CN107338023A - A kind of nano combined microwave absorption and preparation method thereof - Google Patents
A kind of nano combined microwave absorption and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of nano combined microwave absorption and preparation method thereof, belong to microwave absorbing material technical field, the nanometer microwave absorbent is formed mainly by the core shell structure of silicon dioxide coated nano ferroso-ferric oxide in graphene oxide layer.Its preparation process is as follows：(1) preparation of the core shell structure particle of silicon dioxide coated nano ferroso-ferric oxide；(2) preparation of amination modified coated with silica ferriferrous oxide nano-particle；(3) preparation of graphene oxide/silica/ferriferrous oxide nano microwave absorption.Nano combined microwave absorption of the present invention and preparation method thereof devises a kind of graphene oxide/silica/ferriferrous oxide nano microwave absorption and preparation method thereof.This absorbent specific surface area prepared by the present invention is big, and light weight, microwave absorption frequency is wide, and absorption maximum intensity is big, and chemical property is stable, has stronger applicability.
Description
Technical field
The present invention relates to a kind of nanometer microwave absorbent and preparation method thereof, more particularly to a kind of graphene oxide/dioxy
SiClx/ferriferrous oxide nano composite microwave absorbent and preparation method thereof, belongs to microwave absorbing material technical field.
Background technology
Microwave absorbing material is that one kind makes incident electromagnetic wave enter material internal, and can effectively attenuation by absorption enter
Radio magnetic wave, the one kind for converting it into the energy of the other forms such as heat energy and losing or make electromagnetic wave to be disappeared by interference
Functional material.The extensive use of microwave absorbing material, it is dirty to the electromagnetism that people's life is brought can to solve electronic product well
Dye problem.In addition, to adapt to the needs of modern war, stealth technology turns into the strategy that each military power of the world first develops
Emphasis, and also just ground as the core of stealth technology, the research and development of microwave absorbing material with application as war material field
The focus studied carefully.
Microwave absorbing material key component is absorbent, is secondly binding agent and relevant auxiliary agent.The suction of microwave absorbing material
Ripple performance depends primarily on absorbent and its preparation technology.Absorbent is the main body base-material of electromagnetic wave absorption, passes through specific work
Skill technology is prepared.
According to decay mechanism of the absorbent to electromagnetic wave, magnetic loss type and dielectric loss type can be divided into.
Main magnetic loss type absorbent is ferromagnet absorbent, and ferromagnetism absorbent is primarily referred to as ferrous alloy or iron
Oxysome, belong to magnetic material, because it has excellent magnetic loss performance, widely studied and applied as absorbent, its
Shortcoming is that proportion is larger, is oxidized easily.
Dielectric loss type absorbent mainly includes carbon fiber, carbon nano-tube material, in recent years, because of its special two-dimensional structure
And the features such as light weight, graphene are increasingly becoming more popular electrical loss absorbent, its shortcoming is that electromagnetic consumable rate is low.
Therefore, at present, the composite that electromagnetic consumable rate is high, absorption frequency range is wide, frivolous is researched and developed, is electromagnetic absorber
The emphasis of research field.
The content of the invention
An object of the present invention is to provide that a kind of specific surface area big, light weight, microwave absorption frequency be wide, absorption maximum
Intensity is big, chemical property is stable, the microwave absorption with stronger applicability.
To achieve the above object, the present invention takes following technical scheme：
A kind of nano combined microwave absorption, it is characterised in that：The component of the microwave absorption be graphene oxide,
The nano composite material of silica and ferroso-ferric oxide, the microwave absorption are the oxidation of silicon dioxide coated nano four three
The core shell structure of iron, in graphene oxide layer.
Preferably, the mass ratio of the graphene oxide, silica and ferroso-ferric oxide is 90：1：10-10： 9：90.
Preferably, the mass ratio of the graphene oxide, silica and ferroso-ferric oxide is 70：3：30.
Preferably, the mass ratio of the graphene oxide, silica and ferroso-ferric oxide is 50：5：50.
