CN108342183A - A kind of nickeliferous composite wave-suction material and preparation method thereof - Google Patents
A kind of nickeliferous composite wave-suction material and preparation method thereof Download PDFInfo
- Publication number
- CN108342183A CN108342183A CN201810140557.3A CN201810140557A CN108342183A CN 108342183 A CN108342183 A CN 108342183A CN 201810140557 A CN201810140557 A CN 201810140557A CN 108342183 A CN108342183 A CN 108342183A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- obtains
- composite wave
- preparation
- suction material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention provides a kind of nickeliferous composite wave-suction material and preparation method thereof, composite wave-suction material includes graphene oxide matrix, ferrite, nano nickel and nickelous carbonate；The ferrite, nano nickel and nickelous carbonate are supported on the graphene oxide matrix surface.Embodiment the result shows that, when the matching thickness for the composite wave-suction material that the present invention obtains is 2.25mm, absorption maximum 15.16dB is reached in 14.88GHz, effective absorption band of the reflection loss less than 10dB reaches 4GHz, significantly widen it can be seen that inhaling wave frequency band, wave-sucking performance enhancing.
Description
Technical field
The present invention relates to absorbing material technical fields more particularly to a kind of nickeliferous composite wave-suction material and preparation method thereof.
Background technology
With weapon system search, the rapid development of trace ability, stealth technology is increasingly paid attention to by the military of various countries.It is suitable
The needs of modern war, stealth technology are answered to be applied on weaponry as emerging combat forces.Radar invisible skill
Core of the art as stealth technology, can reduce radar scattering section, and the key technology of radar stealth technology is to inhale
The microwave absorbing property of wave material, the good new and effective absorbing material of processability have become the important research class of national defense and military fields
Topic.
Graphene light weight, good conductivity have higher dielectric constant and the easy dielectric relaxor of outer-shell electron and decay
Electromagnetic wave, these excellent electrical properties can make it as preferable dielectric loss wave absorption base material.But high dielectric constant is also led
It causes graphene to there are problems that absorption band narrower width, limits the application of graphene absorbing material.
Invention content
In view of this, the purpose of the present invention is to provide a kind of nickeliferous composite wave-suction material and preparation method thereof, the present invention
The composite wave-suction material absorption band being prepared is wide, and has preferable dielectric loss.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme:
The present invention provides a kind of nickeliferous composite wave-suction material, including lamellar graphene oxide matrix, ferrite particle,
Nano nickel and nickelous carbonate；The ferrite particle, nano nickel and nickelous carbonate are supported on the graphene oxide matrix surface and layer
Between piece.
Preferably, the graphene oxide contains 3~5 synusia layers；The grain size of the nano nickel is 20~100nm；It is described
Grain size≤100nm of ferrite particle.
Preferably, the mass ratio of the graphene oxide matrix, ferrite, nano nickel and nickelous carbonate is 1~2:0.5~3:
1~30:8~20.
The present invention also provides a kind of preparation methods of nickeliferous composite wave-suction material, include the following steps:
(1) iron chloride, nano-nickel powder, surfactant, urea and ethylene glycol are mixed, obtains mixed liquor；
(3) mixed liquor that the step (1) obtains is mixed with graphene oxide, carries out hydro-thermal reaction, obtains hydro-thermal
Reaction material liquid；
(4) supernatant for removing the hydro-thermal reaction feed liquid that the step (2) obtains carries out remaining feed liquid centrifugation and washes successively
It washs and dries, obtain composite wave-suction material.
Preferably, the mass ratio of iron chloride in the step (1), nano-nickel powder, surfactant, urea and ethylene glycol is
1.1:(0.5~4):2:4:(30~60).
Preferably, the surfactant includes polyvinylpyrrolidone.
Preferably, in the step (2), graphene oxide and prepare mixed liquor iron chloride mass ratio be (1~
2):11。
Preferably, the temperature of hydro-thermal reaction is 170~200 DEG C in the step (2), time of hydro-thermal reaction is 18~
24h。
Preferably, the preparation method of the graphene oxide includes:
(I) graphite powder, potassium permanganate, sodium nitrate, the concentrated sulfuric acid and orthophosphoric acid are mixed, obtains mixed liquor；
(II) mixed liquor for obtaining the step (I) carries out Primary Oxidation reaction, obtains just oxidation reaction feed liquid；It is described
The temperature of Primary Oxidation reaction is 50~60 DEG C, and the time of reaction is 12h；
(III) hydrogen peroxide is added in the first oxidation reaction feed liquid obtained to the step (II), carries out reoxidizing reaction, obtains
To reoxidizing reaction material liquid；
(IV) reaction material liquid that reoxidizes that the step (III) obtains is centrifuged, obtains graphene oxide.
