CN108587395A - A kind of bilayer wave-absorbing coating material and preparation method thereof - Google Patents
A kind of bilayer wave-absorbing coating material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention relates to a kind of double-deck wave-absorbing coating material and preparation method thereof, the bilayer wave-absorbing coating material is made of upper layer absorbing material and lower layer's absorbing material, and absorbing material material component and its mass percent are at the middle and upper levels：Lauxite coats redox graphene 6~30%, nano-nickel powder 30~45%, room temperature curing agent 6~15%, matrix resin 20~49%；Lower layer's absorbing material component and its mass percent are：Carbon-encapsulated iron particle 35~50%, room temperature curing agent 11~15%, matrix resin 35~50%.Wave-absorbing coating material provided by the invention has double-layer structure, widened absorbing material suction wave frequency bandwidth (absorbing material reflection loss value be less than 6dB, bandwidth at a lower frequency is 1.6GHz (3.4~5.0GHz), and bandwidth is 1.9GHz (12.5~14.4GHz) under upper frequency).
Description
Technical field
The invention belongs to absorbing material technical fields, it particularly relates to a kind of bilayer wave-absorbing coating material and its preparation
Method.
Background technology
Absorbing material is a kind of functional material of multicomponent wave absorbing agent coordinative role, main component include absorbent and
Binder.Efficient electromagnetic-wave absorbent needs to meet certain operating condition：Incident electromagnetic wave absorbing material surface is not first
Strong reflection occurs, next electromagnetic wave for entering material internal can efficiently be converted into thermal energy by a variety of loss mechanisms.
Microwave absorbing material is widely used in modern electronics industry, can be well for the absorbing material on electronic equipment
Slacken electromagnetic pollution phenomenon.In addition, in military field, Electromagnetic Interference technology is the important means of modern war,
Thus high performance microwave absorbing material research and development with using as Material Field research hotspot.
According to the decaying mechanism to electromagnetic wave, wave absorbing agent can be divided into magnetic loss type and dielectric loss type.Magnetic loss wave absorbing agent master
To include ferrite, magnetic metal, with larger saturation magnetization and smaller coercivity, but have the drawback that ratio
Weight is larger, oxidizable, and electromagnetic wave absorption performance is ideal not to the utmost, although it is big to inhale intensity of wave, effectively absorb frequency range it is narrow, to low frequency
Area absorbs weaker.
Dielectric loss type wave absorbing agent is a kind of absorbing material that new development comes out, with that density is low and conductivity value is larger is excellent
Point.Graphene is as a kind of dielectric loss type wave absorbing agent because with low-density, low-resistivity, highly thermally conductive property, high electron mobility etc.
Feature becomes potential efficient absorbing material.The defects of there are functional groups due to reduced graphene surface, it is residual in graphene sheet layer
Remaining defect and group can not only improve its impedance matching property, promote transition of the electronics to fermi level, can also lack
The electronics dipole relaxation of sunken dielectric relaxor and group, these are conducive to scattering and electromagnetic wave absorption, the disadvantage is that its dielectric is damaged
The power that consumes energy is limited, and does not have magnetic loss ability, cannot be satisfied requirement of the absorbing material to impedance matching, and height restores in addition
Graphene compatibility in organic polymer is also poor.
By graphene and submicron metal it is compound be expected to obtain have both comprehensive advantage graphene/super-fine metal powder
Composite material improves absorbing material impedance matching, gives full play to the synergistic effect of magnetic loss and electrical loss, realizes multiband, height
Efficiency electromagnetic wave absorption, while can also meet the requirement that coating is thin, density is small.Graphene/super-fine metal powder absorbing material at present
[F Meng, H Wang, F Huang, F G Yi, Y W Ze, H are generally prepared by a step hydrothermal reduction method
David.Composites Part B Engineering, 2017,137,260-277], due to the stronger Van der Waals of piece interlayer
Easily there is agglomeration in power, graphene prepared by such method, have seriously affected it in the application for inhaling wave field.Therefore, it opens
Low-density that send out a kind of novel, broadband and the double-deck microwave absorbing material that absorbs by force, which become, inhales the wave technology field task of top priority.
