CN105062092B - A kind of chiral poly- Schiff salt tri compound absorbing material - Google Patents
A kind of chiral poly- Schiff salt tri compound absorbing material Download PDFInfo
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Abstract
A kind of chiral poly- Schiff salt tri compound absorbing material, absorbing medium is made up of CNT, cobalt nickel ferrite and chiral poly- Schiff salt three, and the mass ratio of CNT, cobalt nickel ferrite, chiral poly- Schiff salt and absorbing medium is respectively 11 ~ 17:100、45~65:100 and 18 ~ 44:100.Absorbing medium is 1 with the mass ratio of chiral poly- Schiff salt tri compound absorbing material:2~4:5, paraffin matrix is 1 with the mass ratio of chiral poly- Schiff salt tri compound absorbing material:2~5.Composite wave-suction material of the present invention has that the light weight thin, absorption band of layer is wide, absorption intensity is big, good stability the advantages of, there is good wave-absorbing effect in the GHz of frequency range 8-18, there is important application value in terms of electromagnetic pollution and radar invisible is administered.
Description
Technical field
The present invention is a kind of chiral poly- Schiff salt tri compound absorbing material, more particularly to a kind of CNT/cobalt
The absorbing material of Ni ferrite/chiral poly- Schiff salt tri compound, is a kind of Radar Stealth Composites, belongs to suction ripple material
Material technical field.
Background technology
Absorbing material refers to that can absorb the electromagnetic wave energy for projecting its surface, and dielectric loss by material makes electromagnetism
Wave energy is converted into a class material of the energy of heat energy or other forms.Absorbing material typically requires strong absorption, bandwidth, quality
It is light and structural behaviour stabilization in the environment of use the features such as, conventional absorbing material mainly has：Ferrite, metal is micro-
Powder, semi-conducting material, conduction high polymer, carbon fiber, polycrystalline iron fiber etc..At present, invisible coating traditional both at home and abroad exists big
Amount outstanding problem has to be solved：Narrower absorption frequency range cannot resist the comprehensive scouting of wide-band radar wave；The density of material is big
And the thickness of coating is big, increased system weight, influences the mobility of system.Publication No. CN101203127A, entitled one
Rare earth Fe basis suction wave material and preparation method thereof is planted, the matching thickness up to 6mm that the material is used in most strong absorption is deposited
In the big shortcoming of coating layer thickness；Publication No. CN1206204A, a kind of entitled novel wave-absorbing material and its manufacture method, disclose
The electromagnetic wave absorbent material that a kind of ferrite magnetic material and zinc, cobalt, copper etc. are made through treatment, the material is in low-frequency range
0.6GHz-5GHz have stronger microwave absorbing property, and 93.7% is reached in the absorptivity of centre frequency 3.5GHz, but high band 8-
18GHz wave-absorbing effects are poor, and material is made up of metal oxide and metal, and density is big；Publication No. CN101914722A, it is entitled
A kind of electromagnetic wave absorbent material, discloses a kind of Nd1-xSmxFe14B is made with the mixed merga pass magnetic field orientating treatment of binding material
Composite, the material has strong absorption in the -8GHz of low-frequency range 1, and poor in the -18GHz wave-absorbing effects of high band 8, and material
There is main component for rare-earth iron-boron alloy, equally exist the big shortcoming of density.Publication No. CN103555270A, a kind of entitled hand
Property polyShiff base salt/ferrite wave-absorbing material and preparation method thereof, discloses a kind of chiral binary composite wave-suction material, the material
There is reflection loss to electromagnetic wave in 8-18GHz, maximum reflection loss is-17.2dB, but it is still little to inhale intensity of wave.