Preferably, graphite powder, potassium permanganate, sodium nitrate, the concentrated sulfuric acid and ortho-phosphoric mass ratio are 1 in the step (I):
(2~3):(1~2):(90~110):(10~18)；The mass fraction of the concentrated sulfuric acid is 98%, the ortho-phosphoric quality
A concentration of 1.685g/mL；
The grain size of the graphite powder is 10~20 μm；
In the step (III), hydrogen peroxide and the mass ratio for preparing just oxidation reaction feed liquid graphite powder are 1:(2~3)；
The mass fraction of the hydrogen peroxide is 30%.
The present invention provides a kind of nickeliferous composite wave-suction material, including lamellar graphene oxide matrix, ferrite particle,
Nano nickel and nickelous carbonate；The ferrite particle, nano nickel and nickelous carbonate are supported on the graphene oxide matrix surface and layer
Between piece.The present invention adheres to upper ferrite particle, and, magnetic micro-powder iron composite modified by nano-nickel powder in surface of graphene oxide
Oxysome particle and nano-nickel powder increase eddy-current loss, natural resonance and the magnetic hystersis loss of material, obtain the enhancing of magnetic loss ability, resistance
Anti- matching properties are good, and the polynary composite wave-suction material of mechanism of absorption, absorbability and frequency bandwidth have clear improvement.Implement
Example the result shows that, when the matching thickness of the composite wave-suction material that the present invention obtains is 2.25mm, reach most in 14.88GHz
Big absorption -15.16dB, effective absorption band of the reflection loss less than -10dB reach 4GHz, are higher than
；When matching thickness is 2.35mm, reach absorption maximum -10.16dB in 13.92GHz, reflection loss less than -
Effective absorption band of 10dB reaches 0.17GHz, it is seen that and it inhales wave frequency band and significantly widens, wave-sucking performance enhancing.
Description of the drawings
Fig. 1 is the composite wave-suction material microscopic appearance SEM photograph containing 7.2wt% graphene oxides prepared by embodiment 1；
Fig. 2 is the composite wave-suction material XRD spectrum containing 7.2wt% graphene oxides prepared by embodiment 1；
Fig. 3 is the reflectance curve of the composite wave-suction material containing 7.2wt% graphene oxides prepared by embodiment 1；
Fig. 4 is that the composite wave-suction material microscopic appearance SEM containing 13.5wt% graphene oxides prepared by embodiment 2 shines
Piece；
Fig. 5 is the reflectance curve of the composite wave-suction material containing 13.5wt% graphene oxides prepared by embodiment 2；
Fig. 6 is the reflectance curve of absorbing material prepared by comparative example 1.
Specific implementation mode
The present invention provides a kind of nickeliferous composite wave-suction material, including lamellar graphene oxide matrix, ferrite particle,
Nano nickel and nickelous carbonate；The ferrite particle, nano nickel and nickelous carbonate are supported on the graphene oxide matrix surface and layer
Between piece.
Composite wave-suction material of the present invention includes graphene oxide matrix, and the graphene oxide matrix is preferably synusia
Shape structure, the graphene oxide preferably comprise 3~5 synusia layers, in the graphene oxide thickness in monolayer be preferably 0.7~
0.8μm。
Composite wave-suction material of the present invention includes nano nickel and nickelous carbonate.In the present invention, the grain size of the nano nickel
Preferably 20~100nm, further preferably 30~70nm, more preferably 40~50nm.In the present invention, the nano nickel and
Nickelous carbonate is supported on the graphene oxide matrix surface；The synusia spacing of the graphene oxide matrix is small, only receives on a small quantity
Rice nickel and a small amount of nickelous carbonate are distributed between the synusia of graphene oxide matrix.
Composite wave-suction material of the present invention includes ferrite particle, grain size≤100nm of the ferrite particle, into one
Step is preferably 20~100nm, more preferably 30~60nm；In the present invention, the ferrite particle is supported on the oxidation stone
Between mertenyl body surface face and the synusia of graphene oxide matrix；The synusia spacing of the graphene oxide matrix is small, only on a small quantity
Ferrite particle is distributed between the synusia of graphene oxide matrix.
In the present invention, graphene oxide matrix, ferrite particle, nano nickel and nickelous carbonate in the composite wave-suction material
Mass ratio be preferably 1~2:0.5~3:1~30:8~20, further preferably 1~2:0.5~3:1~30:10~15, more
Preferably 1~2:1.5:10~20:10.
The present invention also provides the preparation methods of composite wave-suction material described in above-mentioned technical proposal, include the following steps:
(1) iron chloride, nano-nickel powder, surfactant, urea and ethylene glycol are mixed, obtains mixed liquor；
(2) mixed liquor that the step (1) obtains is mixed with graphene oxide, carries out hydro-thermal reaction, obtains hydro-thermal
Reaction material liquid；
(3) supernatant for removing the hydro-thermal reaction feed liquid that the step (2) obtains carries out remaining feed liquid centrifugation and washes successively
It washs and dries, obtain composite wave-suction material.