Invention content
The technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide a kind of wideband
Band inhales the high double-deck wave-absorbing coating material and preparation method thereof of wave efficiency.
In order to solve the above technical problems, technical solution provided by the invention is：
A kind of double-deck wave-absorbing coating material is provided, the bilayer wave-absorbing coating material is by upper layer absorbing material (UF@RGO@
Ni/EP absorbing materials) and lower layer's absorbing material (C Fe/EP Wave suction composite materials) composition, absorbing material raw material group at the middle and upper levels
Part and its mass percent are：Lauxite cladding redox graphene (UF@RGO) 6~30%, nano-nickel powder 30~
45%, room temperature curing agent 6~15%, matrix resin 20~49%；Lower layer's absorbing material component and its mass percent are：Carbon packet
Cover iron particle (C@Fe) 35~50%, room temperature curing agent 11~15%, matrix resin 35~50%.
Preferably, the upper layer absorbing material and lower layer's absorbing material thickness are respectively 1~5mm, the double-deck suction wave
Coating material thickness is 2~10mm.
By said program, the specific preparation method of Lauxite cladding redox graphene (UF@RGO) is as follows：
A. the synthesis of urea resin prepolymer：By formaldehyde, urea and phenol in molar ratio 2：1：0.1~0.5 is uniformly mixed
Reaction solution is obtained, it is 8~9 that triethanolamine, which is added, and adjusts reacting liquid pH value, is heated to 60~75 DEG C of 5~10h of reaction, then nature
It is cooled to room temperature to obtain Lauxite (UF) performed polymer, it is spare；
The preparation of b.UF@RGO：Graphene oxide (GO) ultrasonic disperse in water, is obtained into a concentration of 0.25~2mg/mL
Graphene oxide dispersion, urea resin prepolymer obtained by step a, urea resin prepolymer and graphene oxide is then added
Mass ratio is 0.2~5：1, it is stirring evenly and then adding into neopelex, it is 2~3 to adjust pH value, is warming up to 60~75 DEG C
3~5h is reacted, UF@GO suspension is obtained, is cooled to that ammonium hydroxide is added after room temperature to adjust the pH value of suspension is 10~11, stirring is equal
Hydrazine hydrate is added after even, and is heated to 98~100 DEG C of 24~30h of reduction reaction under nitrogen protection, by products therefrom cooling, washes
It washs, be dried to obtain UF@RGO.
Preferably, urea resin prepolymer and graphene oxide mass ratio are 5：1.
By said program, neopelex addition is 0.1~0.3wt% of water.
By said program, the volume mass ratio of hydrazine hydrate addition and graphene oxide is 50~70mL/ grams.
By said program, the nano-nickel powder grain size is 30~70nm.
By said program, the room temperature curing agent is 593 curing agent of epoxy resin；Described matrix resin is bisphenol-A type ring
Oxygen resin, bisphenol F epoxy resin or bisphenol-s epoxy resin.