Preferably, the mass ratio of the graphene oxide, silica and ferroso-ferric oxide is 30：7：70.
It is a further object of the present invention to provide above-mentioned graphene oxide/silica/ferriferrous oxide nano microwave absorption
The preparation method of agent.
The above-mentioned purpose of the present invention reaches by the following technical programs：
A kind of preparation method of nano combined microwave absorption, comprises the following steps：
(1) preparation of the core shell structure particle of silicon dioxide coated nano ferroso-ferric oxide
Ferroferric oxide nano granules are weighed in right amount, are scattered in absolute ethyl alcohol, then ultrasonic disperse, obtain four oxygen
Change three-iron ethanol solution；Ferroso-ferric oxide ethanol solution after will be scattered is transferred in there-necked flask, adds TEOS (tetraethyl orthosilicate)
And NH3·H2O, it is sufficiently stirred reaction；After the completion of reaction, solution is washed repeatedly with absolute ethyl alcohol, until the solution after cleaning
No longer become cloudy；Obtained sediment, vacuum drying, coated with silica ferriferrous oxide nano-particle is obtained；
(2) preparation of amination modified coated with silica ferriferrous oxide nano-particle
The coated with silica ferriferrous oxide nano-particle for taking a certain amount of step (1) to prepare, activation, has been distributed to
In solvent, coated with silica ferriferrous oxide nano-particle activation dispersion liquid is obtained, adds KH550 (γ-aminopropyl
Triethoxysilane), it is sufficiently stirred reaction；Reaction is cooled to room temperature after terminating, then by centrifugation, washing, vacuum drying, obtains
To amination modified coated with silica ferriferrous oxide nano-particle；
(3) preparation of graphene oxide/silica/ferriferrous oxide nano microwave absorption
In the solvent of graphene oxide is dispersed with, amination modified coated with silica prepared by step (2) is added
Ferriferrous oxide nano-particle, EDAC (carbodiimide) and NHS (n-hydroxysuccinimide) is added, is sufficiently stirred reaction, mistake
Filter, wash, vacuum drying, obtain graphene oxide/silica/ferriferrous oxide nano microwave absorption.
Preferably, the concentration of ferroso-ferric oxide ethanol solution is 0.5mg/ml-10mg/ml described in the step (1).
Described ultrasonic disperse power is 150w-300w, and ultrasonic time is -6 hours 20 minutes.
Preferably, the TEOS added described in the step (1) amount is NH3·H2The 10%-80% of O mass；Add
NH3·H2O amount is the 50%-300% of ferroferric oxide nano granules quality.
Preferably, the rotating speed stirred described in the step (1) is 200 revs/min -800 revs/min, and reaction temperature is
20 DEG C -80 DEG C, the time is 1-24 hours.
Preferably, the rotating speed stirred described in the step (2) is 200 revs/min -800 revs/min, and reaction temperature is
20 DEG C -80 DEG C, the time is 1-24 hours.
Preferably, -150 DEG C of vacuum drying temperature 50 C described in the step (1) and step (2), time 8-
24 hours.
Preferably, the temperature activated described in the step (2) is 50 DEG C -120 DEG C, and the time is 1-10 hours.
Preferably, organic solvent described in the step (2) is ethanol, toluene or ethylene glycol.
Preferably, the coated with silica ferriferrous oxide nano-particle described in the step (2) activates dispersion liquid
Concentration is 0.5mg/ml-10mg/ml.
Preferably, the addition of KH550 described in the step (2) is coated with silica ferriferrous oxide nano grain
The 1%-20% of protonatomic mass.
Preferably, the reaction temperature of the addition KH550 described in the step (2) is 60 DEG C -85 DEG C, time 1-10
Hour.
Preferably, the solvent for being dispersed with graphene oxide described in the step (3) include water, ethanol, ethylene glycol or
Toluene.
Preferably, point of the solvent for being dispersed with graphene oxide described in the step (3) and graphene oxide composition
The concentration of dispersion liquid is 0.1mg/ml-5mg/ml.