The present invention mixes iron chloride, nano-nickel powder, surfactant, urea and ethylene glycol, obtains mixed liquor.At this
In invention, the grain size of the nano-nickel powder is consistent with the grain size of nano nickel in composite wave-suction material described in above-mentioned technical proposal,
This is repeated no more.In the present invention, the surfactant preferably includes polyvinylpyrrolidone.The present invention is to the chlorination
Iron, nano-nickel powder, surfactant, urea and ethylene glycol source there is no particular/special requirement, it is ripe using those skilled in the art institute
The commercial goods known.In the present invention, the quality of the iron chloride, nano-nickel powder, surfactant, urea and ethylene glycol
Than being preferably 1.1:(0.5~4):2:4:(30~60), further preferably 1.1:(1~3):2:4:(35~55), more preferably
It is 1.1:1:2:4:45.
In the present invention, the mixing of the iron chloride, nano-nickel powder, surfactant, urea and ethylene glycol preferably comprises
Following steps:Iron chloride, surfactant and urea are added in ethylene glycol, 30~50min of ultrasonic disperse, it is mixed to obtain first
Close feed liquid；Nano-nickel powder is added in first mixed liquor, continues 30~50min of ultrasonic disperse, obtains mixed liquor.
The present invention does not have particular/special requirement, use well known to those skilled in the art the ultrasonic disperse frequency of the different mix stages
, can realize being sufficiently mixed for feed liquid.In the present invention, the ethylene glycol not only acts as certain reduction,
So that ferric ion is converted to ferrous ion in hydrothermal reaction process, dispersant effect is also acted as so that each component is abundant
Mixing.
After obtaining mixed liquor, the present invention mixes the mixed liquor with graphene oxide, carries out hydro-thermal reaction, obtains
Hydro-thermal reaction feed liquid.In the present invention, the graphene oxide and the mass ratio preferably (1 for preparing mixed liquor iron chloride
~2):11, further preferably (1.2~1.7):11, more preferably (1.4~1.5):11.
In the present invention, the preparation method of the graphene oxide preferably comprises following steps:
(I) graphite powder, potassium permanganate, sodium nitrate, the concentrated sulfuric acid and orthophosphoric acid are mixed, obtains mixed liquor；
(II) mixed liquor for obtaining the step (I) carries out Primary Oxidation reaction, obtains just oxidation reaction feed liquid；It is described
The temperature of Primary Oxidation reaction is 50~60 DEG C, and the time of reaction is 12h；
(III) hydrogen peroxide is added in the first oxidation reaction feed liquid obtained to the step (II), carries out reoxidizing reaction, obtains
To reoxidizing reaction material liquid；
(IV) reaction material liquid that reoxidizes that the step (III) obtains is centrifuged, obtains graphene oxide.
In the present invention, the graphite powder, potassium permanganate, sodium nitrate, the concentrated sulfuric acid and ortho-phosphoric mass ratio are preferably 1:
(2~3):(1~2):(90~110):(10~18), further preferably 1:(2.2~2.5):(1.2~1.5):(95~
100):(12~15)；The mass fraction of the concentrated sulfuric acid is preferably 98%, and the ortho-phosphoric mass concentration is preferably
1.685g/mL.In the present invention, the grain size of the graphite powder is preferably 10~20 μm, further preferably 12~18 μm, more excellent
It is selected as 15~16 μm.The present invention is not special to the graphite powder, potassium permanganate, sodium nitrate, the concentrated sulfuric acid and ortho-phosphoric source
It is required that using commercial goods well-known to those skilled in the art.The present invention is to the graphite powder, potassium permanganate, nitric acid
Sodium, the concentrated sulfuric acid and ortho-phosphoric hybrid mode do not have particular/special requirement, using feed liquid mixing side well-known to those skilled in the art
Formula；In an embodiment of the present invention, specific by the way of ultrasonic disperse.
After obtaining mixed liquor, the mixed liquor is preferably carried out Primary Oxidation reaction by the present invention, obtains just oxidation reaction material
Liquid.In the present invention, the temperature of the Primary Oxidation reaction is preferably 50~60 DEG C, further preferably 52~58 DEG C, more excellent
It is selected as 55 DEG C；The time of the Primary Oxidation reaction is preferably 12h.In the present invention, the Primary Oxidation reaction is in high-pressure section
It is carried out under part；Primary Oxidation reaction pressure preferably≤6MPa, further preferably 1~5Mpa.In the present invention, described first
Oxidation reaction carries out preferably in the autoclave with polytetrafluoroethyllining lining.The present invention was reacted in the Primary Oxidation
Cheng Zhong, oxidizing graphite powder, oxygen atom enter graphite layers, are combined with pi-electron, to destroy pi bond in layer, and in graphite
The oxygen-containing functional groups such as carbonyl, carboxyl are formed on alkene lamella, form graphene oxide.