Preferably, described matrix resin is bisphenol A type epoxy resin CYD-127, viscosity at ambient temperature 2500-4500Pa
s。
By said program, the carbon-encapsulated iron grain diameter is 1~5 μm, and wherein the grain size of iron is 300~370nm.Using
Arc discharge method is made that (preparation method is referring to [her China Mining University journal of Liu Tonggang, Bao Jiusheng, Yang Zhi, 2007,36 (2)：
201-204])。
The present invention also provides the preparation methods of the above-mentioned double-deck wave-absorbing coating material, are as follows：
1) upper layer pour mass (UF@RGO@Ni/EP pour mass) is prepared：
A. UF@RGO@Ni are prepared：Graphene oxide (GO) ultrasonic disperse in water, is obtained into a concentration of 0.25~2mg/mL
Graphene oxide dispersion, urea resin prepolymer is then added, urea resin prepolymer is with graphene oxide mass ratio
0.2~5：1, be stirring evenly and then adding into neopelex, it is 2~3 to adjust pH value, be warming up to 60~75 DEG C of reactions 3~
5h obtains UF GO suspension, and it is 10~11 that ammonium hydroxide is added into UF GO suspension and adjusts suspension pH value, stirs evenly, adds
Enter nano-nickel powder, wherein graphene oxide and nano-nickel powder mass ratio are 1~5：35, ultrasonic disperse is uniform, and hydrazine hydrate is added, stirs
It mixes uniformly, is then heated to 98~100 DEG C of 24~30h of reduction reaction in a nitrogen atmosphere, by products therefrom washing, be dried to obtain
UF@RGO@Ni；
B. UF@RGO@Ni ultrasonic disperses obtained by step a are obtained into a concentration of 5~10mg/mL (with the matter of RGO in DMF
Gauge) UF@RGO@Ni dispersion liquids, be then added matrix resin, ultrasonic disperse uniformly removes solvent afterwards, and room temperature curing is added
Agent stirs evenly, obtains upper layer pour mass (UF@RGO@Ni/EP pour mass) after vacuum defoamation；
2) lower layer's pour mass (C@Fe/EP pour mass) is prepared：Matrix resin and room temperature curing agent are uniformly mixed, then added
Enter carbon-encapsulated iron particle, stirs evenly, obtains lower layer's pour mass (C@Fe/EP pour mass) after vacuum defoamation；
3) the double-deck wave-absorbing coating material is prepared：In a mold by lower layer's pour mass cast obtained by step 2), after precuring again
Upper layer pour mass obtained by step 1) is poured into a mould, then solidification obtains the double-deck wave-absorbing coating material.
By said program, step 3) precuring condition is：Be heated under vacuum 80~85 DEG C heat preservation 30min~
1h。
By said program, step 3) condition of cure is：4~5h is heated at 80~85 DEG C.
Compared with prior art, the invention has the advantages that：
(1) wave-absorbing coating material provided by the invention has double-layer structure, contains ureaformaldehyde tree in absorbing material at the middle and upper levels
Fat coats redox graphene (UF@RGO) and nano-nickel powder, contains carbon-encapsulated iron particle (C@Fe) in lower layer's absorbing material,
Since ureaformaldehyde is coated on graphene film layer surface, graphene can be more uniformly dispersed in epoxy resin-base, go forward side by side one
Step improves the compatibility of graphene and epoxy resin in composite material, while a variety of dielectric polarization effects enhancing of graphene,
It inhales wave efficiency to increase, electromagnetic wave penetrates into inside the absorbing material of upper layer, by upper layer absorbing material absorbed inside agent absorption portion
Point energy, when electromagnetic wave reaches lower layer's absorbing material due to lower layer's absorbing material add more magnetic carbon coating iron particles from
And be further attenuated, it is based on Kelvin effect, most of electromagnetic wave is totally reflected and then enters back into upper layer and repeats to absorb, Jin Ertuo
(absorbing material reflection loss value is less than -6dB to the wide suction wave frequency bandwidth of absorbing material, and bandwidth at a lower frequency is
1.6GHz
(3.4~5.0GHz), bandwidth is 1.9GHz (12.5~14.4GHz) under upper frequency)；
(2) the double-deck Wave suction composite material preparation method provided by the invention is simple, easy to operation, highly practical.
Description of the drawings
Fig. 1 is the photo of 50 times of amplification after the RGO prepared by the embodiment of the present invention 1 disperses in the epoxy；
Fig. 2 is the photo of 50 times of amplification after the UF@RGO prepared by embodiment 1 disperse in the epoxy；
Fig. 3 is the SEM figures of gained UF@RGO@Ni/EP composite material sections after sample 1 cures；
Fig. 4 is the SEM figures of gained UF@RGO@Ni/EP composite material sections after sample 5 cures；
Fig. 5 is the SEM figures of gained UF@RGO@Ni/EP composite material surfaces after sample 1 cures；
Fig. 6 is the SEM figures of gained UF@RGO@Ni/EP composite material surfaces after sample 5 cures；
Fig. 7 is the reflection loss curve of gained UF@RGO@Ni/EP composite materials after sample 1~5 cures；
Fig. 8 is the reflection loss curve of gained C@Fe/EP Wave suction composite materials after sample 6~9 cures；
Fig. 9 is the reflection loss curve of the double-deck Wave suction composite material prepared by embodiment 1.