Chiral absorbing material, compared with conventional absorbing material, with three distinguishing features：One is the cross-pole of electromagnetic field
Change, absorption intensity of the enhancing to electromagnetic wave；Two is the chiral parameter of adjustment easier than adjusting dielectric parameter and magnetic conductivity, can compared with
Areflexia requirement is met on frequency band wide；Three be chiral material frequency sensitivity it is smaller than dielectric constant and magnetic conductivity, it is easily real
Existing wideband absorbs.Therefore there is very big potential in terms of improving absorbing property, extension and inhaling wave frequency band.Chiral ternary in the present invention
Composite wave-suction material at frequency 13.2GHz, thickness 1.5mm have most strong reflection loss -33.3dB, and reflection loss reach -
The a width of 7.6GHz of suction wave frequency (10.4-18GHz) of below 5dB.Contrast above-mentioned several patents, the chiral tri compound in the present invention
Absorbing material thickness is small, have strong absorption in the -18GHz of high band 8, and most strong absorption can reach -33.3dB, and contained chirality is gathered
Schiff is the organic material of low-density, solves that usual absorbing material thickness is big, -18GHz the absorption differences of high band 8, material
The big problem of density, therefore the chiral composite wave-suction material has the performance more excellent than existing absorbing material.
The content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a kind of chiral poly- Schiff salt tri compound suction ripple
Material.The absorbing medium of described composite wave-suction material is by CNT, cobalt nickel ferrite and chiral poly- Schiff salt three
Constitute, the mass ratio of CNT, cobalt nickel ferrite, chiral poly- Schiff salt and absorbing medium is respectively 11~17:100、
45~65:100 and 18~44:100；Absorbing medium is 1 with the mass ratio of chiral poly- Schiff salt tri compound absorbing material:
2~4:5, paraffin matrix is 1 with the mass ratio of chiral poly- Schiff salt tri compound absorbing material:2~5.
Preparation process is as follows：
(1) CNT and mixed acid add mixed acid, ultrasonic disperse according to the ratio of 1g/100mL in CNT
30 minutes, heated at 70 DEG C, stirred, flowed back 4 hours；Reaction terminates rear ice-water bath and is cooled to be emerged there is no red cigarette, thereafter
24 hours are stood, after pouring out supernatant liquor, suction filtration is washed with deionized to filtrate pH=7, gained filter cake is done at 100 DEG C
The dry CNT for 24 hours, being purified.
(2) CoCL2 6H2O, six water nickel chlorides and anhydrous ferric chloride press 1:1:4 mol ratio is dissolved in deionized water, then
The CNT of enuatrol and purifying is separately added into, is stirred 1 hour, then heat to 75 DEG C, condensing reflux, and it is slowly added dropwise hydrogen
Sodium hydroxide solution continues to react 1 hour to pH value of solution=11；Reaction solution is transferred in water heating kettle, it is small in reaction 12 at 180 DEG C
Shi Hou, stands cooling and then is filtered, and after filter cake uses water, absolute ethanol washing to pH=7 respectively, then 12 is dried at 70 DEG C
CNT/cobalt nickel ferrite is obtained after hour.
(3) by 1B and KOH in molar ratio 1:In 1 addition absolute ethyl alcohol, at 50 DEG C after magnetic agitation dissolving, then delay
The slow ethanol solution that 1,4-benzoquinone is added dropwise, condition of the maintenance reaction system in 80 DEG C of water-baths, nitrogen protection and condensing reflux
Under, magnetic agitation adds silver nitrate aqueous solution after reacting 22 hours, continues to react 6 hours；Reaction carries out suction filtration, filter cake point after terminating
In 75 DEG C of dryings 7 hours, chiral poly- Schiff salt Yong not be obtained after deionized water, absolute ethanol washing 3 times.
(4) by CNT/cobalt nickel ferrite, chiral poly- Schiff salt addition absolute ethyl alcohol, ultrasonically treated 6 is small
When, solvent evaporated is reheated, thereafter again respectively through dryings in 12 hours, the milled processed of 20 minutes at 70 DEG C, the carbon for obtaining is received
Mitron/cobalt nickel ferrite/chiral poly- Schiff salt tri compound inhales ripple medium with paraffin matrix material according to mass ratio 7:3,
Heating stirring is well mixed, and chiral poly- Schiff salt tri compound absorbing material is obtained.