The present invention controls the pressure condition of the temperature and Primary Oxidation reaction of the Primary Oxidation, can avoid conventional oxidation
In graphene preparation process, the temperature of oxidation reaction hot stage is hot close to the sulfuric acid caused by 100 DEG C-compound between graphite layers
Decomposition reaction occupies leading position, instead of OH-With HSO4 -Displacement reaction, Intercalation reaction object is rapidly from sulfuric acid-graphite linings at this time
Between deviate from, H2SO4The graphite-structure of molecule intercalation will be reduced, and cause hydrone and OH-It cannot be introduced into graphite layers and form oxygen
The problem of graphite alkene；The control of the mild association reaction pressure of reaction temperature of the present invention improves the degree of oxidation of graphite, promotes oxygen
The acquisition of graphite alkene.
After the Primary Oxidation reaction, preferably hydrogen peroxide is added into the obtained first oxidation reaction feed liquid in the present invention,
It carries out reoxidizing reaction, obtains reoxidizing reaction material liquid.In the present invention, the preparation just oxidation reaction feed liquid graphite powder and
The mass ratio of hydrogen peroxide is preferably 1:2~3；The mass fraction of the hydrogen peroxide is preferably 30%.In the present invention, the dioxygen
The addition rate of water is preferably 5~10mL/min, avoids reaction excessively fierce.The present invention reoxidizes reaction process described,
Hydrogen peroxide reacts with remaining potassium permanganate, removes remaining potassium permanganate.
It is described reoxidize reaction after, the present invention preferably by it is described obtain reoxidize reaction material liquid carry out centrifuge washing, obtain
To graphene oxide.In the present invention, the centrifuge washing is preferably deionized water with cleaning solution；The washing of the centrifuge washing
Number is preferably 5~8 times；Lower layer's feed liquid before each centrifuge washing after a centrifuge washing as washings is waited for, successively into
The multiple centrifuge washing of row, using lower layer's feed liquid after last centrifuge washing i.e. as graphene oxide.The present invention washes the centrifugation
The specific implementation mode washed does not have particular/special requirement, using well-known to those skilled in the art.
After the centrifuge washing, lower layer's feed liquid after the centrifuge washing is preferably carried out ultrasonic disperse by the present invention in water
Afterwards, it is dried, obtains graphene oxide.The present invention does not have particular/special requirement to the ultrasonic disperse and dry mode, with reality
Now remove the purpose of impurity and moisture.
After obtaining mixed liquor and graphene oxide, the present invention mixes the mixed liquor and graphene oxide, carries out
Hydro-thermal reaction obtains hydro-thermal reaction feed liquid.In the present invention, the ultrasound that is mixed into of the mixed liquor and graphene oxide is mixed
It closes；The time of the ultrasonic mixing is preferably 30min；The present invention does not have particular/special requirement to the frequency of the ultrasonic mixing, uses
It is well-known to those skilled in the art.In the present invention, the temperature of the hydro-thermal reaction is preferably 170~200 DEG C, into one
Preferably 175~190 DEG C, more preferably 180~185 DEG C of step；The time of the hydro-thermal reaction is preferably 18~for 24 hours, further
Preferably 20~22h.For the present invention in the hydrothermal reaction process, urea provides carbonate and hydroxyl, Fe3+In hydro-thermal reaction
In generated under the reduction of ethylene glycol a part Fe2+, Fe3+With Fe2+It is combined with hydroxyl and generates ferrite, nano nickel
There are a small amount of oxidative phenomenas on surface, generate a certain amount of nickelous carbonate.Surfactant plays in the process prevents reunion
Effect, increases the interfacial effect of material, reinforcing material absorbing property.
After the hydro-thermal reaction, the present invention removal obtained by the hydro-thermal reaction feed liquid supernatant, to remaining feed liquid according to
Secondary progress centrifuge washing and drying, obtain composite wave-suction material.
After the hydro-thermal reaction, after the hydro-thermal reaction feed liquid is preferably cooled to room temperature by the present invention, then remove acquired
The supernatant of the hydro-thermal reaction feed liquid.The composite material that the present invention generates in the hydro-thermal reaction sinks under the effect of gravity
Drop, forms supernatant and lower layer settles feed liquid.The present invention does not have particular/special requirement to the removing method of the supernatant, using ability
The mode of separation supernatant and lower layer's sedimentation feed liquid known to field technique personnel；In an embodiment of the present invention, specially will
The mode that supernatant is poured out from reaction vessel.