Specific implementation mode
It is more apparent from order to which technical characteristic, purpose and the advantageous effect to the present invention have, following embodiment is only
For exemplary illustration, but should not be understood as to the present invention can practical range restriction.
Embodiment 1
The preparation of UF@RGO wave absorbing agents used in the present embodiment：
Step 1：83g formalins (37wt%), 30g urea, 4.7g phenol are placed in 500mL three-necked flasks, normal
For the lower mechanical agitation of temperature at homogeneous solution, it is 8 that triethanolamine, which is added, and adjusts reacting liquid pH value, is subsequently placed in 70 DEG C of oil bath pan anti-
Answer 5 hours, reaction be cooled to room temperature it is spare, products therefrom be urea resin prepolymer (UF).
Step 2：0.1g graphene oxides (are purchased from Nanjing pioneer Nono-material Science ＆ Technology Ltd., cas：7440-44-
0, number：XF033 it) is added in 500mL beakers, 400mL distilled water is added, ultrasonic disperse uniformly obtains a concentration of 0.25mg/
The GO dispersion liquids of mL.Urea-formaldehyde prepolymer is added by different proportion, urea-formaldehyde prepolymer and GO mass ratioes are 1：5、2：4、3：3、4：2、
5：1, and the sample to be not added with urea-formaldehyde prepolymer is stirring evenly and then adding into 1.2g neopelexes as comparative sample, adjusts
PH value is 2~3, is warming up to 70 DEG C of reaction 5h, obtains the suspension of 5 groups of UF@GO, and ammonium hydroxide adjusting suspension is added after being cooled to room temperature
The pH value of liquid is 10, mechanical agitation 0.5h, and hydrazine hydrate is added, and (every gram of GO, which is corresponded to, is added 50mL hydrazine hydrates, and concentration of hydrazine hydrate is
80wt%), it is heated to 98 DEG C of reduction reactions under nitrogen protection for 24 hours, products therefrom is cooled down, ethyl alcohol and distillating filtering is used in combination,
Washing, 10h is dried in vacuo at 40 DEG C, obtains 5 groups of UF@RGO wave absorbing agents (be not added with sample obtained by urea-formaldehyde prepolymer and be denoted as RGO).
1) upper layer pour mass (UF@RGO@Ni/EP pour mass) is prepared：
A. UF@RGO@Ni composite wave-absorbing agent is prepared：
Step 1：0.1g graphene oxides are added in 500mL beakers, 400mL distilled water is added, ultrasonic disperse obtains
0.5g urea resin prepolymers (UF) are added in the GO dispersion liquids of a concentration of 0.25mg/mL, and mechanical agitation is uniform, and 1.2g ten is added
Dialkyl benzene sulfonic acids sodium, it is 2.5 to adjust pH value, is heated to 70 DEG C of reaction 5h, the suspension of UF@GO is obtained, after being cooled to room temperature
It is 10, mechanical agitation 0.5h that ammonium hydroxide, which is added, and adjusts suspension pH value, according to GO and nano-nickel powder (grain size 40nm) according to mass ratio
It is 1：35、2：35、3：35、4：35、5：35,3.5g, 1.75g, 1.17g, 0.875g, 0.7g nano-nickel powder are added to 5 respectively
In the above-mentioned suspension of group, ultrasonic disperse 0.5h obtains the dispersion liquid of 5 groups of UF@GO and nano-nickel powder, every group of UF@GO and nano nickel
5mL hydrazine hydrates are added in the dispersion liquid of powder, mechanical agitation mixes 1h under room temperature, is then heated to 98 DEG C of oil baths under nitrogen atmosphere
For 24 hours, products therefrom is cooled down for reduction reaction in pot, and ethyl alcohol and distilled water is used in combination to filter, and washing is dried in vacuo 10h at 40 DEG C,
Obtain 5 groups of UF@RGO@Ni wave absorbing agents；
B. the UF@RGO@Ni obtained by 4.1g, 4.7g, 5.3g, 5.9g, 6.5g step a are weighed respectively to be dispersed in equipped with DMF
In (1gRGO corresponds to 500mL DMF) beaker, with sonochemistry device ultrasonic disperse 5 minutes, then it is put into ultrasonic cleaning machine and surpasses
Sound disperses 30 minutes, is then respectively adding 4.5g, 3.9g, 3.4g, 2.8g, 2.3g CYD-127, ultrasonic cleaning machine ultrasonic disperse
10 minutes, then heating removed DMF, then in 80 DEG C of vacuum drying chamber it is dry for 24 hours, be separately added into after cooling 1.3g,
593 curing agent of 1.2g, 1g, 0.9g, 0.7g, stirs evenly, and pour mass (UF@RGO@Ni/EP cast in upper layer is obtained after deaeration
Body), material quality part proportioning is shown in Table 1；
1 UF@RGO@Ni/EP composite material each component proportion by weight of table
2) preparation of lower layer's pour mass (C@Fe/EP pour mass)：
By 593 curing agent mixed preparing epoxy glue solution of CYD-127 and epoxy resin, (hardener dose is resin
30wt%, 100g epoxy resin need 593 curing agent of 30g), weigh carbon-encapsulated iron particle 3.5g, 4g, 4.5g, 5g, addition pair
Epoxy resin adhesive liquid 6.5g, 6g, 5.5g, the 5g answered, it is spare after mechanical agitation uniform vacuum deaeration, obtain lower layer pour mass (C
Fe/EP pour mass), material quality part proportioning is shown in Table 2；
2 C@Fe/EP composite material each component proportion by weight of table
3) preparation of the double-deck Wave suction composite material：
Lower layer's pour mass (sample 9) obtained by step 2) is poured into a mould in a mold, mechanical agitation is uniformly poured into mold, very
It is heated to 80 DEG C of precuring 1h (preventing depositional phenomenon) under empty condition, prepares the C@Fe/EP pour mass of 60mm × 10mm × 2mm,
Upper layer pour mass (sample 5) obtained by step 1) is poured into a mould again, and then curing 4h at 80 DEG C obtains the double-deck wave-absorbing coating material, total thickness
Degree is 4mm.
Embodiment 2
Deployment conditions of the RGO and UF@RGO in matrix resin in 1 gained sample of testing example：
Specific sample preparation situation：By the RGO of 1g, 6g UF@RGO (mass ratio RGO：UF=1：5) 150W power ultrasonics are used respectively
Wave separating apparatus is dispersed in the DMF equipped with 500mL (1gRGO corresponds to 500mL DMF) beaker, weighs 99g epoxy resin, and machinery is mixed
After conjunction, after heating volatilization DMF, amplify 50 times with MDA1300/2000 type hand-held USB digital microscopes, observation RGO, UF@RGO
Micro Distribution in epoxy matrix.
Fig. 1 and 2 is respectively the photo for amplifying 50 times after RGO and UF@RGO disperse in the epoxy, it can be seen that ureaformaldehyde
The graphene of resin cladding disperses more uniformly, to compare RGO, dispersibility enhancings of the UF@RGO in matrix resin in resin.
Embodiment 3
5 groups of upper layer pour mass (UF RGO Ni/EP pour mass) prepared by embodiment 1 are poured into a mould in a mold, at 80 DEG C
Solidification 4h obtains the UF@RGO@Ni/EP composite materials of 5 groups of 60mm × 10mm × 2mm.
Using TESCAN MIRA3 field emission scanning electron microscopes, 5 groups of UF@RGO@Ni/EP composite materials of above-mentioned preparation are observed
Surface and cross-section morphology feature.
UF@RGO@Ni/EP composite materials are used into SE-3230 precision engraving machines, it is 3mm, outer diameter 7mm to be engraved as internal diameter
, thickness is the coaxial annulus of 2mm, and using Agilent N5247A types vector network analyzers and auxiliary coaxial air line
(85051-60007), test obtain the electromagnetic parameter of UF@RGO@Ni/EP, and composite material reflection damage is calculated by transmission line formula
Consumption.