Described mixed acid is the mixture of the concentrated sulfuric acid and concentrated nitric acid, and the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3:1.
The mol ratio of described 1B, 1,4-benzoquinone and silver nitrate is 1:1:1.5.
Described chiral poly- Schiff salt and the mass ratio 1 of CNT/cobalt nickel ferrite:1~5.
Advantages of the present invention
The present invention has that the light weight thin, absorption band of layer is wide, absorption intensity is big, good stability the advantages of.Chiral poly- Schiff
Alkali salt is a kind of containing chiral conducting polymer, and the electric conductivity of poly- Schiff can carry out dielectric loss to electromagnetic wave, chiral
The helical structure of material can cause the cross polarization of electromagnetic wave, easily realize that wideband absorbs by adjusting chiral parameter.CNT/
Cobalt nickel ferrite is the absorbing material for having resistive losses and magnetic loss concurrently, by chiral poly- Schiff salt and CNT/cobalt
Ni ferrite is compound can to realize electromagnetic impedance match, by their synergistic function, have in-the 18GHz of frequency range 8 good
Wave-absorbing effect, there is important application value in terms of electromagnetic pollution and radar invisible is administered.
Brief description of the drawings
Fig. 1 is the wave-absorbing effect figure of the embodiment of the present invention 1；
Fig. 2 is the wave-absorbing effect figure of the embodiment of the present invention 2；
Fig. 3 is the wave-absorbing effect figure of the embodiment of the present invention 3.
Specific embodiment
Embodiment 1
(1) 2.00g CNTs are taken to be placed in there-necked flask, 200mL nitration mixture (dense H is added2SO4/ dense HNO3=3:1), surpass
Sound disperses 30 minutes, is heated at 70 DEG C, stirred, flowed back 4 hours.After reaction terminates, reaction solution is poured into beaker and is put into
Cooled down in ice-water bath, add cold water to be emerged until there is no red cigarette.Stand 24 hours, pour out supernatant liquor, suction filtration and spend from
Sub- water cyclic washing is put into baking oven and is dried 24 hours at 100 DEG C to filtrate pH=7, the CNT for being purified.
(2) 4.87g anhydrous ferric chlorides, 1.78g CoCL2 6H2Os, the water nickel chlorides of 1.78g six are taken, 150mL deionizations are dissolved in
In water, it is to be dissolved after be placed in 500mL there-necked flasks, add 0.125g enuatrols, add 0.75g purifying CNT, stir
Mix 1 hour.75 DEG C are then heated to, condensing reflux is slowly added dropwise the sodium hydroxide solution of 3mol/L to pH value of solution=11, continues
Reaction 1 hour.Reaction solution is transferred in water heating kettle and is reacted 12 hours at 180 DEG C, with water and absolute ethyl alcohol cyclic washing to pH
Dried 12 hours at=7,70 DEG C, obtain CNT/cobalt nickel ferrite composite.
(3) in 250mL there-necked flasks add 1.46g mol 1Bs and 0.56g mol KOH, be dissolved in 20mL without
In water-ethanol, magnetic agitation dissolving at 50 DEG C.30mL is slowly dropped to dissolved with the ethanol solution of 0.01mol 1,4-benzoquinone
In stating mixed liquor, in 80 DEG C of water-baths, nitrogen protection and magnetic agitation 22 hours under conditions of condensing reflux.5mL is added afterwards
Dissolved with the aqueous solution of 2.55g silver nitrates, continue to react 6 hours.Suction filtration, filter cake deionized water and absolute ethanol washing 3 times, put
Dried 7 hours in 75 DEG C of air dry ovens, obtain chiral poly- Schiff salt.
(4) take 3.20g CNTs/cobalt nickel ferrite to be placed in beaker with the chiral poly- Schiff salt of 0.80g, add nothing
Water-ethanol ultrasound 6 hours, heats solvent evaporated, is put into and is dried at 70 DEG C in baking oven 12 hours, then grinds 20 minutes, then with
1.71g heating paraffins stir and are mixed to get CNT/cobalt nickel ferrite/chiral poly- Schiff salt composite wave-absorbing material
Material.
(5) material is pressed into the annulus of external diameter 7mm, internal diameter 3mm, thickness 2mm in particular manufacturing craft, HP- is used
The electromagnetic parameter of 8722ES vector network analyzer test materials, test frequency scope is 1-18GHz.Its absorbing property is under
The equation in face is estimated：(2)RL(dB)=20log | (Zin-
1)/(Zin+1)|.The material has the reflection less than -10dB to damage in thickness 1.5mm in the range of the -15.2GHz of frequency 11.9
Consumption, obtains most strong reflection loss -33.2dB, the institute of wave-absorbing effect below figure 1 that the material simulation is calculated at frequency 13.2GHz
Show.
Embodiment 2
(1) step is with embodiment 1.
(2) step is with embodiment 1.
(3) step is with embodiment 1.
(4) take 3.20g CNTs/cobalt nickel ferrite to be placed in beaker with the chiral poly- Schiff salt of 1.60g, add nothing
Water-ethanol ultrasound 6 hours, heats solvent evaporated, is put into and is dried at 70 DEG C in baking oven 12 hours, then grinds 20 minutes, then with
2.06g heating paraffins stir and are mixed to get the compound suction of 6.86g CNTs/cobalt nickel ferrite/chiral poly- Schiff salt
Wave material.
(5) material is pressed into the annulus of external diameter 7mm, internal diameter 3mm, thickness 2mm in particular manufacturing craft, HP- is used
The electromagnetic parameter of 8722ES vector network analyzer test materials, test frequency scope is 1-18GHz.Its absorbing property is under
The equation in face is estimated：(2)RL(dB)=20log | (Zin-
1)/(Zin+1)|.The material has the reflection less than -10dB to damage in thickness 1.5mm in the range of the -15.6GHz of frequency 12.6
Consumption, obtains most strong reflection loss -26.4dB, the institute of wave-absorbing effect below figure 2 that the material simulation is calculated at frequency 13.7GHz
Show.
Embodiment 3
(1) step is with embodiment 1
(2) step is with embodiment 1
(3) step is with embodiment 1
(4) take 2.40g CNTs/cobalt nickel ferrite to be placed in beaker with the chiral poly- Schiff salt of 1.80g, add nothing
Water-ethanol ultrasound 6 hours, heats solvent evaporated, is put into and is dried at 70 DEG C in baking oven 12 hours, then grinds 20 minutes, then with
1.80g heating paraffins stir and are mixed to get the compound suction of 6.00g CNTs/cobalt nickel ferrite/chiral poly- Schiff salt
Wave material.
The material is pressed into the annulus of external diameter 7mm, internal diameter 3mm, thickness 2mm in particular manufacturing craft, is sweared with HP-8722ES
The electromagnetic parameter of Network Analyzer test material is measured, test frequency scope is 1-18GHz.Its absorbing property is according to following equation
Formula is estimated：(2)RL(dB)=20log | (Zin-1)/(Zin+
1)|.The material has the reflection loss less than -10dB, in frequency in thickness 1.3mm in the range of the -18.0GHz of frequency 15.8
Most strong reflection loss -18.2dB is obtained at 17.3GHz, the wave-absorbing effect that the material simulation is calculated is illustrated in fig. 3 shown below.
Note：This patent is by national natural science fund subsidy project (21264011) and aviation fund
(2014ZF56020) is subsidized.