After removing the supernatant, the present invention carries out centrifuge washing and drying successively to remaining feed liquid, obtains composite wave-absorbing
Material.In the present invention, the centrifuge washing is preferably absolute ethyl alcohol with cleaning solution；The number of the centrifuge washing is preferably 3
~5 times.The present invention does not have particular/special requirement, use well known to those skilled in the art the specific implementation mode of the centrifuge washing
, can fully remove remaining ethylene glycol and surfactant.After the centrifuge washing, the present invention is to the centrifuge washing
Solid is dried afterwards, obtains composite wave-suction material.In the present invention, the temperature of the drying is preferably 70~90 DEG C；It is described
The dry time is preferably 12~for 24 hours；The drying is preferably dried in vacuo, and the vacuum drying vacuum degree is preferably -0.6
~0.8MPa.
Composite wave-suction material provided by the invention and preparation method thereof is described in detail with reference to embodiment, but
It is that they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
According to mass ratio 1:3:2:110:18, graphite powder, potassium permanganate, sodium nitrate, the concentrated sulfuric acid and orthophosphoric acid are weighed,
In, it is 98% that the quality of the concentrated sulfuric acid, which crushes, and ortho-phosphoric mass concentration is 1.685g/mL；Then by graphite powder, potassium permanganate,
Sodium nitrate, the concentrated sulfuric acid and orthophosphoric acid ultrasonic mixing it is uniform after, mixed liquor is added to the autoclave of polytetrafluoroethyllining lining
In, insulation reaction 12h under the conditions of 50 DEG C.After products therefrom cooling, according to original graphite powder and hydrogen peroxide 1:2 mass ratio
Hydrogen peroxide (mass fraction of hydrogen peroxide is 30%) is slowly added to the rate of 10mL/min thereto, liquid becomes glassy yellow.
Mixing liquid after reaction is multiple through distilling water washing by the way of centrifugation, and supernatant is outwelled in washing every time, then to residue
Liquid continues centrifuge washing, and after washing repeatedly, lower layer is graphene oxide；Finally graphene oxide is dispersed in water, is surpassed
Sound 4 hours, it is spare after being dried using vacuum drying chamber.
Iron chloride 1.1g, polyvinylpyrrolidone 2g, urea 4g are weighed, is added in the ethylene glycol solvent of 45mL, ultrasound
30min；Nano-nickel powder 1g is weighed again, is added in ultrasonic mixing solution, is continued ultrasound 30min, is obtained mixed liquor.Weigh oxygen
Graphite alkene 0.1g is added in mixed liquor, and the autoclave of polytetrafluoroethyllining lining is then added to after ultrasonic mixing is uniform
In, keep the temperature 12 hours in 200 DEG C of air dry oven.
It is then cooled to room temperature, pours out the supernatant in polytetrafluoroethyllining lining, by lower liquid by way of centrifugation
It is washed 3~5 times through absolute ethyl alcohol.Then, the sample after washing is put into vacuum drying chamber and is dried in vacuo 24 hours for 80 DEG C, obtained
To composite wave-suction material powder.
Obtained composite wave-suction material powder is subjected to SEM morphology observations, the results are shown in Figure 1, composite wave-suction material powder
End is Nano grade, is attached to containing lamellar graphene oxide and uniformly the ferroso-ferric oxide and nanometer of surface of graphene oxide
Nickel powder, nickelous carbonate；The size of ferroso-ferric oxide and nano-nickel powder is all in nanoscale；And high-visible in figure, ferroso-ferric oxide
With nano-nickel powder without apparent agglomeration.
XRD analysis is carried out to obtained composite wave-suction material, testing result is as shown in Figure 2.As shown in Figure 2, the present embodiment
Contain graphene oxide (RGO) and the ferroso-ferric oxide with spinel structure and nanometer in obtained composite wave-suction material
Nickel, nickelous carbonate, nickel, which has partly to react in hydro-thermal reaction, generates nickelous carbonate；Wherein contain in composite wave-suction material
7.2wt% graphene oxides.
The composite wave-suction material that the present embodiment is obtained is with paraffin with 3:2 mass ratio mixing, mold is inserted by mixture
In, the electromagnetic parameter of composite wave-suction material is measured using HP 8722ES vector network analyzers, wherein Fig. 3 is composite wave-absorbing material
The reflectance curve when thickness is 2.35mm is expected, when the matching thickness of this absorbing material is 2.35mm, in 13.92GHz
When reach absorption maximum -10.16dB, effective absorption band of the reflection loss less than -10dB reaches 0.17GHz.
