invention utilizes the special nature and role of hollow carbon fibers pore structure, can make incident electromagnetic wave Multi reflection, refraction etc. occur and maximized loss hertzian wave between hole, reaches the purpose of electromagnetic wave absorption; And on the little hollow carbon fibers carbon nano-tube of density, reach the original position loaded with nano metal particles, make " class tree construction " wave absorbing agent have higher specific inductivity and magnetic permeability, reach and in X-band, have good assimilation effect.
(3) the present invention adopts chemical Vapor deposition process to be prepared wave absorbing agent, and this method is very ripe, and parameter is easily controlled, and is easy to realize industrialization.
The accompanying drawing explanation
Fig. 1 is the suction ripple test curve of " class tree construction " wave absorbing agent of embodiments of the invention 1 preparation.
Fig. 2 is the suction ripple test curve of " class tree construction " wave absorbing agent of embodiments of the invention 2 preparations.
Fig. 3 is the suction ripple test curve of " class tree construction " wave absorbing agent of embodiments of the invention 3 preparations.
Embodiment
The following examples are to further illustrate of the present invention, rather than limit the scope of the invention.
Embodiment 1:(1) " do "---the preparation of-micron order hollow carbon fibers: polyacrylonitrile hollow porous fiber (PANHF) is cut into to 3 ~ 5cm, is immersed in dehydrated alcohol after 24h dry 8h under 80 ℃, make the fiber purifying; After in the baking oven of 230 ℃ preoxidation 1h, temperature rise rate is 1.5 ℃/min; The sample of gained is placed in quartz boat, and quartz boat is put into to tube furnace.Under the condition of logical inert nitrogen gas, raise gradually temperature in tube furnace, temperature rise rate is 1.5 ℃/min, and when temperature reaches 700 ℃ carbonizedfibres 60min, make the carbonization of PAN preoxided thread, thereby finally obtain hollow carbon fibers (HPCF).
(2) " dry-branch " structure---preparation of-hollow carbon fibers/carbon nanotube: the nickel nitrate solution 50ml of configuration 0.1mol/L, the HPCF0.5g of preparation is flooded wherein and magnetic agitation 5h, rear taking-up suction filtration and under 80 ℃ dry 8h, obtain the hollow carbon fibers that the equal load of surfaces externally and internally has Cobalt salts.Then put it in quartz boat and be placed in tube furnace.It is 4.5 ℃/min that temperature rise rate is set, and under the protection of inert nitrogen gas, heats up gradually, and, in the time of 400 ℃, passes into hydrogen, and constant temperature 60min, then stop passing into of hydrogen.Under the protection of nitrogen, be warming up to 700 ℃, pass into carbon source dehydrated alcohol gas; constant temperature 60min; finally stop passing into of dehydrated alcohol gas, at the protection borehole cooling of nitrogen, thereby obtain at surface and the inner hollow carbon fibers (HPCF-CNTs) that carbon nanotube is arranged of all growing.
(3) preparation of " class tree construction " micro-nano wave absorbing agent: get " dry-branch " structure of a certain amount of HPCF-CNTs, it is immersed in to 5h in the nickelous nitrate metallic solution of 0.3mol/L, rear suction filtration, drying.Then put it in quartz boat and be placed in tube furnace.It is 4.5 ℃/min that temperature rise rate is set, and under the protection of inert nitrogen gas, heats up gradually, and, in the time of 400 ℃, passes into hydrogen, and constant temperature 120min, then stop passing into of hydrogen, and reduction obtains metallic particles and loads on the surperficial and inner of fiber.Under the protection of nitrogen, cooling, finally make " class tree construction " wave absorbing agent (ACHF-CNTs-Ni) gradually.
(4) preparation of wave-absorbing and camouflage composite material: claim epoxy resin (E-44) 240.00g, be positioned in the hollow baking oven, be warming up to 120 ℃, constant temperature 1h, to remove the bubble in epoxy resin.Keeping under vacuum tightness-0.1MPa, taking out epoxy resin after slow cooling to 120 ℃, pouring there-necked flask into, 90 ℃ of oil bath constant temperature." class tree construction " wave absorbing agent of certain mass ratio is added to epoxy resin under high-speed stirring in, ultrasonic 0.5h.Add 60.00g phenylenediamine solidifying agent, after high-speed stirring 5min, pour in the 180mm*180mm mould, at 80 ℃ of lower 2h, 160 ℃ of lower 4h, finally make " class tree construction " micro-nano wave absorbing agent/epoxy resin composite wave-absorbing material.
Fig. 1 is the suction ripple test curve of embodiment 1 preparation " class tree construction " wave absorbing agent.This wave absorbing agent an absorption peak occurred at X-band (8-12GHz) as can be seen from Figure 1, and good wave-absorbing effect is arranged, and maximum absorption band appears at the 9.25GHz place in X-band, the frequency range of maximum absorption band be 7.2GHz (R<-5dB).
Embodiment 2:(1) " do "---the preparation of-micron order hollow carbon fibers: polypropylene-base hollow porous fiber (PPHF) is cut into to the staple fibre of 3 ~ 5cm, after be immersed in dehydrated alcohol after 24h dry 8h under 80 ℃, make the fiber purifying.The PPHF of purifying is immersed in to 24h in the resol (PF) that is dissolved in ethanolic soln, then each 2h under 50 ℃, 80 ℃, 120 ℃ and 170 ℃, make the PF resin that is adsorbed on fiber surface slowly solidify, finally obtain load the sample P PHF-PF of PF resin as presoma arranged, then the sample P PHF-PF of gained is placed in to quartz boat, and quartz boat is put into to tube furnace.Under the condition of logical inert nitrogen gas, tube furnace interior temperature gradually raises, temperature rise rate is 2.5 ℃/min, and when temperature reaches 650 ℃ carbonizedfibres 60min, make as the PPHF fiber of template and burnt, phenolic resin carbonized, then utilize CO2 to activate, activation temperature is 800 ℃, and soak time is 50 min, finally obtains hollow porous active carbon fiber (ACHF).
(2) " dry-branch " structure---preparation of-hollow carbon fibers/carbon nanotube: the nickel nitrate solution 50ml of configuration 0.1mol/L, the ACHF0.5g of preparation is flooded to wherein 5h, rear taking-up suction filtration and under 80 ℃ dry 8h, obtain the hollow carbon fibers that the equal load of surfaces externally and internally has nickel salts.All the other steps, with embodiment 1, obtain at surface and the inner hollow carbon fibers (ACHF-CNTs) that carbon nanotube is arranged of all growing.
(3) preparation of " class tree construction " micro-nano wave absorbing agent: get " dry-branch " structure of a certain amount of ACHF-CNTs, it is immersed in to 5h in the nickelous nitrate metallic solution of 0.1mol/L, rear suction filtration, drying.Then put it in quartz boat and be placed in tube furnace.It is 4.5 ℃/min that temperature rise rate is set, and under the protection of inert nitrogen gas, heats up gradually, and, in the time of 400 ℃, passes into hydrogen, and constant temperature 60min, then stop passing into of hydrogen, and reduction obtains metallic particles and loads on the surperficial and inner of fiber.Under the protection of nitrogen, cooling, finally make " class tree construction " wave absorbing agent (ACHF-CNTs-Ni) gradually.
(4) preparation of wave-absorbing and camouflage composite material: claim epoxy resin (E-51) 200.00g, be positioned over 2h in 80 ℃ of baking ovens, make the resin preheating, reduced viscosity, during this period, by solidifying agent 4, 4 diaminodiphenylmethane (DDM) at 90 ℃ down to melting fully, taking mass ratio is that 1-5% " class tree construction " micro-nano wave absorbing agent is placed in the ultrasonic 30min of a certain amount of acetone soln, after add in the epoxy resin of preheating, 80 ℃ of constant temperature water baths, and high-speed stirring to acetone volatilizees fully, take out, add the 50gDDM solidifying agent, after high-speed stirring 5-10min, pour on the mould of 180mm*180mm, at 80 ℃ of lower 2h, 160 ℃ of lower 4h, finally make " class tree construction " micro-nano wave absorbing agent/epoxy resin composite wave-absorbing material.
Fig. 2 is the suction ripple test curve of embodiment 2 preparation " class tree construction " wave absorbing agents.This wave absorbing agent the biabsorption peak occurred at X-band (8-12GHz) as can be seen from Figure 2, good wave-absorbing effect is arranged, the 10.5GHz place that maximum absorption band appears in X-band is-31.036dB, the frequency range of maximum absorption band be 7.1GHz (R<-5dB).
Embodiment 3:(1) " do "---the preparation of-micron order hollow carbon fibers: polyacrylonitrile hollow porous fiber (PANHF) is cut into to 3 ~ 5cm, is immersed in dehydrated alcohol after 24h dry 8h under 80 ℃, make the fiber purifying; After in the baking oven of 230 ℃ preoxidation 1h, temperature rise rate is 1.5 ℃/min; The sample of gained is placed in quartz boat, and quartz boat is put into to tube furnace.Under the condition of logical inert nitrogen gas, raise gradually temperature in tube furnace, temperature rise rate is 2.5 ℃/min, and when temperature reaches 700 ℃ carbonizedfibres 60min, make the carbonization of PAN preoxided thread, thereby finally obtain hollow carbon fibers (HPCF).
(2) " dry-branch " structure---preparation of-hollow carbon fibers/carbon nanotube: the nickel nitrate solution 50ml of configuration 0.1mol/L, the HPCF0.5g of preparation is flooded wherein and magnetic agitation 5h, rear taking-up suction filtration and under 80 ℃ dry 8h, obtain the hollow carbon fibers that the equal load of surfaces externally and internally has nickel salts.Then put it in quartz boat and be placed in tube furnace.It is 4.5 ℃/min that temperature rise rate is set, and under the protection of inert nitrogen gas, heats up gradually, and, in the time of 400 ℃, passes into hydrogen, and constant temperature 60min, then stop passing into of hydrogen.Under the protection of nitrogen, be warming up to 700 ℃, pass into carbon source dehydrated alcohol gas; constant temperature 60min; finally stop passing into of dehydrated alcohol gas, at the protection borehole cooling of nitrogen, thereby obtain at surface and the inner hollow carbon fibers (HPCF-CNTs) that carbon nanotube is arranged of all growing.
(3) preparation of " class tree construction " micro-nano wave absorbing agent: get " dry-branch " structure of a certain amount of HPCF-CNTs, it is immersed in to 5h in the nickelous nitrate metallic solution of 0.2mol/L, rear suction filtration, drying.Then put it in quartz boat and be placed in tube furnace.It is 4.5 ℃/min that temperature rise rate is set, and under the protection of inert nitrogen gas, heats up gradually, and, in the time of 400 ℃, passes into hydrogen, and constant temperature 90min, then stop passing into of hydrogen, and reduction obtains metallic particles and loads on the surperficial and inner of fiber.Under the protection of nitrogen, cooling, finally make " class tree construction " wave absorbing agent (HPCF-CNTs-Ni) gradually.
(4) preparation of wave-absorbing and camouflage composite material: claim epoxy resin (E-51) 85.00g, be positioned over 2h in 80 ℃ of baking ovens, make the resin preheating, reduced viscosity, during this period, taking mass ratio is that 1-5% " class tree construction " micro-nano wave absorbing agent is placed in the ultrasonic 30min of a certain amount of acetone soln, after add in the epoxy resin of preheating, 80 ℃ of constant temperature water baths, and high-speed stirring to acetone volatilizees fully, take out, add 8.5g triethylene tetramine solidifying agent, after high-speed stirring 5-10min, be brushed on the iron plate of 180mm*180mm, under room temperature, solidify, finally make " class tree construction " micro-nano wave absorbing agent/epoxy resin composite wave-absorbing material.
Fig. 3 is the suction ripple test curve of embodiment 3 preparation " class tree construction " wave absorbing agents.This wave absorbing agent an absorption peak occurred at X and Ku wave band (8-18GHz) as can be seen from Figure 3, good wave-absorbing effect is arranged, the 12.55GHz place that maximum absorption band appears in the Ku wave band is-50.305dB, the frequency range of maximum absorption band be 9.0GHz (R<-5dB).
The absorbing property detected result of " class tree construction " wave absorbing agent prepared for embodiment 1-3 by table 1.
" class tree construction " wave absorbing agent of preparing of each embodiment has excellent suction wave system energy at X-band as can be seen from Table 1.
Table 1:
Claims (7)
1. the preparation method of a kind tree construction micro-nano wave absorbing agent/epoxy resin composite wave-absorbing material, it is characterized in that, described absorbing material is the class tree construction, comprise the micron order hollow carbon fibers that is positioned at " doing " section, be positioned at the nano-scale carbon nanotube of " branch " section, be positioned at the nanometer grade gold metal particles of " really " section; Concrete steps are as follows:
(1) " do "---the preparation of-micron order hollow carbon fibers: using the polymer-based carbon hollow porous fiber of purifying as raw material, after it is cut into to the staple fibre of 3 ~ 5cm, at 200 ~ 300 ℃ of lower preoxidation 1 ~ 3h; The sample of gained is at 600 ~ 950 ℃, carbonization in rare gas element, and carbonization time is 30 ~ 120min, then utilizes CO
2Gas activates, and activation temperature is 600 ~ 950 ℃, and soak time is 20 ~ 120 min, obtains hollow carbon fibers;
(2) " dry-branch " structure---preparation of-hollow carbon fibers/carbon nanotube: the hollow carbon fibers that step (1) is obtained is immersed in the metallic solution with katalysis, magnetic agitation 5 ~ 48h, carry out suction filtration, dry, apply again vapour deposition process, in tube furnace, pass through successively rare gas element, hydrogen and carbon-source gas, thereby obtain all growing " dry-branch " of carbon nanotube structure being arranged at the surfaces externally and internally of hollow carbon fibers, wherein, logical hydrogen reducing metallic solution 30 ~ 120min at 400 ~ 700 ℃ of temperature, logical carbon-source gas carbon nano-tube 30 ~ 120min at 500 ~ 900 ℃ of temperature,
(3) preparation of " class tree construction " micro-nano wave absorbing agent: the hollow carbon fibers that obtains in step (2)/carbon nanotube sample is immersed in to 5 ~ 48h in metallic solution, after carrying out suction filtration and drying, in tube furnace, the applied chemistry vapour deposition process is logical rare gas element the temperature to 400 ℃ that raises gradually first, then in temperature, be 400 ~ 700 ℃ of logical hydrogen 30 ~ 120min reducing metal solution, what in quartz boat, obtain is " class tree construction " micro-nano wave absorbing agent;
(4) preparation of wave-absorbing and camouflage composite material: " class tree construction " the micro-nano wave absorbing agent in step (3) is mixed in proportion with epoxy resin and solidifying agent, the curing reaction aftershaping, its working method is: take 50 ~ 100g epoxy resin, be positioned over 1-2h in 80 ℃ of baking ovens, during this period, taking mass ratio is that 1-5% " class tree construction " micro-nano wave absorbing agent is placed in acetone soln, constant temperature water bath 80-100 ℃, the epoxy resin that adds preheating under high-speed stirring, treat that acetone volatilizees fully, add solidifying agent, the mass ratio 1:10 of solidifying agent and epoxy resin, after high-speed stirring 5-10min, pour in mould, de-bubble, solidify, finally made " class tree construction " micro-nano wave absorbing agent/epoxy resin composite wave-absorbing material.
2. the preparation method of class tree construction micro-nano wave absorbing agent/epoxy resin composite wave-absorbing material according to claim 1, is characterized in that the middle institute of step (1) art polymer-based carbon hollow porous fiber is any in polyacrylonitrile-radical hollow porous fiber, polyvinylidene fluoride hollow porous fiber, PVA-based hollow porous fiber or polytetrafluoroethylene (PTFE) base hollow porous fiber.
3. the preparation method of class tree construction micro-nano wave absorbing agent/epoxy resin composite wave-absorbing material according to claim 1, the metallic solution that it is characterized in that having described in step (2) katalysis is any or the many group combination in nickelous nitrate, nickel oxide, nickelous chloride, single nickel salt, iron nitrate, ferrocene, ferric oxide, iron(ic) chloride, ferric sulfate, cobalt oxide, cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol or Vanadium Pentoxide in FLAKES.
4. the preparation method of class tree construction micro-nano wave absorbing agent/epoxy resin composite wave-absorbing material according to claim 1, is characterized in that carbon-source gas described in step (2) is any in ethanol, methyl alcohol, ethane, methane, ethene, benzene, toluene or dimethylbenzene.
5. the preparation method of class tree construction micro-nano wave absorbing agent/epoxy resin composite wave-absorbing material according to claim 1, is characterized in that metallic solution described in step (3) is any or the many group combination in nickelous nitrate, nickel oxide, nickelous chloride, single nickel salt, iron nitrate, ferrocene, ferric oxide, iron(ic) chloride, ferric sulfate, cobalt oxide, cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol or Vanadium Pentoxide in FLAKES.
6. the preparation method of class tree construction micro-nano wave absorbing agent/epoxy resin composite wave-absorbing material according to claim 1, is characterized in that epoxy resin described in step (4) is a kind of in bisphenol A-type E-51, E-44, E-42 or E-54 type epoxy resin.
7. the preparation method of class tree construction micro-nano wave absorbing agent/epoxy resin composite wave-absorbing material according to claim 1, is characterized in that solidifying agent described in step (4) is a kind of in aromatic series agent solidifying agent phenylenediamine, two amido ditans, two amido sulfobenzides, diethylenetriamine, tetraethylene pentamine or triethylene tetramine.
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| CN111039277A (en) * | 2019-12-31 | 2020-04-21 | 江苏领瑞新材料科技有限公司 | Preparation method of PCNF modified resin stealth wave absorber |
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