Claims (3)
1. a kind of chiral poly- Schiff salt tri compound absorbing material, it is characterised in that the absorption of described composite wave-suction material
Medium is made up of CNT, cobalt nickel ferrite and chiral poly- Schiff salt three, CNT, cobalt nickel ferrite, chirality
Poly- Schiff salt is respectively 11~17 with the mass ratio of absorbing medium:100th, 45~65:100 and 18~44:100；Absorb and be situated between
Matter is 1 with the mass ratio of chiral poly- Schiff salt tri compound absorbing material:2~4:5, paraffin matrix and chiral poly- Schiff
The mass ratio of alkali salt tri compound absorbing material is 1:2~5；
Preparation process is as follows：
(1) CNT and mixed acid add mixed acid, 30 points of ultrasonic disperse according to the ratio of 1g/100mL in CNT
Clock, heats at 70 DEG C, stirs, flows back 4 hours；Reaction terminates rear ice-water bath and is cooled to be emerged there is no red cigarette, stands thereafter
24 hours, after pouring out supernatant liquor, suction filtration was washed with deionized to filtrate pH=7, and gained filter cake dries 24 at 100 DEG C
Hour, the CNT for being purified；
(2) CoCL2 6H2O, six water nickel chlorides and anhydrous ferric chloride press 1:1:4 mol ratio is dissolved in deionized water, then is distinguished
The CNT of enuatrol and purifying is added, is stirred 1 hour, then heat to 75 DEG C, condensing reflux, and it is slowly added dropwise hydroxide
Sodium solution continues to react 1 hour to pH value of solution=11；Reaction solution is transferred in water heating kettle, in reaction 12 hours at 180 DEG C
Afterwards, stand cooling and then filtered, filter cake is respectively with after water, absolute ethanol washing to pH=7, then that 12 are dried at 70 DEG C is small
When after obtain CNT/cobalt nickel ferrite；
(3) 1B and KOH in molar ratio 1:In 1 addition absolute ethyl alcohol, at 50 DEG C after magnetic agitation dissolving, then it is slowly added dropwise
The ethanol solution of 1,4-benzoquinone, maintenance reaction system 80 DEG C of water-baths, nitrogen protect and condensing reflux under conditions of, magnetic force
Stirring reaction adds silver nitrate aqueous solution after 22 hours, continue to react 6 hours；Reaction carries out suction filtration after terminating, and filter cake spends respectively
After ionized water, absolute ethanol washing 3 times, in 75 DEG C of dryings 7 hours, chiral poly- Schiff salt is obtained；
(4) in CNT/cobalt nickel ferrite, chiral poly- Schiff salt being added into absolute ethyl alcohol, ultrasonically treated 6 hours, then
Heating solvent evaporated, thereafter again respectively through dryings in 12 hours, the milled processed of 20 minutes at 70 DEG C, the CNT for obtaining/
Cobalt nickel ferrite/chiral poly- Schiff salt tri compound inhales ripple medium with paraffin matrix material according to mass ratio 7:3, heating is stirred
Mix well mixed, chiral poly- Schiff salt tri compound absorbing material is obtained.
2. the chiral poly- Schiff salt tri compound absorbing material of one kind according to claim 1, it is characterised in that described
Mixed acid be the mixture of the concentrated sulfuric acid and concentrated nitric acid, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3:1.
3. the chiral poly- Schiff salt tri compound absorbing material of one kind according to claim 1, it is characterised in that described
1B, 1,4-benzoquinone and silver nitrate mol ratio be 1:1:1.5.
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| WO2018157399A1 (en) * | 2017-03-03 | 2018-09-07 | 深圳市佩成科技有限责任公司 | Preparation method for fe3o4/mwcnts-paraffin composite material |
| WO2018157400A1 (en) * | 2017-03-03 | 2018-09-07 | 深圳市佩成科技有限责任公司 | Preparation method for pani/fe3o4/mwcnts-paraffin composite material |
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| CN101899289A (en) * | 2009-05-31 | 2010-12-01 | 鸿富锦精密工业（深圳）有限公司 | Wave-absorbing heat dissipation material |
| CN103555270B (en) * | 2013-11-07 | 2015-04-15 | 南昌航空大学 | Chiral poly-schiff alkali salt/ferrite wave-adsorbing material and preparation method thereof |
| CN104086953B (en) * | 2014-06-26 | 2017-07-21 | 南昌航空大学 | A kind of chitosan-modified ferrite fills the preparation method of multi-walled carbon nanotube/polythiophene composite wave-suction material |
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