Embodiment 2
According to mass ratio 1:2:1:90:10, weigh graphite powder, potassium permanganate, sodium nitrate, the concentrated sulfuric acid and orthophosphoric acid, wherein
It is 98% that the quality of the concentrated sulfuric acid, which crushes, and ortho-phosphoric mass concentration is 1.685g/mL；Then by graphite powder, potassium permanganate, nitric acid
Sodium, the concentrated sulfuric acid and orthophosphoric acid ultrasonic mixing it is uniform after, mixed liquor is added in the autoclave of polytetrafluoroethyllining lining,
Insulation reaction 12h under the conditions of 60 DEG C.After products therefrom cooling, according to original graphite powder and hydrogen peroxide 1:2 mass ratio to its
In hydrogen peroxide (mass fraction of hydrogen peroxide be 30%) is slowly added to the rate of 10mL/min, liquid becomes glassy yellow.It will be anti-
Mixing liquid after answering is multiple through distilling water washing by the way of centrifugation, and supernatant is outwelled in washing every time, then to remaining liq
Continue centrifuge washing, after washing repeatedly, lower layer is graphene oxide；Finally graphene oxide is dispersed in water, ultrasound 4 is small
When, it is spare after being dried using vacuum drying chamber.
Iron chloride 1.1g, polyvinylpyrrolidone 2g, urea 4g are weighed, is added in the ethylene glycol solvent of 45mL, ultrasound
30min；Nano-nickel powder 1g is weighed again, is added in ultrasonic mixing solution, is continued ultrasound 30min, is obtained mixed liquor.Weigh oxygen
Graphite alkene 0.2g is added in mixed liquor, and the autoclave of polytetrafluoroethyllining lining is then added to after ultrasonic mixing is uniform
In, keep the temperature 12 hours in 200 DEG C of air dry oven.
It is then cooled to room temperature, pours out the supernatant in polytetrafluoroethyllining lining, by lower liquid by way of centrifugation
It is washed 3~5 times through absolute ethyl alcohol.Then, the sample after washing is put into vacuum drying chamber and is dried in vacuo 24 hours for 80 DEG C, obtained
To composite wave-suction material powder.
Obtained composite wave-suction material powder is subjected to SEM morphology observations, the results are shown in Figure 4, composite wave-suction material powder
End is Nano grade, is attached to containing lamellar graphene oxide and uniformly the ferroso-ferric oxide and nanometer of surface of graphene oxide
Nickel powder, nickelous carbonate；The size of ferroso-ferric oxide and nano-nickel powder is all in nanoscale；And high-visible in figure, ferroso-ferric oxide
With nano-nickel powder and nickelous carbonate without apparent agglomeration.Wherein in composite wave-suction material stone is aoxidized containing 13.5wt%
Black alkene.
The composite wave-suction material containing 13.5wt% graphene oxides that the present embodiment is obtained is with paraffin with 3:2 quality
Than mixing, mixture is inserted in mold, the electromagnetism that composite wave-suction material is measured using HP 8722ES vector network analyzers is joined
Number, wherein Fig. 5 is reflectance curve of the composite wave-suction material when thickness is 2.25mm, when the matching of this absorbing material is thick
When degree is 2.25mm, absorption maximum -15.16dB is reached in 14.88GHz, reflection loss is less than effective absorption band of -10dB
Up to 4GHz, inhales wave frequency band and significantly widen, wave-sucking performance enhancing.
Comparative example 1
Composite wave-suction material is prepared in the way of embodiment 2, difference lies in do not add nano-nickel powder, obtain inhaling wave material
Material.
The absorbing material that this comparative example is obtained is with paraffin with 3:2 mass ratio mixing, mixture is inserted in mold, is made
The electromagnetic parameter of nanometer ferrite is measured with HP 8722ES vector network analyzers, wherein Fig. 6 is composite wave-suction material in thickness
Reflectance curve when degree is 2.4mm, it is maximum anti-in 14.09GHz when the matching thickness of this absorbing material is 2.4mm
It is only -11.21dB to penetrate loss, and effective absorption band of the reflection loss less than -10dB is only 1.70GHz, it is seen that is not added with nickel powder
Absorbing material suction wave frequency band and maximum reflection loss be respectively less than graphene/ferroso-ferric oxide/nano-nickel powder composite wave-absorbing material
Expect suction wave frequency bandwidth angle value detected under equal conditions.
As seen from the above embodiment, the present invention adheres to upper ferrite particle in surface of graphene oxide, and passes through nano nickel
Powder compound modified, the polynary composite wave-suction material of the mechanism that is absorbed, absorbability and frequency bandwidth have clear improvement.
Preparation method provided by the invention is simple, can be produced by one step hydro thermal method ferritic while in graphite oxide
The load on alkene surface, while upper nano-nickel powder is loaded, realize the diversification of mechanism.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of nickeliferous composite wave-suction material, including lamellar graphene oxide matrix, ferrite particle, nano nickel and carbonic acid
Nickel；The ferrite particle, nano nickel and nickelous carbonate are supported between the graphene oxide matrix surface and synusia.
2. nickeliferous composite wave-suction material according to claim 1, which is characterized in that the graphene oxide contains 3~5 layers
Lamella；The grain size of the nano nickel is 20~100nm；Grain size≤100nm of the ferrite particle.