Preferably, the addition of the graphene oxide described in the step (3) is the oxygen of amination coated with silica four
Change the 10%-900% of three Fe nanometer particles quality.
Preferably, the addition of the EDAC (carbodiimide) described in the step (3) is the 20%- of NHS mass
100%, EDAC and NHS gross weight are that graphene oxide and amination coated with silica ferriferrous oxide nano-particle are total
The 50%-150% of weight.
Advantages of the present invention：
Nano combined microwave absorption and preparation method thereof of the present invention devise a kind of graphene oxide/silica/
Ferriferrous oxide nano microwave absorption and preparation method thereof.This absorbent specific surface area prepared by the present invention is big, quality
Gently, microwave absorption frequency is wide, and absorption maximum intensity is big, and chemical property is stable, has stronger applicability.
Below by the drawings and specific embodiments, the present invention will be further described, but is not meant to the present invention
The limitation of protection domain.
Brief description of the drawings
Fig. 1 is graphene oxide, ferroferric oxide nano granules and graphene oxide/silica/ferroso-ferric oxide
Nano-absorbent XRD test charts.
Fig. 2-1 to Fig. 2-6 is respectively ferroferric oxide nano granules, coated with silica ferriferrous oxide nano-particle
And the transmissioning electric mirror test figure of graphene oxide/silica/ferriferrous oxide nano absorbent.
Fig. 3-1 to Fig. 3-4 is respectively graphene oxide, ferroferric oxide nano granules, the oxidation of coated with silica four three
The ELECTROMAGNETIC REFLECTION rate of Fe nanometer particles and graphene oxide/silica/ferriferrous oxide nano absorbent.
Embodiment
Embodiment 1：
A kind of preparation of graphene oxide/silica/ferriferrous oxide nano microwave absorption, its step are as follows：
(1) the commercially available ferroferric oxide nano granules of 100mg are weighed, are scattered in 200ml commercial anhydrous ethanol, Ran Houyong
150w ultrasonic disperse machines, ultrasonic disperse 1 hour, obtain ferroso-ferric oxide ethanol solution；Ferroso-ferric oxide ethanol after will be scattered
Solution is poured into there-necked flask, adds 25mg commercially available TEOS, 100mg commercially available NH3·H2O, with high speed agitator with 400 turns/
The rotating speed stirring of minute, reaction temperature are 35 DEG C, stirring reaction 1 hour；After the completion of reaction, by solution commercial anhydrous ethanol
Wash repeatedly, until the solution after cleaning no longer becomes cloudy；Obtained sediment, with vacuum drying chamber at 80 DEG C vacuum
Dry 12 hours, obtain 107mg coated with silica ferriferrous oxide nano-particles；
(2) by 100mg steps (1) obtained by coated with silica ferriferrous oxide nano-particle, activate 4 at 70 DEG C
Hour, it is distributed in the commercially available toluene of 100ml, adds the commercially available KH550 of 1mg, with high speed agitator with 400 revs/min of rotating speed
Stirring, reaction temperature are 80 DEG C, and stirring reaction 1 hour, reaction is cooled to room temperature after terminating, then by centrifugation, washing, with true
Empty drying box is dried in vacuo 12 hours at 80 DEG C, obtains the amination modified coated with silica ferroso-ferric oxides of 101mg
Nano-particle；
(3) in the 200ml water for being dispersed with the commercially available graphene oxides of 70mg, the amination that 30mg steps (2) obtain is added
Modified coated with silica ferriferrous oxide nano-particle, the commercially available EDAC of 25mg are added, the commercially available NHS of 50mg, use high-speed stirring
Mix device to stir with 400 revs/min of rotating speed, reaction temperature is 30 DEG C, stirring reaction 1 hour, filtering, washing, with vacuum drying
Case is dried in vacuo 12 hours at 80 DEG C, obtains 100mg graphene oxides/silica/ferriferrous oxide nano absorbent.
Embodiment 2：
A kind of preparation of graphene oxide/silica/ferriferrous oxide nano microwave absorption, its step are as follows：
(1) the commercially available ferroferric oxide nano granules of 100mg are weighed, are scattered in 100ml commercial anhydrous ethanol, Ran Houyong
200w ultrasonic disperse machines, ultrasonic disperse 3 hours, obtain ferroso-ferric oxide ethanol solution；Ferroso-ferric oxide ethanol after will be scattered
Solution is poured into there-necked flask, adds 30mg commercially available TEOS, 120mg commercially available NH3·H2O, with 500 revs/min of high speed agitator
Clock, reaction temperature are 45 DEG C, stirring reaction 4 hours；After the completion of reaction, solution is washed repeatedly with commercial anhydrous ethanol, until
Solution after cleaning no longer becomes cloudy；Obtained sediment, with vacuum drying chamber at 70 DEG C, it is dried in vacuo 15 hours, obtains
To 108mg coated with silica ferriferrous oxide nano-particles；
(2) by 100mg steps (1) obtained by coated with silica ferriferrous oxide nano-particle, activate 3 at 60 DEG C
Hour, it is distributed in the commercially available ethanol of 50ml, adds the commercially available KH550 of 5mg, with 500 revs/min of high speed agitator, reaction temperature
For 60 DEG C, stirring reaction 2 hours, reaction is cooled to room temperature after terminating, then by centrifugation, washing, with vacuum drying chamber at 70 DEG C
Lower vacuum drying 24 hours, obtains the amination modified coated with silica ferriferrous oxide nano-particles of 105mg；
(3) in the commercially available ethanol of 100ml of the commercially available graphene oxides of 50mg is dispersed with, add prepared by 50mg steps (2)
Amination modified coated with silica ferriferrous oxide nano-particle, the 30mg commercially available NHS of commercially available EDAC, 50mg are added, with height
Fast 500 revs/min of agitator, reaction temperature are 30 DEG C, stirring reaction 24 hours, filtering, washing, with vacuum drying chamber 70
It is dried in vacuo 15 hours at DEG C, obtains 100mg graphene oxides/silica/ferriferrous oxide nano absorbent.
Embodiment 3：
A kind of preparation of graphene oxide/silica/ferriferrous oxide nano microwave absorption, its step are as follows：
(1) weigh the commercially available ferroferric oxide nano granules of 100mg, be scattered in 70ml commercial anhydrous ethanol, Ran Houyong
250w ultrasonic disperse machines, ultrasonic disperse 2 hours, obtain ferroso-ferric oxide ethanol solution；Ferroso-ferric oxide ethanol after will be scattered
Solution is transferred in there-necked flask, adds the commercially available NH of 40mg commercially available TEOS, 140mg3·H2O, with 500 revs/min of high speed agitator, instead
It is 50 DEG C to answer temperature, stirring reaction 2 hours；After the completion of reaction, solution is washed repeatedly with commercial anhydrous ethanol, until cleaning
Solution afterwards no longer becomes cloudy；Obtained sediment, it is dried in vacuo 12 hours, is obtained at 90 DEG C with vacuum drying chamber
111mg coated with silica ferriferrous oxide nano-particles；
(2) by 100mg steps (1) obtained by coated with silica ferriferrous oxide nano-particle, activate 2 at 50 DEG C
Hour, it is distributed in the commercially available ethylene glycol of 70ml, adds the commercially available KH550 of 4mg, with 300 revs/min of high speed agitator, reaction temperature
Spend for 70 DEG C, stirring reaction 3 hours, reaction is cooled to room temperature after terminating, then by centrifugation, washing, is existed with vacuum drying chamber
It is dried in vacuo 8 hours at 120 DEG C, obtains the amination modified coated with silica ferriferrous oxide nano-particles of 104mg；
(3) in the commercially available toluene of 70ml of the commercially available graphene oxides of 30mg is dispersed with, add prepared by 70mg steps (2)
Amination modified coated with silica ferriferrous oxide nano-particle, the 35mg commercially available NHS of commercially available EDAC, 60mg are added, with height
Fast 500 revs/min of agitator, reaction temperature are 25 DEG C, stirring reaction 15 hours, filtering, washing, with vacuum drying chamber 80
It is dried in vacuo 24 hours at DEG C, obtains 100mg graphene oxides/silica/ferriferrous oxide nano absorbent.
Embodiment 4
A kind of preparation of graphene oxide/silica/ferriferrous oxide nano microwave absorption, its step are as follows：
(1) weigh the commercially available ferroferric oxide nano granules of 100mg, be scattered in 120ml commercial anhydrous ethanol, then
With 300w ultrasonic disperse machines, ultrasonic disperse 2 hours, ferroso-ferric oxide ethanol solution is obtained；Ferroso-ferric oxide second after will be scattered
Alcoholic solution is transferred in there-necked flask, adds the commercially available NH of 40mg commercially available TEOS, 140mg3·H2O, with 300 revs/min of high speed agitator,
Reaction temperature is 45 DEG C, stirring reaction 4 hours；After the completion of reaction, solution is washed repeatedly with commercial anhydrous ethanol, until clear
Solution after washing no longer becomes cloudy；Obtained sediment, it is dried in vacuo 8 hours, is obtained at 70 DEG C with vacuum drying chamber
111mg coated with silica ferriferrous oxide nano-particles；
(2) by 100mg steps (1) obtained by coated with silica ferriferrous oxide nano-particle, activate 8 at 80 DEG C
Hour, it is distributed in the commercially available ethanol of 80ml, adds the commercially available KH550 of 5mg, with 500 revs/min of high speed agitator, reaction temperature
For 85 DEG C, stirring reaction 4 hours, reaction is cooled to room temperature after terminating, then by centrifugation, washing, it is true with 60 DEG C of vacuum drying chamber
Sky is dried 10 hours, obtains the amination modified coated with silica ferriferrous oxide nano-particles of 105mg；
(3) in the commercially available ethylene glycol of 200ml of the commercially available graphene oxides of 70mg is dispersed with, add obtained by 30mg steps (2)
Amination modified coated with silica ferriferrous oxide nano-particle, the 25mg commercially available NHS of commercially available EDAC, 50mg are added, with height
Fast 400 revs/min of agitator, reaction temperature are 30 DEG C, stirring reaction 4 hours, filtering, washing, with vacuum drying chamber 150
It is dried in vacuo 8 hours at DEG C, obtains 100mg graphene oxide/silica/ferriferrous oxide nano absorbent.
The change of phase composition before and after compound is analyzed with X-ray diffraction (X-ray diffraction, XRD).With transmission
Electron microscope (Transmission Electron Microscope) observes compound pattern.Use microwave network analyzer
The electromagnetic parameter of microwave absorption is tested, and calculates ELECTROMAGNETIC REFLECTION rate of the microwave absorption in 2-18GHz.
Performance test：
1) combined multifunctional horizontal X-x ray diffractometer x (Ultima IV, Rigaku, Japan) test analysis oxidation is utilized
Graphene, ferroferric oxide nano granules and graphene oxide/silica/ferriferrous oxide nano absorber component become
Change, analysis condition is:Voltage 40KV, electric current 100mA, the θ of angle 2 are 2 ° -90 °.
To in embodiment 1-4, graphene oxide, ferroferric oxide nano granules and graphene oxide/titanium dioxide
Silicon/ferriferrous oxide nano absorbent carries out XRD component analyses, as a result as shown in figure 1, wherein, in Fig. 1 from top to bottom successively
For：The XRD spectrum of graphene oxide, the XRD spectrum of ferroferric oxide nano granules, the oxygen of graphene oxide/silica/tetra-
Change the XRD spectrum of three-iron nano-absorbent.
As can be seen from Figure 1：The XRD spectrum of graphene oxide, which is shown in 2 θ=11.8 °, sharp peak, corresponding to oxygen
(001) crystal face of graphite alkene.The XRD collection of illustrative plates of graphene oxide/silica/ferriferrous oxide nano absorbent shows peak
Appear at 30.3,35.7,43.4,53.7,57.1 and 62.8, the position at these peaks and pure ferroso-ferric oxide it is closely similar,
(220), (311), (400), (422), (511) and (440) crystal face (JCPDS of spinel-type ferroso-ferric oxide is corresponded to respectively
No.19-0629), class graphene-like structure (002) can be attributed in 23.2 ° of broad peaks, this shows graphene oxide major part
Oxygen-containing functional group be removed during embedded amination coated with silica ferroferric oxide nano granules.
2) with transmission electron microscope (Transmission Electron Microscope) observation compound pattern
To in embodiment 1-4, ferroferric oxide nano granules, coated with silica ferriferrous oxide nano-particle with
And graphene oxide/silica/ferriferrous oxide nano absorbent carries out transmission electron microscope morphology analysis, takes 10ul test specimens
Product dispersant liquid drop is added in BZ1101XX types micro-grid and supports film surface, and F20 types are selected with 200KV accelerating potential after natural drying
TEM characterizes the micromorphology of material, as shown in Fig. 2-1 to Fig. 2-6, is aoxidized for ferroso-ferric oxide, coated with silica four
The transmissioning electric mirror test figure of three Fe nanometer particles and graphene oxide/silica/ferriferrous oxide nano absorbent, its
In, Fig. 2-1 shows the TEM image (200nm resolution ratio) of ferroferric oxide nano granules, it may be seen that four oxidations three
Iron it is dispersed poor.Fig. 2-2 shows TEM image (the 200nm resolutions of coated with silica ferriferrous oxide nano-particle
Rate), silica significantly improves the dispersiveness of ferroso-ferric oxide.Fig. 2-3 shows the oxygen of graphene oxide/silica/tetra-
Change the amplification TEM image (50nm resolution ratio) of three-iron nano-absorbent, it can be seen that ferroso-ferric oxide ball is completely by porous knot
The Silica-coated of structure.Scheme from the low range TEM of graphene oxide/silica/ferriferrous oxide nano absorbent
(200nm/100nm resolution ratio) (resolution ratio that Fig. 2-4 resolution ratio is 200nm and Fig. 2-5 is 100nm), it can be seen that dioxy
SiClx coated ferriferrous oxide nano-particle is uniformly embedded on graphene oxide, and a diameter of the 20 of ferriferrous oxide nano-particle
~30nm, there is good dispersiveness.In addition, almost without discovery Fe3O4Nano particle is outside stannic oxide/graphene nano piece, table
Bright condensation reaction synthesis graphene oxide/silica/ferriferrous oxide nano absorbent efficiency is higher.Fig. 2-6 is four oxidations
The full resolution pricture (2nm resolution ratio) of three iron nano-particles, show that ferriferrous oxide nano-particle is mono-crystalline structures, lattice bar
Interplanar distance 0.484nm between line, corresponding corresponding (311) crystal face of (111) crystal face and 0.258nm.Can from transmission electron microscope picture
To find out this absorbent, because having graphene film Rotating fields, specific surface area is big, light weight；Due to silica pair
The cladding of ferroso-ferric oxide, make the ferroso-ferric oxide in material be not easy to be oxidized, add the applicability of absorbent.
3) the ELECTROMAGNETIC REFLECTION rate of microwave absorption is tested with microwave network analyzer
To in embodiment 1-4, graphene oxide, ferroferric oxide nano granules, coated with silica ferroso-ferric oxide
Nano-particle and graphene oxide/silica/ferriferrous oxide nano absorbent carry out ELECTROMAGNETIC REFLECTION rate analysis, use
The electromagnetic parameter of vector network analyzer (VNA, N5234A PAN-L, Agilent, the U.S.) analysis of material, test frequency scope
For 2-18GHz, as shown in figure 3-1, to dose ELECTROMAGNETIC REFLECTION rate of the graphene oxide as 5 mm of thickness samples of absorbent,
Maximum reflection loss is only -14.3dB at 7.7GHz；As shown in figure 3-2, inhaled to dose ferroferric oxide nano granules and being used as
The ELECTROMAGNETIC REFLECTION rate of 5 mm of thickness samples of agent is received, maximum reflection loss is 35.3dB in 9.6GHz；As shown in Fig. 3-3, it is
ELECTROMAGNETIC REFLECTION rate of the coated with silica ferriferrous oxide nano-particle as 5 mm of thickness samples of absorbent is dosed, it is maximum
Reflection loss is that 51.3dB is lost apparently higher than ferroso-ferric oxide in 8.9GHz, its maximum reflection.As shown in Figure 3-4, to dose
ELECTROMAGNETIC REFLECTION of the graphene oxide/silica/ferriferrous oxide nano absorbent as 4.5 mm of thickness samples of absorbent
Rate, maximum reflection loss are -56.4dB in 8.1GHz, suction of the reflection loss in -10dB (90% electromagnetic wave is absorbed) below
Take-up is wide to reach 4.1GHz (from 6.5 to 10.6GHz).As a result show：Graphene oxide/silica of the present invention/tetra- aoxidize
Three-iron nanometer microwave absorbent, it is wide with the reflection loss and absorption band bigger than graphene oxide and ferroso-ferric oxide, this
Kind of composite can the microwave absorption powerful as a kind of absorbent properties use.
Graphene oxide/silica/ferriferrous oxide nano composite of the present invention is as microwave absorption.Graphite
The electrical conductivity and thermal conductivity of alkene are high, and specific surface area is big, light weight, and these performances are advantageous to the absorption and decay of electromagnetic wave, iron oxygen
The introducing of body particle can strengthen the ferromagnetism of graphene, composite is had magnetic loss and electrical loss concurrently, be advantageously implemented electricity
Magnetic matches.The reflectance loss of ferroso-ferric oxide typically occurs in lower frequency ranges (＜ 10GHz), and graphite material is anti-
Penetrate rate loss and be usually located at high frequency region, therefore, two kinds of the compound of material also help widening for absorption band.Silica can
To improve the dispersiveness of ferroso-ferric oxide, and prevent the ferroso-ferric oxide in composite from being aoxidized in wet environment, carry
The applicability of high material.
Claims (10)
- A kind of 1. nano combined microwave absorption, it is characterised in that：The component of the microwave absorption is graphene oxide, dioxy The nano composite material of SiClx and ferroso-ferric oxide, the microwave absorption are the core of silicon dioxide coated nano ferroso-ferric oxide Shell structure, in graphene oxide layer.
- 2. nano combined microwave absorption as claimed in claim 1, it is characterised in that：The graphene oxide, silica Mass ratio with ferroso-ferric oxide is 90：1：10-10：9：90.
- 3. nano combined microwave absorption as claimed in claim 1, it is characterised in that：The graphene oxide, silica Mass ratio with ferroso-ferric oxide is 70：3：30；Or it is 50：5：50；Or it is 30：7：70.
- 4. the preparation method of nano combined microwave absorption, comprises the following steps as any one of claim 1-3：(1) preparation of the core shell structure particle of silicon dioxide coated nano ferroso-ferric oxideFerroferric oxide nano granules are weighed in proportion, are scattered in absolute ethyl alcohol, then ultrasonic disperse, obtain four oxidations three Iron ethanol solution；Ferroso-ferric oxide ethanol solution after will be scattered is transferred in there-necked flask, adds tetraethyl orthosilicate and NH3·H2O, It is sufficiently stirred reaction；After the completion of reaction, solution is washed repeatedly with absolute ethyl alcohol, until the solution after cleaning no longer becomes cloudy； Obtained sediment, vacuum drying, coated with silica ferriferrous oxide nano-particle is obtained；(2) preparation of amination modified coated with silica ferriferrous oxide nano-particleThe coated with silica ferriferrous oxide nano-particle for taking a certain amount of step (1) to prepare in proportion, activation, has been distributed to In solvent, coated with silica ferriferrous oxide nano-particle activation dispersion liquid is obtained, then be proportionally added into γ-aminopropyl Triethoxysilane, it is sufficiently stirred reaction；Reaction is cooled to room temperature after terminating, then by centrifugation, washing, vacuum drying, obtains Amination modified coated with silica ferriferrous oxide nano-particle；(3) preparation of graphene oxide/silica/ferriferrous oxide nano microwave absorptionIn the solvent for being dispersed with the graphene oxide being proportionally added into, amination modified dioxy prepared by step (2) is added SiClx coated ferriferrous oxide nano-particles, carbodiimide and n-hydroxysuccinimide are added, is sufficiently stirred reaction, filtered, Washing, vacuum drying, obtains graphene oxide/silica/ferriferrous oxide nano microwave absorption.
- 5. the preparation method of nano combined microwave absorption as claimed in claim 4, it is characterised in that：In the step (1) The concentration of the ferroso-ferric oxide ethanol solution is 0.5mg/ml-10mg/ml, and the ultrasonic power in the step (1) is 150w- 300w, ultrasonic time are -6 hours 20 minutes.
- 6. the preparation method of nano combined microwave absorption as claimed in claim 5, it is characterised in that：In the step (1) The amount of the tetraethyl orthosilicate (TEOS) of the addition is NH3·H2The 10%-80% of O amounts；The NH of addition3·H2O amount is four oxygen Change the 50%-300% of three iron nano-particle amounts；The rotating speed stirred described in the step (1) is 200 revs/min -800 revs/min Clock, reaction temperature are 20 DEG C -80 DEG C, and the time is 1-24 hours.
- 7. the preparation method of nano combined microwave absorption as claimed in claim 6, it is characterised in that：In the step (2) The rotating speed of the stirring is 200 revs/min -800 revs/min, and reaction temperature is 20 DEG C -80 DEG C, and the time is 1-24 hours.
- 8. the preparation method of nano combined microwave absorption as claimed in claim 7, it is characterised in that：The step (1) and - 150 DEG C of vacuum drying temperature 50 C described in step (2), time are 8-24 hours.
- 9. the preparation method of nano combined microwave absorption as claimed in claim 8, it is characterised in that：In the step (2) The temperature of the activation is 50 DEG C -120 DEG C, and the time is 1-10 hours；Organic solvent described in the step (2) is ethanol, first Benzene or ethylene glycol；The concentration of coated with silica ferriferrous oxide nano-particle activation dispersion liquid described in the step (2) For 0.5mg/ml-10mg/ml；The addition of γ-aminopropyl triethoxysilane is silica described in the step (2) The 1%-20% of coated ferriferrous oxide nano-particle quality；Addition γ-ethoxy of aminopropyl three described in the step (2) The reaction temperature of base silane is 60 DEG C -85 DEG C, and the time is 1-10 hours.
- 10. the preparation method of nano combined microwave absorption as claimed in claim 9, it is characterised in that：In the step (3) The described solvent for being dispersed with graphene oxide includes water, ethanol, ethylene glycol or toluene；It is scattered described in the step (3) The concentration for the dispersion liquid being made up of the solvent and graphene oxide of graphene oxide is 0.1mg/ml-5mg/ml；The step (3) Described in graphene oxide addition be amination coated with silica ferriferrous oxide nano-particle quality 10%- 900%；The addition of carbodiimide described in the step (3) is the 20%-100% of n-hydroxysuccinimide quality, The gross weight of carbodiimide and n-hydroxysuccinimide is graphene oxide and amination coated with silica ferroso-ferric oxide The 50%-150% of nano-particle gross weight.
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| CN115466596A (en) * | 2022-07-20 | 2022-12-13 | 哈尔滨工业大学 | Fe-Fe 3 O 4 @mSiO 2 @ RGO composite material and magnetic property controllable preparation method and application thereof |
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