Nickel cross-section morphology in UF RGO Ni/EP composite materials can be seen that by Fig. 3 and Fig. 4, illustrate that high level is added
In the case of UF@RGO (sample 5), nickel powder can disperse more uniform in resin, and the bulky grain of soilless sticking.Fig. 5 and figure
6 can be seen that nickel surface topography in UF@RGO@Ni/EP composite materials, and it is heavier to illustrate that the UF@RGO of high level can improve
Nickel powder particle deposits and agglomeration.Section and Analysis of Surface Topography illustrate that UF@RGO can improve dispersion of the nickel powder in resin
Situation.
Fig. 7 is the reflection loss curve of gained UF@RGO@Ni/EP composite materials after sample 1-5 solidifications, as a result illustrates to increase
UF@RGO contents can improve absorbing property, and when RGO contents are 5wt% (sample 5), composite material reflection loss minimum can
Reach -20.1dB, respective frequencies 8.13GHz.
Embodiment 4
4 groups of lower layer's pour mass (C@Fe/EP pour mass) prepared by embodiment 1 are poured into mold, under vacuum environment in
The C@Fe/EP Wave suction composite materials of 4 groups of 60mm × 10mm × 2mm are prepared in 80 DEG C of rapid curing 4h.
4 groups of C@Fe/EP Wave suction composite materials of gained are used into SE-3230 precision engraving machines, it is 3mm to be engraved as internal diameter, outside
Diameter is 7mm's, and thickness is the coaxial annulus of 2mm.And it is coaxial using Agilent N5247A types vector network analyzers and auxiliary
Air line (85051-60007), test obtain the electromagnetic parameter of C@Fe/EP, and composite material reflection is calculated by transmission line formula
Loss.
Fig. 8 is the reflection loss curve of gained C@Fe/EP Wave suction composite materials after sample 6-9 solidifications, the results showed that C@Fe/
EP composite materials have certain absorbing property, and when C@Fe contents are 50wt% (sample 9), reflection loss minimum value RL=-
20.5dB, this is attributed to the C@Fe that more content is added, and the magnetic loss ability of composite material increases, and then absorbing property improves.
Embodiment 5
The double-deck Wave suction composite material prepared by embodiment 1 uses SE-3230 precision engraving machines, and it is 3mm to be engraved as internal diameter,
Outer diameter is 7mm's, and thickness is the coaxial annulus of 4mm.And it is same using Agilent N5247A types vector network analyzers and auxiliary
Axis air line (85051-60007), test obtain the electromagnetic parameter of double-layer composite material, and composite wood is calculated by transmission line formula
Expect reflection loss.
Fig. 9 is the reflection loss curve of the double-deck Wave suction composite material prepared by embodiment 1, the results showed that reflection loss value is low
In -6dB, the bandwidth of composite material at a lower frequency is 1.6GHz (3.4~5.0GHz), and bandwidth is 1.9GHz under upper frequency
(12.5~14.4GHz) illustrates dual attenuation of the upper and lower composite material to electromagnetic wave so that the frequency of composite material
Duan Zengkuan has taken into account the strong absorption to composite material under high and low frequency.
Claims (9)
1. a kind of bilayer wave-absorbing coating material, which is characterized in that the bilayer wave-absorbing coating material is by upper layer absorbing material under
Layer absorbing material composition, absorbing material material component and its mass percent are at the middle and upper levels：Lauxite coats reduction-oxidation
Graphene 6~30%, nano-nickel powder 30~45%, room temperature curing agent 6~15%, matrix resin 20~49%；Wave material is inhaled by lower layer
Material component and its mass percent are：Carbon-encapsulated iron particle 35~50%, room temperature curing agent 11~15%, matrix resin 35~
50%.
2. bilayer wave-absorbing coating material according to claim 1, which is characterized in that the upper layer absorbing material and lower layer inhale
Wave material thickness is respectively 1~5mm, and the bilayer wave-absorbing coating material thickness is 2~10mm.
3. bilayer wave-absorbing coating material according to claim 1, which is characterized in that the Lauxite coats reduction-oxidation
The specific preparation method of graphene is as follows：
A. the synthesis of urea resin prepolymer：By formaldehyde, urea and phenol in molar ratio 2：1：0.1~0.5 be uniformly mixed obtain
Reaction solution, it is 8~9 that triethanolamine, which is added, and adjusts reacting liquid pH value, is heated to 60~75 DEG C of 5~10h of reaction, then natural cooling
Urea resin prepolymer is obtained to room temperature, it is spare；
B. the preparation of Lauxite cladding redox graphene：By graphene oxide ultrasonic disperse in water, obtain a concentration of
Then urea resin prepolymer obtained by step a, urea resin prepolymer is added in the graphene oxide dispersion of 0.25~2mg/mL
It is 0.2~5 with graphene oxide mass ratio：1, it is stirring evenly and then adding into neopelex, it is 2~3 to adjust pH value, is risen
Temperature obtains UF@GO suspension to 60~75 DEG C of 3~5h of reaction, is cooled to ammonium hydroxide is added after room temperature to adjust the pH value of suspension and is
10~11, it is stirring evenly and then adding into hydrazine hydrate, and be heated to 98~100 DEG C of 24~30h of reduction reaction under nitrogen protection, by institute
Product cooling is obtained, washs, be dried to obtain Lauxite cladding redox graphene.
4. it is according to claim 1 bilayer wave-absorbing coating material, which is characterized in that the nano-nickel powder grain size be 30~
70nm。
5. bilayer wave-absorbing coating material according to claim 1, which is characterized in that the room temperature curing agent is epoxy resin
593 curing agent；Described matrix resin is bisphenol A type epoxy resin, bisphenol F epoxy resin or bisphenol-s epoxy resin.
6. bilayer wave-absorbing coating material according to claim 1, which is characterized in that the carbon-encapsulated iron grain diameter is 1
~5 μm, the wherein grain size of iron is 300~370nm.
7. a kind of preparation method of any double-deck wave-absorbing coating materials of claim 1-6, which is characterized in that specific steps
It is as follows：
1) upper layer pour mass is prepared：
A. UF@RGO@Ni are prepared：By graphene oxide ultrasonic disperse in water, the oxidation stone of a concentration of 0.25~2mg/mL is obtained
Black alkene dispersion liquid, is then added urea resin prepolymer, and urea resin prepolymer is 0.2~5 with graphene oxide mass ratio：1,
It is stirring evenly and then adding into neopelex, it is 2~3 to adjust pH value, is warming up to 60~75 DEG C of 3~5h of reaction, obtains UF@
GO suspension, it is 10~11 that ammonium hydroxide is added into UF GO suspension and adjusts suspension pH value, stirs evenly, nano-nickel powder is added,
Wherein graphene oxide and nano-nickel powder mass ratio are 1~5：35, ultrasonic disperse is uniform, and hydrazine hydrate is added, stirs evenly, then
It is heated to 98~100 DEG C of 24~30h of reduction reaction in a nitrogen atmosphere, by products therefrom washing, is dried to obtain UF@RGO@Ni；
B. by UF@RGO@Ni ultrasonic disperses obtained by step a in DMF, the UF@RGO@Ni dispersions of a concentration of 5~10mg/mL are obtained
Then matrix resin is added in liquid, ultrasonic disperse uniformly removes solvent afterwards, and room temperature curing agent is added, stirs evenly, after vacuum defoamation
Obtain upper layer pour mass；
2) lower layer's pour mass is prepared：Matrix resin and room temperature curing agent are uniformly mixed, carbon-encapsulated iron particle, stirring is then added
Uniformly, lower layer's pour mass is obtained after vacuum defoamation；
3) the double-deck wave-absorbing coating material is prepared：Lower layer's pour mass cast obtained by step 2) in a mold, is poured into a mould again after precuring
Upper layer pour mass obtained by step 1), then solidification obtain the double-deck wave-absorbing coating material.
8. preparation method according to claim 7, which is characterized in that step 3) precuring condition is：Under vacuum
It is heated to 80~85 DEG C of heat preservation 30min~1h.
9. preparation method according to claim 7, which is characterized in that step 3) condition of cure is：4 are heated at 80~85 DEG C
~5h.
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