3. nickeliferous composite wave-suction material according to claim 1 or 2, which is characterized in that the graphene oxide matrix, iron
The mass ratio of oxysome, nano nickel and nickelous carbonate is 1~2:0.5~3:1~30:8~20.
4. the preparation method of any one of claims 1 to 3 nickeliferous composite wave-suction material, includes the following steps:
(1) iron chloride, nano-nickel powder, surfactant, urea and ethylene glycol are mixed, obtains mixed liquor；
(2) mixed liquor that the step (1) obtains is mixed with graphene oxide, carries out hydro-thermal reaction, obtains hydro-thermal reaction
Feed liquid；
(3) supernatant for removing the hydro-thermal reaction feed liquid that the step (2) obtains, remaining feed liquid is carried out successively centrifuge washing and
It is dry, obtain composite wave-suction material.
5. preparation method according to claim 4, which is characterized in that iron chloride, nano-nickel powder, table in the step (1)
The mass ratio of face activating agent, urea and ethylene glycol is 1.1:(0.5~4):2:4:(30~60).
6. preparation method according to claim 4 or 5, which is characterized in that the surfactant includes polyvinyl pyrrole
Alkanone.
7. preparation method according to claim 4, which is characterized in that in the step (2), graphene oxide and preparation are mixed
The mass ratio for closing feed liquid iron chloride is (1~2):11.
8. the preparation method according to claim 4 or 7, which is characterized in that the temperature of hydro-thermal reaction is in the step (2)
170~200 DEG C, time of hydro-thermal reaction is 18~for 24 hours.
9. preparation method according to claim 4, which is characterized in that the preparation method of the graphene oxide includes:
(I) graphite powder, potassium permanganate, sodium nitrate, the concentrated sulfuric acid and orthophosphoric acid are mixed, obtains mixed liquor；
(II) mixed liquor for obtaining the step (I) carries out Primary Oxidation reaction, obtains just oxidation reaction feed liquid；It is described first
The temperature of oxidation reaction is 50~60 DEG C, and the time of reaction is 12h；
(III) hydrogen peroxide is added in the first oxidation reaction feed liquid obtained to the step (II), carries out reoxidizing reaction, obtains again
Oxidation reaction feed liquid；
(IV) reaction material liquid that reoxidizes that the step (III) obtains is centrifuged, obtains graphene oxide.
10. preparation method according to claim 4, which is characterized in that graphite powder, potassium permanganate, nitre in the step (I)
Sour sodium, the concentrated sulfuric acid and ortho-phosphoric mass ratio are 1:(2~3):(1~2):(90~110):(10~18)；The concentrated sulfuric acid
Mass fraction is 98%, and the ortho-phosphoric mass concentration is 1.685g/mL；
The grain size of the graphite powder is 10~20 μm；
In the step (III), it is 1 to prepare the just mass ratio of oxidation reaction feed liquid graphite powder and hydrogen peroxide:(2~3)；It is described
The mass fraction of hydrogen peroxide is 30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810140557.3A CN108342183B (en) | 2018-02-11 | 2018-02-11 | A kind of nickeliferous composite wave-suction material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810140557.3A CN108342183B (en) | 2018-02-11 | 2018-02-11 | A kind of nickeliferous composite wave-suction material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108342183A true CN108342183A (en) | 2018-07-31 |
| CN108342183B CN108342183B (en) | 2019-07-16 |
Family
ID=62958856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810140557.3A Active CN108342183B (en) | 2018-02-11 | 2018-02-11 | A kind of nickeliferous composite wave-suction material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108342183B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114071982A (en) * | 2021-09-27 | 2022-02-18 | 兰州大学 | Honeycomb reduced graphene oxide foam/nickel nanoparticle wave absorbing agent and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658144A (en) * | 2012-05-16 | 2012-09-12 | 东华大学 | Graphene oxide interlayer supported nano cobalt oxide catalyst and preparation method thereof |
| CN103400967A (en) * | 2013-07-18 | 2013-11-20 | 上海交通大学 | Three-dimensional porous cobalt-based/graphene composite material and preparation method thereof |
| CN103450845A (en) * | 2013-08-28 | 2013-12-18 | 张宇 | Preparation method of wave-absorbing material |
| CN103571432A (en) * | 2013-11-22 | 2014-02-12 | 北京理工大学 | Ferrite hollow sphere-graphene composite wave-absorbing material and preparation method thereof |
| CN104209531A (en) * | 2013-05-31 | 2014-12-17 | 北京化工大学 | Cobalt/graphene composite nano wave-absorbing material and preparation method thereof |
| CN104310381A (en) * | 2014-09-28 | 2015-01-28 | 北京理工大学 | Method for on-scale continuous production of three-dimensional graphene membrane and application |
