CN109704306A - A kind of N doping magnetism carbon-based composite wave-absorbing material and preparation method thereof - Google Patents
A kind of N doping magnetism carbon-based composite wave-absorbing material and preparation method thereof Download PDFInfo
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- CN109704306A CN109704306A CN201910078229.XA CN201910078229A CN109704306A CN 109704306 A CN109704306 A CN 109704306A CN 201910078229 A CN201910078229 A CN 201910078229A CN 109704306 A CN109704306 A CN 109704306A
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Abstract
The invention discloses a kind of preparation methods of magnetic carbon-based composite wave-absorbing material, comprising: prepare precast body: resin precursor and magnetic metal salt are mixed, the compound of magnetic metal oxide and resin is obtained as precast body by hydro-thermal reaction, wherein, the resin precursor contains nitrogen so that containing nitrogen in the resin of the precast body；And roast the precast body: by the precast body in the mixed gas of hydrogen and protective gas, in 600 DEG C of -700 DEG C of sintering, so that the magnetic metal oxide is reduced to metallic particles, and the resin is made to be converted into the carbon-based material of N doping.Compared to the prior art, resin precursor and magnetic metal salt are directly mixed with precast body, simple process by the preparation method of magnetic carbon-based composite wave-absorbing material of the invention；Moreover, because roasting in hydrogen and protective gas, the magnetic carbon-based composite wave-absorbing material of the carbon-based material composition of metallic particles and N doping can be obtained under 600 DEG C -700 DEG C of sintering temperature.
Description
Technical field
The present invention relates to nanocomposite research field, in particular to a kind of absorbing material and preparation method.
Background technique
In numerous materials, carbon material is because of its excellent dielectric properties, good composite attribute, relatively small density,
It is widely studied as absorbing material.Carbon-based absorbing material have it is corrosion-resistant, anti-oxidant, thermal expansion coefficient is low, have both inhale wave with
The various aspects advantage such as enhancing structure intensity, has broad application prospects.It is traditional as the absorbing material with application value
Carbon material is not met by requirement, and introducing defect or pore structure all in carbon material is the effective hand for enhancing carbon material absorbing property
One of section, it is a kind of effective method for introducing defect that other atoms are adulterated in carbon material, in addition, by carbon material
The impedance matching of material can be enhanced in the middle pore structure that introduces, and then guarantees that the loss characteristic of carbon composite wood plays, and realizes and improves
The absorbing property of material.It is now recognized that pure carbon material only leans on dielectric polarization loss decaying to realize the absorption of electromagnetic wave, therefore, separately
A kind of thinking of absorbing property promoting carbon material is that magnetic loss is introduced in carbon material, researcher usually by ferromagnetic material with
The compound method of carbon material come realize carbon material have magnetic loss ability.There is presently no a kind of methods to draw in carbon material
When entering hetero atom and pore structure, while it is dispersed in ferromagnetic metallic granular system in carbon material.
For example, mixing in the prior art with resin precursor and metal Fe salt, precast body is obtained by hydro-thermal reaction.So
Afterwards, by precast body high-temperature calcination under argon atmosphere, to obtain Fe/C or Fe-Fe3C@C particle.This method is since it is desired that benefit
It by the redox of the iron of lossless ability is the stronger Zero-valent Iron of magnetic loss ability with the reproducibility of carbon itself, it is necessary to by temperature
It is set as 900 DEG C of high temperature, because of high-temperature process, the reserved of carbon can be reduced, and carbon is easier to send out with the iron restored
Raw effect forms more by-products, in addition, the iron restored has catalytic action to the graphitization of carbon at high temperature, makes carbon
Degree of graphitization is higher, and material itself is without introducing hetero-atoms in addition, so the impedance matching of material is poor, electromagnetic wave can not
Into composite inner, material loss ability is made to be difficult to play, composite material is finally made not show preferably to inhale
Wave effect.
In the Chinese patent application application No. is 201811022379.0, Chen Ping et al. discloses a kind of nitrogen-doped carbon packet
Cover the preparation method of magnetic nano-particle complex microsphere, comprising: step (1) synthetic glycerine metal precursor；It is prepared with step (2)
Nitrogen-doped carbon coated magnetic Nanocomposites microballoon.Wherein, step (1) includes: that 5- is added in every 25-200ml isopropanol
25ml glycerol or 10-50ml ethylene glycol after being thoroughly mixed uniformly, then 200-1000mg metal are added into above-mentioned solution
Salt stirs 5-10min to after completely dissolution under ultrasound condition, uniformly mixed solution is poured into reaction kettle, in 120-200
DEG C reaction temperature under react 6-18h, product is repeatedly centrifuged after reaction, alcohol is washed, washed solid product is put
Enter in baking oven and be dried, finally obtains glycerol metal precursor.Step (2) includes: to add in every 100ml deionized water
Enter 0.5-2.0g surfactant, after being uniformly dissolved, the glycerol metal precursor that 0.1-0.2g step (1) is prepared be added,
0.5-1.5h is stirred under ultrasound condition, and uniform suspension is mixed to formation；It is added that 0.1-0.4g is nitrogenous has into suspension again
Machine monomer after stirring 1-3h, then is added dropwise 10-20ml into above-mentioned system and shifts to an earlier date the oxygen that configured concentration is 0.1-0.4mol/L
Agent solution then proceedes to reaction 3-6h；To after reaction, solid product is repeatedly washed to washing lotion be it is colourless, be put into baking
Case is dried to obtain product；Product is uniformly distributed in ceramic Noah's ark, Noah's ark is placed in horizontal pipe furnace flat-temperature zone, lazy
Property protective atmosphere in, be warming up to 600-900 DEG C of calcining 0.5-4.0h, and coat magnetic with furnace natural cooling to get to nitrogen-doped carbon
Property Nanocomposites microballoon.However, the material of above method preparation is complex microsphere, pore structure can not be introduced in the material,
In the past research shows that introducing pore structure in material is also to adjust one of the effective means of Radar Absorbing Properties of Composites；In addition, the party
The complex microsphere kernel of method preparation is Fe3O4Particle, and it is unable to get Fe metallic particles, Fe3O4It is inverse spinel ferrite knot
Structure is limited by the Snoek limit, to the absorption of electromagnetic wave in low frequency, with Fe3O4Difference, since feeromagnetic metal has high saturation magnetic
Change by force, so ferromagnetic particle there can be the performance absorbed by force in high frequency, therefore the composite particles of this method preparation are in 2-18GHz
Absorbing property improve it is limited.Moreover, this method elder generation synthetic glycerine metal precursor, then by the glycerol metal precursor with contain
Nitrogen organic monomer reacts to obtain precast body, is finally sintered the precast body, complex process.
Summary of the invention
The present invention provides a kind of preparation method of the magnetic carbon-based composite wave-absorbing material of simple process.
A kind of preparation method of magnetism carbon-based composite wave-absorbing material comprising following steps:
It prepares precast body: resin precursor and magnetic metal salt is mixed, magnetic metal oxidation is obtained by hydro-thermal reaction
The compound of object and resin is as precast body, wherein the resin precursor contains nitrogen so that the precast body
Contain nitrogen in resin；And
Roast the precast body: by the precast body in the mixed gas of hydrogen and protective gas, in 600 DEG C of -700 DEG C of burnings
Knot, makes the magnetic metal oxide be reduced to metallic particles, and the resin is made to be converted into the carbon-based material of N doping.
Such as the preparation method of above-mentioned magnetic carbon base composite wave-absorbing material, wherein described the step of preparing precast body specifically wraps
It includes:
By 3- amino-phenol, hexa and FeCl3·6H2O is uniformly mixed in distilled water and obtains mixed solution；
The mixed solution is transferred in reaction kettle, is heated to obtaining after reacting 4-10 hours between 160 DEG C -220 DEG C anti-
Answer product；And
Fe is inlayed after the reaction product is cleaned and dried2O3The amido phenolic resin of nanoparticle.
Such as the preparation method of above-mentioned magnetic carbon base composite wave-absorbing material, wherein the 3- amino-phenol and FeCl3·6H2O
Molar ratio be 1:0.7-1:5.
Such as the preparation method of above-mentioned magnetic carbon base composite wave-absorbing material, wherein the 3- amino-phenol and hexa-methylene four
The molar ratio of amine is 1:0.3-1:1.
Such as the preparation method of above-mentioned magnetic carbon base composite wave-absorbing material, wherein the step of roasting precast body specifically wraps
It includes:
By embedding the Fe2O3The amido phenolic resin of nanoparticle is put into reaction chamber；
The air of the reaction chamber is discharged, and is continually fed into protection gas in the reaction chamber, with 1 DEG C/min -5 DEG C/min
Heating rate the reaction chamber is heated to 600 DEG C -700 DEG C；
Open hydrogen and protect the mixing air valve switch of gas, Xiang Suoshu reaction chamber is passed through gaseous mixture, in gaseous mixture hydrogen with
It protects the volume ratio of gas within the scope of 4%:96% to 10%:90%, maintains such mixed atmosphere in 600 DEG C of -700 DEG C of reactions
- 6 hours 2 hours；
And cooling, mixing air valve switch is closed in temperature-fall period.
Such as the preparation method of above-mentioned magnetic carbon base composite wave-absorbing material, wherein the protective gas is nitrogen or indifferent gas
Body.
Such as the preparation method of above-mentioned magnetic carbon base composite wave-absorbing material, wherein the magnetic metal salt is ferric sulfate, sulfuric acid
One of cobalt, nickel sulfate, ferric nitrate, cobalt nitrate, nickel nitrate, iron chloride, cobalt chloride and nickel chloride or combinations thereof.
A kind of magnetic carbon-based composite wave-absorbing material prepared using the above method, by carbon-based material and multiple is dispersed in
Magnetic-particle composition in carbon-based material；Wherein, the carbon-based material is the carbon-based material of N doping and the magnetic-particle is
Metallic particles.
Such as above-mentioned magnetic carbon base composite wave-absorbing material, wherein the carbon-based material is network-like skeleton, and the metal
Grain is embedded in the network-like skeleton.
Such as above-mentioned magnetic carbon base composite wave-absorbing material, wherein the metallic particles is Fe particle, Co particle and Ni particle
One of or it is a variety of.
Compared to the prior art, the preparation method of magnetic carbon-based composite wave-absorbing material of the invention is directly by resin precursor
Precast body, simple process are mixed with magnetic metal salt；Moreover, because roasted in hydrogen and protective gas, it can be 600
The magnetic carbon-based composite wave-absorbing material of the carbon-based material composition of metallic particles and N doping is obtained under DEG C -700 DEG C of sintering temperature.
Other features and advantages of the present invention will be illustrated in the following description, also, partly becomes from specification
It obtains it is clear that understand through the implementation of the invention.The objectives and other advantages of the invention can be by written explanation
Specifically noted structure is achieved and obtained in book, claims and attached drawing.
Below by drawings and examples, technical scheme of the present invention will be described in further detail.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Figure 1A is the XRD test result of precast body prepared by the embodiment of the present invention 1.
Figure 1B is the XRD test result of magnetic carbon-based composite wave-absorbing material prepared by the embodiment of the present invention 1.
Fig. 1 C is the transmission electron microscope photo of precast body prepared by the embodiment of the present invention 1.
Fig. 1 D is the transmission electron microscope photo of magnetic carbon-based composite wave-absorbing material prepared by the embodiment of the present invention 1.
Fig. 1 E is the hysteresis loop figure of magnetic carbon-based composite wave-absorbing material prepared by the embodiment of the present invention 1.
Fig. 1 F is the absorbing property curve graph of magnetic carbon-based composite wave-absorbing material prepared by the embodiment of the present invention 1.
Fig. 1 G is that the x-ray photoelectron spectroscopy (XPS) of magnetic carbon-based composite wave-absorbing material prepared by the embodiment of the present invention 1 is surveyed
Test result.
Fig. 1 H is that power spectrum test result is swept in the face of magnetic carbon-based composite wave-absorbing material prepared by the embodiment of the present invention 1.
Fig. 2A -2F is the test result of precast body prepared by the embodiment of the present invention 2 and magnetic carbon-based composite wave-absorbing material, tool
Body test content is corresponding with Figure 1A -1F of embodiment 1.
Fig. 3 A-3F is the test result of precast body prepared by the embodiment of the present invention 3 and magnetic carbon-based composite wave-absorbing material, tool
Body test content is corresponding with Figure 1A -1F of embodiment 1.
Fig. 4 A-4F is the test result of precast body prepared by the embodiment of the present invention 4 and magnetic carbon-based composite wave-absorbing material, tool
Body test content is corresponding with Figure 1A -1F of embodiment 1.
Fig. 5 A-5F is the test result of precast body prepared by the embodiment of the present invention 5 and magnetic carbon-based composite wave-absorbing material, tool
Body test content is corresponding with Figure 1A -1F of embodiment 1.
Fig. 6 A-6F is the test result of precast body prepared by the embodiment of the present invention 6 and magnetic carbon-based composite wave-absorbing material, tool
Body test content is corresponding with Figure 1A -1F of embodiment 1.
Fig. 7 is the XRD test result of the magnetic carbon-based composite wave-absorbing material of comparative example 1 of the present invention preparation.
Fig. 8 is the transmission electron microscope photo of the magnetic carbon-based composite wave-absorbing material of comparative example 1 of the present invention preparation.
Fig. 9 is the absorbing property curve graph of the magnetic carbon-based composite wave-absorbing material of comparative example 1 of the present invention preparation.
Figure 10 is the XRD test result of the magnetic carbon-based composite wave-absorbing material of comparative example 2 of the present invention preparation.
Figure 11 is the absorbing property curve graph of the magnetic carbon-based composite wave-absorbing material of comparative example 2 of the present invention preparation.
Figure 12 is the XRD test result of the magnetic carbon-based composite wave-absorbing material of comparative example 3 of the present invention preparation.
Figure 13 is the absorbing property curve graph of the magnetic carbon-based composite wave-absorbing material of comparative example 3 of the present invention preparation.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Embodiment 1
Measuring 80mL distilled water makes its temperature be stably maintained at 30 DEG C.Successively dissolve 2mmol 3- amino-phenol (3-AP),
The FeCl of the hexa (HMT) of 0.57mmol, 1.4mmol3·6H2O is in distilled water.It mechanical stirring 2 hours, is formed
Stablizing solution.The solution is transferred into the reaction kettle of 100mL polytetrafluoroethylliner liner and seals it.Reaction kettle is put into
In baking oven hydro-thermal reaction 4 hours at a temperature of 160 DEG C, taken out after cooled to room temperature.Filter separation sample, a large amount of water elution
Sample to washing lotion is neutrality, and then sample is placed in convection oven with 60 DEG C of dry 8h, and obtaining loading has the particle size to be
The Fe of 40nm2O3The netted amido phenolic resin of particle is as precast body.Above-mentioned precast body is placed in quartz boat, by quartz boat
It is placed in tube furnace.Argon gas is passed through the air discharge in tube furnace and into the tube furnace as protecting gas, and with 1 DEG C/
The heating rate of minute is by the diamond heating to 650 DEG C.Then hydrogen threshold switch is opened, hydrogen is passed through and protects the mixed of gas
Gas is closed, and guarantees that the volume ratio of hydrogen and argon gas is 5%:95% in the gaseous mixture being passed through, and heat preservation 4 is small at a temperature of 650 DEG C
When, gaseous mixture is continually fed into insulating process.Then cool down, uniformly inlayed the netted carbon material of Fe nanometer particles.It should
Inlay the i.e. magnetic carbon-based composite wave-absorbing material of netted carbon material of Fe nanometer particles.In temperature-fall period, closes hydrogen valve and open
It closes.Figure 1A -1H is the test result of precast body prepared by the embodiment of the present invention 1 and magnetic carbon-based composite wave-absorbing material.Figure 1A is
The XRD test result of precast body.Figure 1B is the XRD test result of magnetic carbon-based composite wave-absorbing material.Fig. 1 C is the saturating of precast body
Penetrate electromicroscopic photograph.Fig. 1 D is the transmission electron microscope photo of magnetic carbon-based composite wave-absorbing material.Fig. 1 E is magnetic carbon-based composite wave-absorbing material
The hysteresis loop figure of material.Fig. 1 F is the absorbing property curve graph of magnetic carbon-based composite wave-absorbing material.Fig. 1 G is magnetic carbon-based compound
X-ray photoelectron spectroscopy (XPS) test result of absorbing material.Fig. 1 H is that power spectrum survey is retouched in the face of magnetic carbon-based composite wave-absorbing material
Test result.
By Figure 1A -1F as it can be seen that in the present embodiment, when 3- amino-phenol: FeCl3·6H2When O=1:0.7, obtained APF tree
Rouge load has Fe2O3Nanoparticle.The microstructure of gained Fe/C composite material is iron nanometer after mixed gas is heat-treated
Uniform particle is embedded within carbon material, and wherein Fe nanometer particles particle size is 40-100nm.Fe/C composite material is satisfied
It is 15.5emu/g with the intensity of magnetization, matching thickness 1.85mm, minimal reflection loss is -65.7dB, and effective Absorber Bandwidth is
5.5GHz.By Fig. 1 G-1H as it can be seen that the carbon-based material of the Fe/C composite material is the carbon-based material of N doping.
Embodiment 2
Measuring 80mL distilled water makes its temperature be stably maintained at 30 DEG C.Successively dissolve 2mmol 3- amino-phenol (3-AP),
The FeCl of the hexa (HMT) of 0.67mmol, 2mmol3·6H2O is in distilled water.It mechanical stirring 2 hours, is formed steady
Determine solution.The solution is transferred into the reaction kettle of 100mL polytetrafluoroethylliner liner and seals it.Reaction kettle is put into baking
In case hydro-thermal reaction 4 hours at a temperature of 160 DEG C, taken out after cooled to room temperature.Separation sample is filtered, a large amount of water elute sample
Product to washing lotion is neutrality, and then sample is placed in convection oven with 60 DEG C of dry 8h, obtains load to have particle size being 40nm
Fe2O3The netted amido phenolic resin of particle is as precast body.Above-mentioned precast body is placed in quartz boat, quartz boat is placed in
In tube furnace.
Argon gas is passed through as protection gas using the air discharge in tube furnace and into the tube furnace, and with 1 DEG C/min
Heating rate is by the diamond heating to 650 DEG C.Then hydrogen threshold switch is opened, hydrogen is passed through and protects the gaseous mixture of gas,
And guarantee that the volume ratio of hydrogen and argon gas is 5%:95% in the gaseous mixture being newly passed through, and keep the temperature 4 hours at a temperature of 650 DEG C,
Hydrogen is continually fed into insulating process.Then cool down, uniformly inlayed the netted carbon material of Fe nanometer particles.This is inlayed
The netted carbon material of Fe nanometer particles is magnetic carbon-based composite wave-absorbing material.In temperature-fall period, mixing air valve switch is closed.
Fig. 2A -2F is the test result of precast body prepared by the embodiment of the present invention 2 and magnetic carbon-based composite wave-absorbing material.Figure
2A is the XRD test result of precast body.Fig. 2 B is the XRD test result of magnetic carbon-based composite wave-absorbing material.Fig. 2 C is precast body
Transmission electron microscope photo.Fig. 2 D is the transmission electron microscope photo of magnetic carbon-based composite wave-absorbing material.Fig. 2 E is magnetic carbon-based compound suction
The hysteresis loop figure of wave material.Fig. 2 F is the absorbing property curve graph of magnetic carbon-based composite wave-absorbing material.
By Fig. 2A -2F as it can be seen that in the present embodiment, when 3- amino-phenol: FeCl3·6H2When O=1:1, obtained APF resin
Load has Fe2O3Nanoparticle.Gained Fe/C composite material, wherein Fe nanometer particles particle after mixed gas is heat-treated
Having a size of 50-200nm.The saturation magnetization of Fe/C composite material is 16.3emu/g, matching thickness 3.55mm, and minimum is anti-
Penetrating loss is -50.2dB, and effective Absorber Bandwidth is 4.7GHz.
Embodiment 3
Measuring 80mL distilled water makes its temperature be stably maintained at 30 DEG C.Successively dissolve 2mmol 3- amino-phenol (3-AP),
The FeCl of the hexa (HMT) of 1mmol, 4mmol3·6H2O is in distilled water.Mechanical stirring 2 hours, formation was stablized molten
Liquid.The solution is transferred into the reaction kettle of 100mL polytetrafluoroethylliner liner and seals it.Reaction kettle is put into baking oven
Hydro-thermal reaction 4 hours, takes out after cooled to room temperature at a temperature of 160 DEG C.Separation sample is filtered, a large amount of water elution samples are extremely
Washing lotion is neutrality, and then sample is placed in convection oven with 60 DEG C of dry 8h, obtains load to have particle size being 40nm's
Fe2O3The netted amido phenolic resin of particle is as precast body.Above-mentioned precast body is placed in quartz boat, quartz boat is placed in pipe
In formula furnace.Argon gas is passed through as protection gas using the air discharge in tube furnace and into the tube furnace, and with 1 DEG C/min
Heating rate is by the diamond heating to 650 DEG C.Then mixing air valve switch is opened, gaseous mixture is passed through, and guarantees newly to be passed through
Gaseous mixture in the volume ratio of hydrogen and argon gas be 5%:95%, and keep the temperature 4 hours at a temperature of 650 DEG C, held in insulating process
It is continuous to be passed through hydrogen.Then cool down, uniformly inlayed the netted carbon material of Fe nanometer particles.This inlays Fe nanometer particles
Netted carbon material is magnetic carbon-based composite wave-absorbing material.In temperature-fall period, hydrogen threshold switch is closed.
Fig. 3 A-3F is the test result of precast body prepared by the embodiment of the present invention 3 and magnetic carbon-based composite wave-absorbing material.Figure
3A is the XRD test result of precast body.Fig. 3 B is the XRD test result of magnetic carbon-based composite wave-absorbing material.Fig. 3 C is precast body
Transmission electron microscope photo.Fig. 3 D is the transmission electron microscope photo of magnetic carbon-based composite wave-absorbing material.Fig. 3 E is magnetic carbon-based compound suction
The hysteresis loop figure of wave material.Fig. 3 F is the absorbing property curve graph of magnetic carbon-based composite wave-absorbing material.
By Fig. 3 A-3F as it can be seen that in the present embodiment, when 3- amino-phenol: FeCl3·6H2When O=1:2, obtained APF resin
Load has Fe2O3Nanoparticle.Gained Fe/C composite material, wherein Fe nanometer particles particle after mixed gas is heat-treated
Having a size of 400nm.The saturation magnetization of Fe/C composite material is 20.4emu/g, matching thickness 3.88mm, minimal reflection damage
Consumption is -70.1dB, and effective Absorber Bandwidth is 3.76GHz.
Embodiment 4
Measuring 80mL distilled water makes its temperature be stably maintained at 30 DEG C.Successively dissolve 2mmol 3- amino-phenol (3-AP),
The FeCl of the hexa (HMT) of 1.33mmol, 6mmol3·6H2O is in distilled water.It mechanical stirring 2 hours, is formed steady
Determine solution.The solution is transferred into the reaction kettle of 100mL polytetrafluoroethylliner liner and seals it.Reaction kettle is put into baking
In case hydro-thermal reaction 4 hours at a temperature of 160 DEG C, taken out after cooled to room temperature.Separation sample is filtered, a large amount of water elute sample
Product to washing lotion is neutrality, and then sample is placed in convection oven with 60 DEG C of dry 8h, obtains load to have particle size being 40nm
Fe2O3The netted amido phenolic resin of particle is as precast body.Above-mentioned precast body is placed in quartz boat, quartz boat is placed in
In tube furnace.Argon gas is passed through as protection gas using the air discharge in tube furnace and into the tube furnace, and with 1 DEG C/min
Heating rate by the diamond heating to 650 DEG C.Then hydrogen threshold switch is opened, gaseous mixture is passed through, and guarantees newly to be passed through
Gaseous mixture in the volume ratio of hydrogen and argon gas be 5%:95%, and keep the temperature 4 hours at a temperature of 650 DEG C, held in insulating process
It is continuous to be passed through hydrogen.Then cool down, uniformly inlayed the netted carbon material of Fe nanometer particles.This inlays Fe nanometer particles
Netted carbon material is magnetic carbon-based composite wave-absorbing material.In temperature-fall period, hydrogen threshold switch is closed.
Fig. 4 A-4F is the test result of precast body prepared by the embodiment of the present invention 4 and magnetic carbon-based composite wave-absorbing material.Figure
4A is the XRD test result of precast body.Fig. 4 B is the XRD test result of magnetic carbon-based composite wave-absorbing material.Fig. 4 C is precast body
Transmission electron microscope photo.Fig. 4 D is the transmission electron microscope photo of magnetic carbon-based composite wave-absorbing material.Fig. 4 E is magnetic carbon-based compound suction
The hysteresis loop figure of wave material.Fig. 4 F is the absorbing property curve graph of magnetic carbon-based composite wave-absorbing material.
By Fig. 4 A-4F as it can be seen that in the present embodiment, when 3- amino-phenol: FeCl3·6H2When O=1:3, obtained APF resin
Load has Fe2O3Nanoparticle.Gained Fe/C composite material, wherein Fe nanometer particles particle after mixed gas is heat-treated
Having a size of 100-500nm.The saturation magnetization of Fe/C composite material is 12.2emu/g, matching thickness 1.74mm, and minimum is anti-
Penetrating loss is -48.6dB, and effective Absorber Bandwidth is 5.9GHz.
Embodiment 5
Measuring 80mL distilled water makes its temperature be stably maintained at 30 DEG C.Successively dissolve 2mmol 3- amino-phenol (3-AP),
The FeCl of the hexa (HMT) of 1.67mmol, 8mmol3·6H2O is in distilled water.It mechanical stirring 2 hours, is formed steady
Determine solution.The solution is transferred into the reaction kettle of 100mL polytetrafluoroethylliner liner and seals it.Reaction kettle is put into baking
In case hydro-thermal reaction 4 hours at a temperature of 160 DEG C, taken out after cooled to room temperature.Separation sample is filtered, a large amount of water elute sample
Product to washing lotion is neutrality, and then sample is placed in convection oven with 60 DEG C of dry 8h, obtains load to have particle size being 40nm
Fe2O3The netted amido phenolic resin of particle is as precast body.Above-mentioned precast body is placed in quartz boat, quartz boat is placed in
In tube furnace.Argon gas is passed through as protection gas using the air discharge in tube furnace and into the tube furnace, and with 1 DEG C/min
Heating rate by the diamond heating to 650 DEG C.Then hydrogen threshold switch is opened, is passed through hydrogen, and guarantee newly to be passed through
The volume ratio of hydrogen and argon gas is 5%:95%, and keeps the temperature 4 hours at a temperature of 650 DEG C, and hydrogen is continually fed into insulating process.
Then cool down, uniformly inlayed the netted carbon material of Fe nanometer particles.This inlays the netted carbon material of Fe nanometer particles
I.e. magnetic carbon-based composite wave-absorbing material.In temperature-fall period, mixing air valve switch is closed.
Fig. 5 A-5F is the test result of precast body prepared by the embodiment of the present invention 5 and magnetic carbon-based composite wave-absorbing material.Figure
5A is the XRD test result of precast body.Fig. 5 B is the XRD test result of magnetic carbon-based composite wave-absorbing material.Fig. 5 C is precast body
Transmission electron microscope photo.Fig. 5 D is the transmission electron microscope photo of magnetic carbon-based composite wave-absorbing material.Fig. 5 E is magnetic carbon-based compound suction
The absorbing property curve graph of wave material.Fig. 5 F is the hysteresis loop figure of magnetic carbon-based composite wave-absorbing material.
By Fig. 5 A-5F as it can be seen that in the present embodiment, when 3- amino-phenol: FeCl3·6H2When O=1:4, obtained APF resin
Load has Fe2O3Nanoparticle.Gained Fe/C composite material, wherein Fe nanometer particles particle after mixed gas is heat-treated
Having a size of 200-500nm.The saturation magnetization of Fe/C composite material is 27.4emu/g, matching thickness 2.57mm, and minimum is anti-
Penetrating loss is -67.1dB, and effective Absorber Bandwidth is 5.6GHz
Embodiment 6
Measuring 80mL distilled water makes its temperature be stably maintained at 30 DEG C.Successively dissolve 2mmol 3- amino-phenol (3-AP),
The FeCl of the hexa (HMT) of 2mmol, 10mmol3·6H2O is in distilled water.It mechanical stirring 2 hours, is formed and is stablized
Solution.The solution is transferred into the reaction kettle of 100mL polytetrafluoroethylliner liner and seals it.Reaction kettle is put into baking oven
In hydro-thermal reaction 4 hours at a temperature of 160 DEG C, taken out after cooled to room temperature.Separation sample is filtered, a large amount of water elute sample
It is neutrality to washing lotion, then sample is placed in convection oven with 60 DEG C of dry 8h, obtains load to have particle size being 40nm's
Fe2O3The netted amido phenolic resin of particle is as precast body.Above-mentioned precast body is placed in quartz boat, quartz boat is placed in pipe
In formula furnace.Argon gas is passed through as protection gas using the air discharge in tube furnace and into the tube furnace, and with 1 DEG C/min
Heating rate is by the diamond heating to 650 DEG C.Then hydrogen threshold switch is opened, is passed through gaseous mixture, and guarantee newly to be passed through
The volume ratio of hydrogen and argon gas is 5%:95% in gaseous mixture, and keeps the temperature 4 hours at a temperature of 650 DEG C, is continued in insulating process
It is passed through gaseous mixture.Then cool down, uniformly inlayed the netted carbon material of Fe nanometer particles.This inlays Fe nanometer particles
Netted carbon material is magnetic carbon-based composite wave-absorbing material.In temperature-fall period, mixing air valve switch is closed.
Fig. 6 A-6F is the test result of precast body prepared by the embodiment of the present invention 6 and magnetic carbon-based composite wave-absorbing material.Figure
6A is the XRD test result of precast body.Fig. 6 B is the XRD test result of magnetic carbon-based composite wave-absorbing material.Fig. 6 C is precast body
Transmission electron microscope photo.Fig. 6 D is the transmission electron microscope photo of magnetic carbon-based composite wave-absorbing material.Fig. 6 E is magnetic carbon-based compound suction
The absorbing property curve graph of wave material.Fig. 6 F is the hysteresis loop figure of magnetic carbon-based composite wave-absorbing material.
By Fig. 6 A-6F as it can be seen that in the present embodiment, 3- amino-phenol: FeCl3·6H2When O=1:5, obtained APF resin is negative
It is loaded with Fe2O3Nanoparticle.Gained Fe/C composite material, wherein Fe nanometer particles particle ruler after mixed gas is heat-treated
Very little is 50-500nm.The saturation magnetization of Fe/C composite material is 53.0emu/g, matching thickness 1.99mm, minimal reflection
Loss is -34.1dB, and effective Absorber Bandwidth is 3.7GHz.
The method of the embodiment of the present invention 1 to embodiment 6 is essentially identical, is distinguished as 3- amino-phenol and FeCl3·6H2O's
Ratio is different.Comparative example 1 is to embodiment 6 it is found that with FeCl3·6H2The content of O increases, and obtained magnetism is carbon-based compound
Fe nanoparticle content in absorbing material increases, and is accompanied by a small amount of Fe3C occurs, but Fe does not occur3O4Particle.
Embodiment 7
The embodiment of the present invention 7 is substantially the same manner as Example 1, the difference is that, the mixing that embodiment 7 is passed through in insulating process
The volume ratio of hydrogen and argon gas is 4%:96% in gas, and soaking time is 6 hours.In the present embodiment, at gaseous mixture body heat
The microstructure of gained Fe/C composite material is that Fe nanometer particles are uniformly embedded within carbon material after reason.Fe/C composite material
With apparent ferromagnetic property and good absorbing property.
Embodiment 8
The embodiment of the present invention 8 is substantially the same manner as Example 1, the difference is that, the mixing that embodiment 8 is passed through in insulating process
The volume ratio of hydrogen and argon gas is 10%:90% in gas, and soaking time is 2 hours.In the present embodiment, at gaseous mixture body heat
The microstructure of gained Fe/C composite material is that Fe nanometer particles are uniformly embedded within carbon material after reason.Fe/C composite material
With apparent ferromagnetic property and good absorbing property.
Embodiment 9
The embodiment of the present invention 9 is substantially the same manner as Example 1, the difference is that, the sintering temperature of embodiment 9 is 600 DEG C.This reality
It applies in example, the microstructure of gained Fe/C composite material is that Fe nanometer particles are uniformly embedded in after mixed gas is heat-treated
Within carbon material.Fe/C composite material has apparent ferromagnetic property and good absorbing property.
Embodiment 10
The embodiment of the present invention 10 is substantially the same manner as Example 1, the difference is that, the sintering temperature of embodiment 10 is 700 DEG C.This
In embodiment, the microstructure of gained Fe/C composite material is that Fe nanometer particles are uniformly inlayed after mixed gas is heat-treated
Within carbon material.Fe/C composite material has apparent ferromagnetic property and good absorbing property.
Comparative example 1
Comparative example 1 of the present invention is substantially the same manner as Example 1, the difference is that, the sintering atmosphere whole process of comparative example 1 is pure protection
Gas.Fig. 7-9 is the test result of the magnetic carbon-based composite wave-absorbing material of comparative example 1 of the present invention preparation.Fig. 7 is magnetic carbon-based multiple
Close the XRD test result of absorbing material.Fig. 8 is the transmission electron microscope photo of magnetic carbon-based composite wave-absorbing material.Fig. 9 is magnetic carbon-based
The absorbing property curve graph of composite wave-suction material.
Comparative example 2
Comparative example 2 and comparative example 1 of the present invention are essentially identical, the difference is that, the sintering temperature of comparative example 2 is 700 DEG C.Figure
10-11 is the test result of the magnetic carbon-based composite wave-absorbing material of comparative example 2 of the present invention preparation.Figure 10 is magnetic carbon-based compound suction
The XRD test result of wave material.Figure 11 is the absorbing property curve graph of magnetic carbon-based composite wave-absorbing material.
Comparative example 3
Comparative example 3 and comparative example 1 of the present invention are essentially identical, the difference is that, the sintering temperature of comparative example 3 is 800 DEG C.Figure
12-13 is the test result of the magnetic carbon-based composite wave-absorbing material of comparative example 3 of the present invention preparation.Figure 12 is magnetic carbon-based compound suction
The XRD test result of wave material.Figure 13 is the absorbing property curve graph of magnetic carbon-based composite wave-absorbing material.
Comparative example 3 and 1,2 comparisons can be seen that absorbing property declines to a great extent as temperature increases, this is primarily due to height
Warm treatment process will cause the loss of a large amount of nitrogen.
Referring to Fig. 7, a large amount of Fe is contained in the Fe/C composite material that comparative example 1 obtains3O4Particle, and part Fe particle
It reacts to form Fe with carbon3C.Comparison diagram 1D and Fig. 8 is as it can be seen that the Fe/C of the Fe/C composite material relatively example 1 of embodiment 1 is compound
Material microscopic appearance is almost the same, is that magnetic nano-particle is uniformly inlayed inside carbon material.Comparison diagram 1F and Fig. 9 is as it can be seen that reality
The Fe/C Composite Microwave absorption intensity for applying the Fe/C composite material relatively example 1 of example 1 is bigger, and effective Absorber Bandwidth is more
Width, matching thickness are thinner.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (10)
1. a kind of preparation method of magnetism carbon-based composite wave-absorbing material comprising following steps:
Prepare precast body: resin precursor and magnetic metal salt mixed, by hydro-thermal reaction obtain magnetic metal oxide with
The compound of resin is as precast body, wherein the resin precursor contain nitrogen so that the precast body resin
In contain nitrogen；And
It roasts the precast body: by the precast body in the mixed gas of hydrogen and protective gas, in 600 DEG C of -700 DEG C of sintering, making
The magnetic metal oxide is reduced to metallic particles, and the resin is made to be converted into the carbon-based material of N doping.
2. the preparation method of magnetism carbon-based composite wave-absorbing material as described in claim 1, which is characterized in that it is described prepare it is prefabricated
The step of body, specifically includes:
By 3- amino-phenol, hexa and FeCl3·6H2O is uniformly mixed in distilled water and obtains mixed solution；
The mixed solution is transferred in reaction kettle, is heated to obtaining reaction production after reacting 4-10 hours between 160 DEG C -220 DEG C
Object；And
Fe is inlayed after the reaction product is cleaned and dried2O3The amido phenolic resin of nanoparticle.
3. the preparation method of magnetism carbon-based composite wave-absorbing material as claimed in claim 2, which is characterized in that the 3- aminobenzene
Phenol and FeCl3·6H2The molar ratio of O is 1:0.7-1:5.
4. the preparation method of magnetism carbon-based composite wave-absorbing material as claimed in claim 2, which is characterized in that the 3- aminobenzene
The molar ratio of phenol and hexa is 1:0.3-1:1.
5. the preparation method of magnetism carbon-based composite wave-absorbing material as claimed in claim 2, which is characterized in that the roasting is prefabricated
The step of body, specifically includes:
By embedding the Fe2O3The amido phenolic resin of nanoparticle is put into reaction chamber；
The air of the reaction chamber is discharged, the reaction chamber is heated to 600 with 1 DEG C/min -5 DEG C/min of heating rate
DEG C -700 DEG C, and protection gas is continually fed into temperature-rise period into the reaction chamber；
It opens hydrogen and protects the mixing air valve switch of gas, Xiang Suoshu reaction chamber is passed through gaseous mixture, and guarantees the gaseous mixture being passed through
Middle hydrogen and protection gas volume ratio within the scope of 4%:96% to 10%:90%, and 600 DEG C -700 DEG C keep 2 hours -
6 hours；And
Mixing air valve switch is closed in cooling in temperature-fall period.
6. the preparation method of magnetism carbon-based composite wave-absorbing material as claimed in claim 5, which is characterized in that the protective gas
For nitrogen or inert gas.
7. the preparation method of magnetism carbon-based composite wave-absorbing material as described in claim 1, which is characterized in that the magnetic metal
Salt is one in ferric sulfate, cobaltous sulfate, nickel sulfate, ferric nitrate, cobalt nitrate, nickel nitrate, iron chloride, cobalt chloride and nickel chloride
Kind or combinations thereof.
8. it is a kind of using the method as described in claim 1 prepare magnetic carbon-based composite wave-absorbing material, by carbon-based material with
And multiple magnetic-particle compositions being dispersed in carbon-based material；It is characterized in that, the carbon-based material is the carbon substrate of N doping
Material and the magnetic-particle are metallic particles.
9. magnetism carbon-based composite wave-absorbing material as claimed in claim 8, which is characterized in that the carbon-based material is network-like bone
Frame, and the metallic particles is embedded in the network-like skeleton.
10. magnetism carbon-based composite wave-absorbing material as claimed in claim 9, which is characterized in that the metallic particles be Fe particle,
One of Co particle and Ni particle are a variety of.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110918060A (en) * | 2019-12-16 | 2020-03-27 | 扬州大学 | Pyrolytic carbon-loaded zero-valent iron composite material and preparation method and application thereof |
| CN113265223A (en) * | 2021-05-24 | 2021-08-17 | 西北工业大学 | Nitrogen-doped iron-carbon composite wave-absorbing material and preparation method and application thereof |
| CN114554817A (en) * | 2022-02-21 | 2022-05-27 | 厦门大学 | Preparation method of Fe/C composite material with wave-absorbing and sound-absorbing functions |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103908947A (en) * | 2014-04-03 | 2014-07-09 | 上海应用技术学院 | Preparation method of magnetic porous carbon/ ferric oxide nano composite material for oil-water separation |
| CN104300231A (en) * | 2014-10-23 | 2015-01-21 | 大连理工大学 | Method for wave absorbing material and application of wave absorbing material |
| CN105032355A (en) * | 2015-08-24 | 2015-11-11 | 东华大学 | Preparation method for core-shell structure type carbon-coated magnetic nano particles |
| CN107176598A (en) * | 2016-03-08 | 2017-09-19 | 中国科学院青岛生物能源与过程研究所 | A kind of N doping mesoporous carbon-loaded cobalt-oxidation cobalt nanocomposites and its preparation method and application |
| CN107887614A (en) * | 2017-10-30 | 2018-04-06 | 天津晨祥丰凯新材料科技有限公司 | The preparation method of carbon aerogel composite material |
| CN109014245A (en) * | 2018-09-03 | 2018-12-18 | 大连理工大学 | A kind of nitrogen-doped carbon coated magnetic Nanocomposites microballoon and preparation method thereof |
| CN109243853A (en) * | 2018-07-27 | 2019-01-18 | 青岛科技大学 | A method of height ratio capacity nanocomposite is prepared using double-template |
-
2019
- 2019-01-28 CN CN201910078229.XA patent/CN109704306A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103908947A (en) * | 2014-04-03 | 2014-07-09 | 上海应用技术学院 | Preparation method of magnetic porous carbon/ ferric oxide nano composite material for oil-water separation |
| CN104300231A (en) * | 2014-10-23 | 2015-01-21 | 大连理工大学 | Method for wave absorbing material and application of wave absorbing material |
| CN105032355A (en) * | 2015-08-24 | 2015-11-11 | 东华大学 | Preparation method for core-shell structure type carbon-coated magnetic nano particles |
| CN107176598A (en) * | 2016-03-08 | 2017-09-19 | 中国科学院青岛生物能源与过程研究所 | A kind of N doping mesoporous carbon-loaded cobalt-oxidation cobalt nanocomposites and its preparation method and application |
| CN107887614A (en) * | 2017-10-30 | 2018-04-06 | 天津晨祥丰凯新材料科技有限公司 | The preparation method of carbon aerogel composite material |
| CN109243853A (en) * | 2018-07-27 | 2019-01-18 | 青岛科技大学 | A method of height ratio capacity nanocomposite is prepared using double-template |
| CN109014245A (en) * | 2018-09-03 | 2018-12-18 | 大连理工大学 | A kind of nitrogen-doped carbon coated magnetic Nanocomposites microballoon and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JINGYA SONG ET AL.: ""Core-shell Co/CoNx@C nanoparticles enfolded by Co-N doped carbon nanosheets as a highly efficient electrocatalyst for oxygen reduction reaction"", 《CARBON》 * |
| TIANYU YANG ET AL.: ""A synthetic strategy for carbon nanospheres impregnated with highly monodispersed metal nanoparticles"", 《NPG ASIA MATERIALS》 * |
| 丁晓晖: ""自组装有机前驱体制备可控微孔碳分子筛微球与储氢性能研究"", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技1辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110918060A (en) * | 2019-12-16 | 2020-03-27 | 扬州大学 | Pyrolytic carbon-loaded zero-valent iron composite material and preparation method and application thereof |
| CN113265223A (en) * | 2021-05-24 | 2021-08-17 | 西北工业大学 | Nitrogen-doped iron-carbon composite wave-absorbing material and preparation method and application thereof |
| CN114554817A (en) * | 2022-02-21 | 2022-05-27 | 厦门大学 | Preparation method of Fe/C composite material with wave-absorbing and sound-absorbing functions |
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