CN102127392B - Preparation method of rare earth-doped ferrite-titanium dioxide/polythiophene/carbon nanotube microwave absorbent - Google Patents
Preparation method of rare earth-doped ferrite-titanium dioxide/polythiophene/carbon nanotube microwave absorbent Download PDFInfo
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Abstract
The invention discloses a preparation method of a rare earth-doped ferrite-titanium dioxide/polythiophene/carbon nanotube microwave absorbent. The preparation method comprises the following steps of: A, dissolving barium nitrate, ferric nitrate, neodymium nitrate and lanthanum nitrate into distilled water and stirring until the components are dissolved to obtain a clarified solution; B, adding citric acid into the solution in a metric ratio; C, putting a light-green solution into a water bath with the temperature of 70 DEG C and uniformly stirring; D, obtaining a black powdery doped ferrite-titanium dioxide composite; and E, preparing the rare earth-doped ferrite-titanium dioxide/polythiophene/carbon nanotube microwave absorbent. The method has the advantages that: rare earth elements are doped, so that the magnetocrystalline anisotropy field of ferrite crystals can be increased, the coercive force is enhanced, the magnetic hysteresis loss in an alternating electromagnetic field is increased, the average crystal grain size of the crystals is increased, the grain boundary resistivity is lowered, the overall resistivity of the crystals is lowered, the eddy-current loss is improved, and the domain wall resonance loss can be increased.
Description
Technical field
The present invention relates to a kind of preparation method of microwave absorption, relate in particular to the preparation method of a kind of rear-earth-doped ferrite-titanium dioxide/Polythiophene/carbon nanotube microwave absorption.
Background technology
Absorbing material is to absorb the electromagnetic wave energy that projects its surface, and changes a class material of heat energy into by the loss of material.Classify from loss mechanism, absorbing material can be divided into resistor-type, dielectric type and the large class of magneticmedium type 3.Under the same performance condition, ferrite is generally thin than dielectric medium wave-absorber, and good absorbing effect, cost are low, thereby is widely used, develops very fast.
At present, in the absorbing material of all multiple types, ferrite be study comparative maturity, use more a kind of absorbing material, the oxide compound that is composited with other one or more suitable metallic element that generally refers to iron group.It has higher magnetic permeability at high band, and assimilated efficiency is high, bandwidth, and preparation cost is low, has certain absorbing property.Ferrite comprises spinel type, carbuncle type and Magnetoplumbate-type, and they all have gyromagnetism, and this is the key property that absorbing material produces electromagnetic consumable.Many studies show that, best with the absorbing property of hexaplanar magneto-plumbite type ferrite in 3 kinds of ferrites, because the hexaplanar magneto-plumbite type ferrite has sheet structure, and sheet is the optimum shape that absorbs microwave.Secondly the hexaplanar magneto-plumbite type ferrite has the standby anisotropy equivalent field of higher magnetic, thereby higher natural resonant frequency is arranged.Natural resonance is the main mechanism of ferrite electromagnetic wave absorption.So-called natural resonance refers to ferrite in the situation that do not add outer permanent magnetic field, by the alternating magnetic field of incident and the magnetic anisotropy equivalent field H of crystal
kThe precessional resonance that acting in conjunction produces.As the angular frequency of alternating magnetic field and the magnetic anisotropy equivalent field H of crystal
kWhen the ω * k of the intrinsic radian frequency that determines equated, ferrite wave-absorbing material was with a large amount of electromagnetic wave absorptions.
Along with the development of nano material, the preparations of nanomaterials method is also more and more, has good absorbing property in order to guarantee ferrite.The method for preparing nanometer ferrite mainly contains: Physical and chemical method.Chemical method mainly contains: sol-gel method, chemical coprecipitation, hydrothermal synthesis method, microemulsion method, self propagating high temperature synthesis method, these methods compare with conventional iron oxysome preparation technology have less energy-consumption, the advantage such as non-environmental-pollution, high quality, the iron oxysome properties of powder of producing is stable, particle size distribution is even, can be used for making high performance ferrite component, has broad application prospects.
This M type barium ferrite is magneto-plumbite type ferrite, and symmetry is low, has very high magnetocrystalline anisotropy field H
A, utilize its natural resonance can obtain higher complex permeability, can utilize simultaneously the overlapping broadening absorption band of its natural resonance absorption peak,, there is bonding force between the two in compound by with titanium dioxide simultaneously, can strengthen ferritic magnetic loss.Therefore this ferrite doped calcium-titanium dioxide has good frequency response characteristic and absorbing property.Polythiophene is a kind of conducting polymer, by with carbon nanotube π-pi-conjugated, strengthen its dielectric loss ability, then compound with ferrite-titanium dioxide, advantage in conjunction with the three, can widen absorption band, improve absorbing property, thereby can satisfy the target of absorbing material desired " thin, light, wide, strong ", prepare the microwave absorbing material of superior performance.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of rear-earth-doped ferrite-titanium dioxide/Polythiophene/carbon nanotube microwave absorption, the ferrite microwave absorption of present stage preparation, have some defectives, requirement-bandwidth, the quality that is difficult to satisfy modern absorbing material is light, absorption is strong, thin thickness.The present invention is directed to the problems referred to above, developed a kind of compound microwave absorbing material, can effectively solve the present stage problem that faces of microwave absorbing material.
The present invention is achieved like this, major ingredient is nitrate of baryta, iron nitrate, neodymium nitrate and lanthanum nitrate, auxiliary material is thiophene monomer, titania gel, carbon nanotube, trichloromethane, citric acid, Anhydrous Ferric Chloride, wherein the mol ratio of citric acid and nitrate radical is 1:2, mole doping of neodymium is 0.02-0.07, mole doping of lanthanum is 0.03-0.06, the mass ratio of ferrite and titanium dioxide is 5:5, the mass ratio of ferrite-titanium dioxide compound and thiophene monomer is 0.4:1, and the mass ratio of carbon nanotube and thiophene monomer is 0.4:1;
Its preparation process is as follows:
A, nitrate of baryta, iron nitrate, neodymium nitrate and lanthanum nitrate are dissolved in distilled water, are stirred to dissolving, obtain settled solution;
B, the citric acid that will measure ratio add in mentioned solution, obtain brown-red solution, then slowly drip ammoniacal liquor, and at 8-9, solution becomes light green to the pH value of solution;
C, light green solution is placed in the water-bath of 70 ℃, until the moisture in solution evaporates fully, obtains the ferrite gel of viscosity 110cp, then with titania gel in mass ratio 5:5 mix, stir;
D, with the mixed gel self-propagating combustion, remove citric acid wherein, obtain the ferrite doped calcium of black-titanium dioxide compound precursor, then with precursor after calcining 3h under 1200 ℃, obtain the ferrite doped calcium-titanium dioxide compound of black powder shape;
E, with ferrite doped calcium-titanium dioxide compound, carbon nanotube and thiophene monomer in mass ratio joins in chloroform soln ultra-sonic oscillation 3h, they are mixed, then add Anhydrous Ferric Chloride, carry out the in situ chemical oxidation reaction in the ice bath of 0 ℃, reaction 20h;
After F, reaction are completed, with the solvent evaporate to dryness, pour the HCI solution of 2 mol/L under room temperature, stirring at room 20 h, suction filtration, water washing repeats 2-3 time, until the filtrate clarification will be deposited in 70 ℃ of lower vacuum-drying 24h, make rear-earth-doped ferrite-titanium dioxide/Polythiophene/carbon mano-tube composite.
The mol ratio of described barium and lanthanum is 1:(0.02-0.07), the mol ratio of barium and neodymium is 1:(0.03-0.06), the mass ratio of ferrite and titanium dioxide is 3:5, the mass ratio of ferrite-titanium dioxide compound and thiophene monomer is 0.4:1, and the mass ratio of carbon nanotube and thiophene monomer is 0.4:1.
Advantage of the present invention is: doped with rare-earth elements in the present invention, can increase the magnetocrystalline anisotropy field of ferrite matrix, improve coercive force, thereby be increased in the magnetic hysteresis loss in alternating electromagnetic field, the average grain size of crystal is increased, thereby the grain boundary resistance rate is reduced, and then the resistivity of crystal integral body is reduced, improve eddy-current loss, can increase the domain wall resonance loss simultaneously.Simultaneously, the controlled doping amount can be regulated the range of frequency of Ferrite Material absorption peak, reaching the range of application of expection, and can expand the absorption band width, improves the high temperature absorbing property.Ferrite and titanium dioxide are compound, there is coupling between the nano particle of barium ferrite and titanium dioxide, anisotropy constant and the saturation magnetization of barium ferrite have been reduced, but the speed that the speed that anisotropy constant reduces reduces greater than saturation magnetization, so under both effects, the imaginary part of complex permeability has risen on the contrary, has improved the ability of barium ferrite magnetic loss.Polythiophene is a kind of conducting polymer, by with carbon nanotube π-pi-conjugated, strengthen its dielectric loss ability.Then be combined with ferrite, take full advantage of the dielectric loss ability of Polythiophene excellence, strengthen ferrite to the electrical loss ability of microwave, improve its wave-sucking performance.Simultaneously, reduce ferritic consumption, reduce the consumption of Ferrite Absorber.Therefore, this matrix material is the absorbing material of a superior performance.
Embodiment
Provide following case study on implementation in conjunction with above-mentioned summary of the invention.
Case study on implementation 1:
Step 1: quantitative iron nitrate, nitrate of baryta, lanthanum nitrate (molar content is 0.02) and neodymium nitrate (molar content is 0.02) are joined in deionized water, be stirred to dissolving.Add the citric acid of dose ratio, mix.Heat in the water-bath of 70 ℃, until form viscosity 110cp wet gel.
Step 2: after 5:5 mixes in mass ratio with wet gel and titania gel, carry out self-propagating combustion, obtain black powder, then at 1200 ℃ of calcining 3h, get black ferrite-titanium dioxide compound.
Step 3: 0.4g black ferrite-titanium dioxide compound, 0.4g carbon nanotube and 1g thiophene monomer are joined in chloroform in mass ratio, and ultra-sonic dispersion 3h is dispersed in chloroform their homogeneous, under 0 ℃ of condition, with the anhydrous FeCl of 0.5mol
3Join in the three-necked bottle of chloroformic solution stirring reaction 20h.After reaction is completed, with the solvent evaporate to dryness, pour the HCI solution of 120 mL 2 mol/L under room temperature, stirring at room 20 h, suction filtration, water washing repeats 2-3 time, is colourless to filtrate, 70 ℃ of vacuum-drying 24h, namely make composite wave-suction material, absorption peak can reach 60% greater than the frequency span of-30dB, and the highest absorption peak can reach-45dB.
Case study on implementation 2
Step 1: quantitative iron nitrate, nitrate of baryta, lanthanum nitrate (molar content is 0.03) and neodymium nitrate (molar content is 0.01) are joined in deionized water, be stirred to dissolving.Add the citric acid of dose ratio, mix.Heat in the water-bath of 70 ℃, until form the wet gel of viscosity 110cp.
Step 2: after 5:5 mixes in mass ratio with wet gel and titania gel, carry out self-propagating combustion, obtain black powder, then at 1200 ℃ of calcining 3h, get black ferrite-titanium dioxide compound.
Step 3: 0.8 black ferrite-titanium dioxide compound, 0.8 carbon nanotube and 2g thiophene monomer are joined in chloroform in mass ratio, and ultra-sonic dispersion 3h is dispersed in chloroform their homogeneous, under 0 ℃ of condition, with the anhydrous FeCl of 1.5mol
3Join in the three-necked bottle of chloroformic solution stirring reaction 20h.After reaction is completed, with the solvent evaporate to dryness, pour the HCI solution of 150 mL 2mol/L under room temperature, stirring at room 20 h, suction filtration, water washing repeats 2-3 time, is colourless to filtrate, 70 ℃ of vacuum-drying 24h, namely make composite wave-suction material, absorption peak can reach 70% greater than the frequency span of-25dB, and the highest absorption peak can reach-40dB.
Case study on implementation 3
Step 1: quantitative iron nitrate, nitrate of baryta, lanthanum nitrate (molar content is 0.03) and neodymium nitrate (molar content is 0.03) are joined in deionized water, be stirred to dissolving.Add the citric acid of dose ratio, mix.Heat in the water-bath of 70 ℃, until form the wet gel of viscosity 110cp.
Step 2: after 5:5 mixes in mass ratio with wet gel and titania gel, carry out self-propagating combustion, obtain black powder, then at 1200 ℃ of calcining 3h, get black ferrite-titanium dioxide compound.
Step 3: 0.2 black ferrite-titanium dioxide compound, 0.2 carbon nanotube and 0.5g thiophene monomer are joined in chloroform in mass ratio, and ultra-sonic dispersion 3h is dispersed in chloroform their homogeneous, under 0 ℃ of condition, with the anhydrous FeCl of 0.2mol
3Join in the three-necked bottle of chloroformic solution stirring reaction 20h.After reaction is completed, with the solvent evaporate to dryness, pour the HCI solution of 100mL 2mol/L under room temperature, stirring at room 20 h, suction filtration, water washing repeats 2-3 time, is colourless to filtrate, 70 ℃ of vacuum-drying 24h, namely make composite wave-suction material, absorption peak can reach 60% greater than the frequency span of-20dB, and the highest absorption peak can reach-43dB.
Claims (2)
1. the preparation method of rear-earth-doped ferrite-titanium dioxide/Polythiophene/carbon nanotube microwave absorption, it is characterized in that major ingredient is nitrate of baryta, iron nitrate, neodymium nitrate and lanthanum nitrate, auxiliary material is thiophene monomer, titania gel, carbon nanotube, trichloromethane, citric acid, Anhydrous Ferric Chloride, wherein the mol ratio of citric acid and nitrate radical is 1:2, the mol ratio of barium and lanthanum is 1:(0.02-0.07), the mol ratio of barium and neodymium is 1:(0.03-0.06), the mass ratio of ferrite and titania gel is 5:5, the mass ratio of ferrite-titanium dioxide compound and thiophene monomer is 0.4:1, the mass ratio of carbon nanotube and thiophene monomer is 0.4:1,
Its preparation process is as follows:
A, nitrate of baryta, iron nitrate, neodymium nitrate and lanthanum nitrate are dissolved in distilled water, are stirred to dissolving, obtain settled solution;
B, the citric acid that will measure ratio add in mentioned solution, obtain brown-red solution, then slowly drip ammoniacal liquor, and at 8-9, solution becomes light green to the pH value of solution;
C, light green solution is placed in the water-bath of 70 ℃, until the moisture in solution evaporates fully, obtains the ferrite gel of viscosity 110cp, then with titania gel in mass ratio 5:5 mix, stir;
D, with the mixed gel self-propagating combustion, remove citric acid wherein, obtain the ferrite doped calcium of black-titanium dioxide compound presoma, then with presoma after calcining 3h under 1200 ℃, obtain the ferrite doped calcium-titanium dioxide compound of black powder shape;
E, with ferrite doped calcium-titanium dioxide compound, carbon nanotube and thiophene monomer in mass ratio joins in chloroform soln ultra-sonic oscillation 3h, they are mixed, then add Anhydrous Ferric Chloride, carry out the in situ chemical oxidation reaction in the ice bath of 0 ℃, reaction 20h;
After F, reaction are completed, with the solvent evaporate to dryness, pour the HCl solution of 2 mol/L under room temperature, stirring at room 20 h, suction filtration, water washing repeats 2-3 time, until the filtrate clarification will be deposited in 70 ℃ of lower vacuum-drying 24h, make rear-earth-doped ferrite-titanium dioxide/Polythiophene/carbon mano-tube composite.
2. the preparation method of a kind of rear-earth-doped ferrite-titanium dioxide according to claim 1/Polythiophene/carbon nanotube microwave absorption, the mol ratio that it is characterized in that described barium and lanthanum is 1:(0.02-0.07), the mol ratio of barium and neodymium is 1:(0.03-0.06), the mass ratio of ferrite and titania gel is 5:5, the mass ratio of ferrite-titanium dioxide compound and thiophene monomer is 0.4:1, and the mass ratio of carbon nanotube and thiophene monomer is 0.4:1.
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| CN103632797B (en) * | 2013-12-03 | 2016-05-18 | 南昌航空大学 | A kind of polythiophene clad nano CoFe2O4The preparation method of particle magnetic liquid |
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| CN111848084A (en) * | 2020-07-21 | 2020-10-30 | 兰州理工大学 | High-strength gypsum-based wall body for weakening electromagnetic radiation and carrying out photocatalysis on harmful gas |
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