| CN105032430A (en) * | 2015-08-05 | 2015-11-11 | 万华化学集团股份有限公司 | Method for preparing eggshell type Co-Ni-Fe@SiO2 catalyst, prepared catalyst and application thereof |
-
2018
- 2018-02-11 CN CN201810140557.3A patent/CN108342183B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658144A (en) * | 2012-05-16 | 2012-09-12 | 东华大学 | Graphene oxide interlayer supported nano cobalt oxide catalyst and preparation method thereof |
| CN104209531A (en) * | 2013-05-31 | 2014-12-17 | 北京化工大学 | Cobalt/graphene composite nano wave-absorbing material and preparation method thereof |
| CN103400967A (en) * | 2013-07-18 | 2013-11-20 | 上海交通大学 | Three-dimensional porous cobalt-based/graphene composite material and preparation method thereof |
| CN103450845A (en) * | 2013-08-28 | 2013-12-18 | 张宇 | Preparation method of wave-absorbing material |
| CN103571432A (en) * | 2013-11-22 | 2014-02-12 | 北京理工大学 | Ferrite hollow sphere-graphene composite wave-absorbing material and preparation method thereof |
| CN104310381A (en) * | 2014-09-28 | 2015-01-28 | 北京理工大学 | Method for on-scale continuous production of three-dimensional graphene membrane and application |
| CN105032430A (en) * | 2015-08-05 | 2015-11-11 | 万华化学集团股份有限公司 | Method for preparing eggshell type Co-Ni-Fe@SiO2 catalyst, prepared catalyst and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| YU.S.DEDKOV: "Structural and electronic properties of Fe3O4/graphene/Ni(111)junctions", 《PHYS.STATUS SOLIDI RRL》 * |
| 刘子瑜: "点击反应制备RGO/钴铁氧体复合吸波材料的研究", 《中国优秀硕士学位论文全文数据库（电子期刊），工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114071982A (en) * | 2021-09-27 | 2022-02-18 | 兰州大学 | Honeycomb reduced graphene oxide foam/nickel nanoparticle wave absorbing agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108342183B (en) | 2019-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111629575B (en) | Preparation method of MXene-based nano composite wave-absorbing material | |
| CN108034408B (en) | Preparation method of graphene-based composite wave-absorbing material | |
| CN110790316B (en) | Iron oxide-nitrogen doped carbon micron tube composite wave-absorbing material and preparation method thereof | |
| CN101179921B (en) | Method for preparing electromagnetic shielding light graphite based nanometer magnetic metal composite material | |
| CN113697863B (en) | Ferroferric oxide/carbon nanosheet composite material with excellent electromagnetic wave absorption performance and preparation method and application thereof | |
| CN108307614B (en) | One kind composite wave-suction material containing cobalt and preparation method thereof | |
| CN112375541A (en) | Nitrogen-doped graphene nickel ferrite composite wave-absorbing material and preparation method thereof | |
| CN107338024A (en) | A kind of Co Fe alloys/carbon ball composite microwave absorbent and preparation method thereof | |
| CN111704115A (en) | A granular α -Fe2O3Preparation of Fe having microwave absorbing Properties4Method of N | |
| CN105384146A (en) | Graphene-loaded nanometer Fe<3>O<4>/ZnO composite and preparation method thereof | |
| CN104673185A (en) | Method for preparing reduced graphene oxide/CoFe2O4/Ag composite wave-absorbing material | |
| CN111154455A (en) | Boron-doped mesoporous flower-like ferroferric oxide/carbon composite wave-absorbing material and preparation method thereof | |
| CN117998830B (en) | Preparation method of functional reduced graphene oxide/metal-polyphenol framework composite aerogel | |
| CN107454815B (en) | Cu2O/MWCNTs composite material, preparation method and electromagnetic wave absorption application | |
| CN108342183B (en) | A kind of nickeliferous composite wave-suction material and preparation method thereof | |
| CN111014711B (en) | Porous napped NiFe/C/Na2MoO4Composite wave-absorbing material and preparation method thereof | |
| CN113512274A (en) | Modified graphene oxide and preparation method and application thereof | |
| CN110028930B (en) | HalS-Fe3O4@ C composite material and preparation method and application thereof | |
| CN113438883B (en) | Preparation method and application of binary heterostructure wave-absorbing material molybdenum oxide-molybdenum phosphide | |
| CN108192565A (en) | A kind of preparation method of nano combined absorbing material | |
| CN108393088B (en) | Preparation method of gamma-ferric oxide/rGO composite material with flower-like microsphere structure | |
| CN113597247A (en) | Magnetic metal nanoparticle modified carbon hollow sphere wave-absorbing material and preparation method thereof | |
| CN109627488A (en) | Graphene composite Nano Fe3O4Material obsorbing radar waves and preparation method thereof | |
| WO2023197954A1 (en) | High-entropy alloy sulfide/two-dimensional nano composite material, preparation method therefor, and application thereof | |
| CN114498068A (en) | MOFs derived carbon-coated ferrite wave-absorbing material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |