CN107690271A - Rear-earth-doped barium ferrite magnetoelectric composites preparation method - Google Patents
Rear-earth-doped barium ferrite magnetoelectric composites preparation method Download PDFInfo
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Abstract
Rear-earth-doped barium ferrite magnetoelectric composites preparation method, attapulgite is removed into the removal of impurity, calcining and activating, is scattered in the mixed liquor of hydrochloric acid and citric acid and stirred, filtered, clean after reaction, drying, grinding, obtaining attapulgite modified；At room temperature by citric acid, barium nitrate, ferric nitrate, lanthanum nitrate（Cerium）It is soluble in water to be configured to solution, it is placed in stirred in water bath formation colloidal sol after ammoniacal liquor regulation pH value is added dropwise；Attapulgite modified mixed above-mentioned with the colloidal sol formed, reacted under ultrasound, stirring, after gel to be formed, light in atmosphere and bring it about self-propagating combustion reaction, obtain fluffy coralloid brown powder body material, then high-temperature heat treatment, room temperature is cooled to, obtains attapulgite modified composite rare earth doping level barium ferrite magnetic material.The rear-earth-doped barium ferrite of concave convex rod soil matrix and monomer aniline are added in hydrochloric acid solution, the attapulgite clay compounded rear-earth-doped level barium ferrite magnetic material of polyaniline-coated is made using situ aggregation method.
Description
Technical field
The present invention relates to technical field of composite materials, and in particular to the attapulgite modified composite rare earth doping of polyaniline-coated
Level barium ferrite magnetic material technology of preparing.
Background technology
As increasing electronic product enters the living environment of people, its adjoint electromagenetic wave radiation also generates shadow
It is potentially hazardous to ring environmental and human health impacts etc..At present, electromagnetic pollution is administered, searching can be kept out and weaken the suction of electromagenetic wave radiation
Wave material, it has also become the study hotspot of environmentally conscious materialses science.Conventional microwave absorbing material mainly have micro-, ultramicro magnetic metal and
Alloy powder absorbent and Ferrite Absorber, they are because having the characteristics that absorption frequency range is wide, absorptivity is high, matching thickness is thin
As most popular magnetic material, but both it is maximum the shortcomings that be exactly that density is too big, be unfavorable for preparing the suction of light weight
Wave material, especially ferrite proportion limit greatly its application in some fields.To meet absorbing material " thin, light, wide, strong "
Effect, need the high performance microwave absorbing material of research and development badly.
The present Research of ferrite magnetic material is shown both at home and abroad, the electrostatic theory such as saturation magnetic of magneto-plumbite type ferrite
Change intensity and coercivity and electromagnetic performance such as magnetic conductivity and dielectric constant etc., can be substituted by appropriate metal ion to change
Kind, so as to adjust its application, these metal ions are usually the Mn of divalence or trivalent2+, Mg2+, Zn2+And Sr2+Plasma.
And rare earth ion is because having more not paired 4f electronics, the effect of its SO coupling is stronger than in general d areas transition metal,
With special magnetic.Again due to lanthanide contract so that rule is presented with the increase of atomic number in the property of rare earth ion
The change of property.Therefore the synthesis and its basic research of the magneto-plumbite type ferrite substituted to different rare earth ions, to improving it
Electromagnetic performance and microwave absorbing property, disclose the universal law of different rare earth ions influence and widen rare earth application market, all have
There is important meaning.
Attapulgite is a kind of clay mineral of zeopan containing Shuifu County with chain layer structure.Attapulgite has crystalline substance
Body structure, preferable molecular formula are Mg5Si8O20(OH)2(OH2)4·4H2O, its main chemical compositions are SiO2, outside very big
Specific surface area and inner ratio surface area（Cellular endoporus duct with 0.38nm × 0.63nm）, show very strong surface-active
And absorption property, the good physicochemical property of attapulgite is realizes that its recycling provides good platform.If recessed
The convex rear-earth-doped barium ferrite particle of rod soil area load, using polyaniline film as clad, can prepare cheap, lightweight,
Novel magnetic composite of good performance, and be applied to and inhale ripple field, it is China's national defense industry and electromagnetic radiation protection
Novel absorbing material is provided, while new approach can be also provided for the recycling of attapulgite and rare earth.
The content of the invention
It is an object of the invention to provide a kind of rear-earth-doped barium ferrite magnetoelectric composites preparation method.
The present invention is rear-earth-doped barium ferrite magnetoelectric composites preparation method, and its step is：
（1）Surface modification treatment is carried out to attapulgite, first attapulgite is dispersed in water, makes the solid-liquid of attapulgite and water
Mass ratio g/L is 1:10 ~ 20, mechanical agitation 2h, natural subsidence 2h, after removing upper strata impurity, suction filtration, it is placed in 350 DEG C after drying
Lower calcining and activating 2h, is ground into powder；It is 1 that above-mentioned activation attapulgite is scattered in into hydrochloric acid and citric acid mol ratio afterwards:1~3
Mixed acid solution in, make the solid-liquid mass ratio g/L of activation attapulgite and mixed acid solution be 1:After 6,2 ~ 4h of mechanical agitation
Filter, it is 7 to be washed to pH, after drying, is ground into powder, produces attapulgite modified；
（2）Prepare attapulgite modified composite rare earth doping level barium ferrite magnetic material ATP/Ba1-xRexFe12O19, first by Ba
(NO3)2、Fe(NO3)3·9H2O、Re(NO3)3·6H2O, wherein Re=La or Ce, are dissolved with water, are added containing citric acid
C6H8O7·H2In the O aqueous solution, Ba is controlled2+、Fe3+Mol ratio with citric acid is 1.0:12.0:15.6；Under stirring, then to its
Middle dropwise addition NH3·H2O, adjust pH value of solution=7；Then add in above-mentioned solution, make attapulgite modified by attapulgite modified
Quality g and Ba2+Material amount mol than g/mol be 100 ~ 200:1, successively by its first room temperature ultrasound 0.5h, then in 80 DEG C of perseverances
The lower stirring reaction 5h of temperature, forms it into wet gel；Then, 8 ~ 12h then by wet gel is dried at 160 DEG C, grey black is obtained and does
Gel, then it is lighted in atmosphere, self-propagating combustion reaction is brought it about, obtains fluffy coralloid brown ceramic powder；By its
1h is calcined at 900 ~ 1200 DEG C, then, it naturally cools to room temperature, that is, obtains attapulgite modified composite rare earth doping barium iron
Oxysome magnetic material ATP/Ba1-xRexFe12O19；
（3）Prepare the attapulgite clay compounded rear-earth-doped level barium ferrite magnetic material ATP/Ba of polyaniline-coated1-xRexFe12O19/
PANI, first by attapulgite modified composite rare earth doping level barium ferrite magnetic material ATP/Ba1-xRexFe12O19It is 1 in concentration
Ultrasonic disperse 0.5h, makes ATP/Ba in mol/L hydrochloric acid solutions1-xRexFe12O19Quality g and aniline monomer material amount mol
Than for 10 ~ 60:1, then thereto successively by aniline monomer, sulfamic acid and citric acid mol ratio be 1:1 mixed acid solution adds
Enter, it is 0.9 ~ 5 to make mixed acid solution and aniline monomer mol ratio:1, mixture 0.5h is stirred, then will to be dissolved in 1mol/L hydrochloric acid molten
Oxidant ammonium persulfate in liquid, is added drop-wise in said mixture, and it is 0.4 ~ 1.2 to make ammonium persulfate and aniline monomer mol ratio:
1；2h ~ 8h is reacted at 0 ~ 40 DEG C, mixture solution is changed into blackish green, then, then the mixture filtered, washing, 60 DEG C it is true
Sky obtains ATP/Ba after dry, pulverize1-xRexFe12O19/ PANI composites.
Usefulness of the present invention is：Synthesized with sol-gel self-propagating method has good reason so that attapulgite is this
The material for changing performance is the attapulgite clay compounded rear-earth-doped level barium ferrite magnetic material of the polyaniline-coated of matrix, and product has
Higher magnetic and absorbing property, and generated time is short, synthesis technique is simple, can be in microwave absorption, electromagnetic shielding, high density information
The fields such as magnetic recording are applied.Synthesis attapulgite used is green non-poisonous innocuous materials.
Brief description of the drawings
Fig. 1 be the material of embodiment 6 transmission electron microscope picture, Fig. 2 be the material of embodiment 6 hysteresis curve figure, Fig. 3 embodiments 6
The reflection loss curve map of material.
Embodiment
The present invention is rear-earth-doped barium ferrite magnetoelectric composites preparation method, and its step is：
（1）Surface modification treatment is carried out to attapulgite, first attapulgite is dispersed in water, makes the solid-liquid of attapulgite and water
Mass ratio g/L is 1:10 ~ 20, mechanical agitation 2h, natural subsidence 2h, after removing upper strata impurity, suction filtration, it is placed in 350 DEG C after drying
Lower calcining and activating 2h, is ground into powder；It is 1 that above-mentioned activation attapulgite is scattered in into hydrochloric acid and citric acid mol ratio afterwards:1~3
Mixed acid solution in, make the solid-liquid mass ratio g/L of activation attapulgite and mixed acid solution be 1:After 6,2 ~ 4h of mechanical agitation
Filter, it is 7 to be washed to pH, after drying, is ground into powder, produces attapulgite modified；
（2）Prepare attapulgite modified composite rare earth doping level barium ferrite magnetic material ATP/Ba1-xRexFe12O19, first by Ba
(NO3)2、Fe(NO3)3·9H2O、Re(NO3)3·6H2O, wherein Re=La or Ce, are dissolved with water, are added containing citric acid
C6H8O7·H2In the O aqueous solution, Ba is controlled2+、Fe3+Mol ratio with citric acid is 1.0:12.0:15.6；Under stirring, then to its
Middle dropwise addition NH3·H2O, adjust pH value of solution=7；Then add in above-mentioned solution, make attapulgite modified by attapulgite modified
Quality g and Ba2+Material amount mol than g/mol be 100 ~ 200:1, successively by its first room temperature ultrasound 0.5h, then in 80 DEG C of perseverances
The lower stirring reaction 5h of temperature, forms it into wet gel；Then, 8 ~ 12h then by wet gel is dried at 160 DEG C, grey black is obtained and does
Gel, then it is lighted in atmosphere, self-propagating combustion reaction is brought it about, obtains fluffy coralloid brown ceramic powder；By its
1h is calcined at 900 ~ 1200 DEG C, then, it naturally cools to room temperature, that is, obtains attapulgite modified composite rare earth doping barium iron
Oxysome magnetic material ATP/Ba1-xRexFe12O19；
（3）Prepare the attapulgite clay compounded rear-earth-doped level barium ferrite magnetic material ATP/Ba of polyaniline-coated1-xRexFe12O19/
PANI, first by attapulgite modified composite rare earth doping level barium ferrite magnetic material ATP/Ba1-xRexFe12O19It is 1 in concentration
Ultrasonic disperse 0.5h, makes ATP/Ba in mol/L hydrochloric acid solutions1-xRexFe12O19Quality g and aniline monomer material amount mol
Than for 10 ~ 60:1, then thereto successively by aniline monomer, sulfamic acid and citric acid mol ratio be 1:1 mixed acid solution adds
Enter, it is 0.9 ~ 5 to make mixed acid solution and aniline monomer mol ratio:1, mixture 0.5h is stirred, then will to be dissolved in 1mol/L hydrochloric acid molten
Oxidant ammonium persulfate in liquid, is added drop-wise in said mixture, and it is 0.4 ~ 1.2 to make ammonium persulfate and aniline monomer mol ratio:
1；2h ~ 8h is reacted at 0 ~ 40 DEG C, mixture solution is changed into blackish green, then, then the mixture filtered, washing, 60 DEG C it is true
Sky obtains ATP/Ba after dry, pulverize1-xRexFe12O19/ PANI composites.
Embodiment 1：
According to the solid-liquid mass ratio of attapulgite and water（g）1:10, by attapulgite in H2Mix, natural subsidence 2h, remove in O
Calcining and activating 2h, grinding at 350 DEG C are placed in after the impurity of upper strata, after suction filtration, drying to weigh；Above-mentioned attapulgite is scattered in afterwards
In the mixed liquor of 300 mL 1mol/L HCl and 1mol/L citric acids（Mol ratio 1:1）, make activation attapulgite and mixed acid
The solid-liquid mass ratio of solution（g）For 1:Filtered after 6, mechanical agitation 4h, it is 7 to be washed to pH, after being dried in vacuo 12h, grinding, is produced
It is attapulgite modified（ATP）.Then by 0.0027mol Ba (NO3)2、0.036mol Fe(NO3)3·9H2O、0.0003mol La
(NO3)3·6H2O is dissolved with water, is sequentially added containing 0.0468mol citric acids C6H8O7·H2In the O aqueous solution, under stirring, then
NH is added dropwise thereto3·H2O, adjust pH value of solution=7.Then, add 0.05g is attapulgite modified in above-mentioned solution, then by its
Ultrasonic 0.5h, then the stirring reaction 5h under 80 DEG C of constant temperature, forms it into wet gel；Then, then by wet gel done at 160 DEG C
Dry 12h, grey black xerogel is obtained, then it is lighted in atmosphere, brought it about self-propagating combustion reaction, obtain fluffy coral
The brown ceramic powder of shape.It is calcined into 1h at 1000 DEG C again, then, it naturally cools to room temperature, obtains attapulgite modified multiple
Close rear-earth-doped level barium ferrite magnetic material（ATP/Ba1-xRexFe12O19）.Finally, by the attapulgite modified compound rare-earths of 0.1g
Adulterate level barium ferrite magnetic material（ATP/Ba1-xRexFe12O19）The ultrasonic disperse 0.5h in the mol/L hydrochloric acid solutions of 20 mL 1,
Sequentially add the mixed solution of 0.011mol aniline monomer, 0.011mol sulfamic acid and citric acid thereto again（Mole
Than for 1:1）, stir mixture 0.5h, then the hydrochloric acid solution by 0.0044mol oxidant ammonium persulfates（Concentration of hydrochloric acid is 1mol/
L）It is added drop-wise in said mixture.6h is reacted at 0 ~ 5 DEG C, mixture solution is changed into blackish green, then, then the mixture is taken out
Filter, washing, 60 DEG C of vacuum drying, ATP/Ba is obtained after crushing1-xRexFe12O19/ PANI composites.
Embodiment 2：
According to the solid-liquid mass ratio of attapulgite and water（g）1:10, by attapulgite in H2Mix, natural subsidence 2h, remove in O
Calcining and activating 2h, grinding at 350 DEG C are placed in after the impurity of upper strata, after suction filtration, drying to weigh；Above-mentioned attapulgite is scattered in afterwards
In the mixed liquor of 300 mL 1mol/L HCl and 1mol/L citric acids（Mol ratio 1:1）, make activation attapulgite and mixed acid
The solid-liquid mass ratio of solution（g）For 1:Filtered after 6, mechanical agitation 4h, it is 7 to be washed to pH, after being dried in vacuo 12h, grinding, is produced
It is attapulgite modified（ATP）.Then by 0.0027mol Ba (NO3)2、0.036mol Fe(NO3)3·9H2O、0.0003mol La
(NO3)3·6H2O is dissolved with water, is sequentially added containing 0.0468mol citric acids C6H8O7·H2In the O aqueous solution, under stirring, then
NH is added dropwise thereto3·H2O, adjust pH value of solution=7.Then, add 0.1g is attapulgite modified in above-mentioned solution, then surpassed
Sound 0.5h, then the stirring reaction 5h under 80 DEG C of constant temperature, forms it into wet gel；Then, then by wet gel dried at 160 DEG C
12h, grey black xerogel is obtained, then it is lighted in atmosphere, brought it about self-propagating combustion reaction, obtain fluffy coralliform
Brown ceramic powder.It is calcined into 1h at 1000 DEG C again, then, it naturally cools to room temperature, obtains attapulgite modified compound
Rear-earth-doped level barium ferrite magnetic material（ATP/Ba1-xRexFe12O19）.Finally, the attapulgite modified compound rare-earths of 0.1g are mixed
Miscellaneous level barium ferrite magnetic material（ATP/Ba1-xRexFe12O19）The ultrasonic disperse 0.5h in the mol/L hydrochloric acid solutions of 20 mL 1, then
The mixed solution of 0.011mol aniline monomer, 0.011mol sulfamic acid and citric acid is sequentially added thereto（Mol ratio
For 1:1）, stir mixture 0.5h, then the hydrochloric acid solution by 0.0044mol oxidant ammonium persulfates（Concentration of hydrochloric acid is 1mol/L）
It is added drop-wise in said mixture.6h is reacted at 0 ~ 5 DEG C, mixture solution is changed into blackish green, then, then the mixture is taken out
Filter, washing, 60 DEG C of vacuum drying, ATP/Ba is obtained after crushing1-xRexFe12O19/ PANI composites.
Embodiment 3：
According to the solid-liquid mass ratio of attapulgite and water（g）1:10, by attapulgite in H2Mix, natural subsidence 2h, remove in O
Calcining and activating 2h, grinding at 350 DEG C are placed in after the impurity of upper strata, after suction filtration, drying to weigh；Above-mentioned attapulgite is scattered in afterwards
In the mixed liquor of 300 mL 1mol/L HCl and 1mol/L citric acids（Mol ratio 1:1）, make activation attapulgite and mixed acid
The solid-liquid mass ratio of solution（g）For 1:Filtered after 6, mechanical agitation 4h, it is 7 to be washed to pH, after being dried in vacuo 12h, grinding, is produced
It is attapulgite modified（ATP）.Then by 0.0027mol Ba (NO3)2、0.036mol Fe(NO3)3·9H2O、0.0003mol La
(NO3)3·6H2O is dissolved with water, is sequentially added containing 0.0468mol citric acids C6H8O7·H2In the O aqueous solution, under stirring, then
NH is added dropwise thereto3·H2O, adjust pH value of solution=7.Then, add 0.05g is attapulgite modified in above-mentioned solution, then by its
Ultrasonic 0.5h, then the stirring reaction 5h under 80 DEG C of constant temperature, forms it into wet gel；Then, then by wet gel done at 160 DEG C
Dry 12h, grey black xerogel is obtained, then it is lighted in atmosphere, brought it about self-propagating combustion reaction, obtain fluffy coral
The brown ceramic powder of shape.It is calcined into 1h at 1000 DEG C again, then, it naturally cools to room temperature, obtains attapulgite modified multiple
Close rear-earth-doped level barium ferrite magnetic material（ATP/Ba1-xRexFe12O19）.Finally, by the attapulgite modified compound rare-earths of 0.3g
Adulterate level barium ferrite magnetic material（ATP/Ba1-xRexFe12O19）The ultrasonic disperse 0.5h in the mol/L hydrochloric acid solutions of 20 mL 1,
Sequentially add the mixed solution of 0.011mol aniline monomer, 0.011mol sulfamic acid and citric acid thereto again（Mole
Than for 1:1）, stir mixture 0.5h, then the hydrochloric acid solution by 0.0044mol oxidant ammonium persulfates（Concentration of hydrochloric acid is 1mol/
L）It is added drop-wise in said mixture.6h is reacted at 0 ~ 5 DEG C, mixture solution is changed into blackish green, then, then the mixture is taken out
Filter, washing, 60 DEG C of vacuum drying, ATP/Ba is obtained after crushing1-xRexFe12O19/ PANI composites.
Embodiment 4：
According to the solid-liquid mass ratio of attapulgite and water（g）1:10, by attapulgite in H2Mix, natural subsidence 2h, remove in O
Calcining and activating 2h, grinding at 350 DEG C are placed in after the impurity of upper strata, after suction filtration, drying to weigh；Above-mentioned attapulgite is scattered in afterwards
In the mixed liquor of 300 mL 1mol/L HCl and 1mol/L citric acids（Mol ratio 1:1）, make activation attapulgite and mixed acid
The solid-liquid mass ratio of solution（g）For 1:Filtered after 6, mechanical agitation 4h, it is 7 to be washed to pH, after being dried in vacuo 12h, grinding, is produced
It is attapulgite modified（ATP）.Then by 0.0027mol Ba (NO3)2、0.036mol Fe(NO3)3·9H2O、0.0003mol La
(NO3)3·6H2O is dissolved with water, is sequentially added containing 0.0468mol citric acids C6H8O7·H2In the O aqueous solution, under stirring, then
NH is added dropwise thereto3·H2O, adjust pH value of solution=7.Then, add 0.05g is attapulgite modified in above-mentioned solution, then by its
Ultrasonic 0.5h, then the stirring reaction 5h under 80 DEG C of constant temperature, forms it into wet gel；Then, then by wet gel done at 160 DEG C
Dry 12h, grey black xerogel is obtained, then it is lighted in atmosphere, brought it about self-propagating combustion reaction, obtain fluffy coral
The brown ceramic powder of shape.It is calcined into 1h at 1000 DEG C again, then, it naturally cools to room temperature, obtains attapulgite modified multiple
Close rear-earth-doped level barium ferrite magnetic material（ATP/Ba1-xRexFe12O19）.Finally, by the attapulgite modified compound rare-earths of 0.5g
Adulterate level barium ferrite magnetic material（ATP/Ba1-xRexFe12O19）The ultrasonic disperse 0.5h in the mol/L hydrochloric acid solutions of 20 mL 1,
Sequentially add the mixed solution of 0.011mol aniline monomer, 0.011mol sulfamic acid and citric acid thereto again（Mole
Than for 1:1）, stir mixture 0.5h, then the hydrochloric acid solution by 0.0044mol oxidant ammonium persulfates（Concentration of hydrochloric acid is 1mol/
L）It is added drop-wise in said mixture.6h is reacted at 0 ~ 5 DEG C, mixture solution is changed into blackish green, then, then the mixture is taken out
Filter, washing, 60 DEG C of vacuum drying, ATP/Ba is obtained after crushing1-xRexFe12O19/ PANI composites.
Embodiment 5：
According to the solid-liquid mass ratio of attapulgite and water（g）1:10, by attapulgite in H2Mix, natural subsidence 2h, remove in O
Calcining and activating 2h, grinding at 350 DEG C are placed in after the impurity of upper strata, after suction filtration, drying to weigh；Above-mentioned attapulgite is scattered in afterwards
In the mixed liquor of 300 mL 1mol/L HCl and 1mol/L citric acids（Mol ratio 1:1）, make activation attapulgite and mixed acid
The solid-liquid mass ratio of solution（g）For 1:Filtered after 6, mechanical agitation 4h, it is 7 to be washed to pH, after being dried in vacuo 12h, grinding, is produced
It is attapulgite modified（ATP）.Then by 0.0027mol Ba (NO3)2、0.036mol Fe(NO3)3·9H2O、0.0003mol La
(NO3)3·6H2O is dissolved with water, is sequentially added containing 0.0468mol citric acids C6H8O7·H2In the O aqueous solution, under stirring, then
NH is added dropwise thereto3·H2O, adjust pH value of solution=7.Then, add 0.05g is attapulgite modified in above-mentioned solution, then by its
Ultrasonic 0.5h, then the stirring reaction 5h under 80 DEG C of constant temperature, forms it into wet gel；Then, then by wet gel done at 160 DEG C
Dry 12h, grey black xerogel is obtained, then it is lighted in atmosphere, brought it about self-propagating combustion reaction, obtain fluffy coral
The brown ceramic powder of shape.It is calcined into 1h at 1000 DEG C again, then, it naturally cools to room temperature, obtains attapulgite modified multiple
Close rear-earth-doped level barium ferrite magnetic material（ATP/Ba1-xRexFe12O19）.Finally, by the attapulgite modified compound rare-earths of 0.1g
Adulterate level barium ferrite magnetic material（ATP/Ba1-xRexFe12O19）The ultrasonic disperse 0.5h in the mol/L hydrochloric acid solutions of 20 mL 1,
Sequentially add the mixed solution of 0.011mol aniline monomer, 0.022mol sulfamic acid and citric acid thereto again（Mole
Than for 1:1）, stir mixture 0.5h, then the hydrochloric acid solution by 0.0044mol oxidant ammonium persulfates（Concentration of hydrochloric acid is 1mol/
L）It is added drop-wise in said mixture.6h is reacted at 0 ~ 5 DEG C, mixture solution is changed into blackish green, then, then the mixture is taken out
Filter, washing, 60 DEG C of vacuum drying, ATP/Ba is obtained after crushing1-xRexFe12O19/ PANI composites.
Embodiment 6：
According to the solid-liquid mass ratio of attapulgite and water（g）1:10, by attapulgite in H2Mix, natural subsidence 2h, remove in O
Calcining and activating 2h, grinding at 350 DEG C are placed in after the impurity of upper strata, after suction filtration, drying to weigh；Above-mentioned attapulgite is scattered in afterwards
In the mixed liquor of 300 mL 1mol/L HCl and 1mol/L citric acids（Mol ratio 1:1）, make activation attapulgite and mixed acid
The solid-liquid mass ratio of solution（g）For 1:Filtered after 6, mechanical agitation 4h, it is 7 to be washed to pH, after being dried in vacuo 12h, grinding, is produced
It is attapulgite modified（ATP）.Then by 0.0015mol Ba (NO3)2、0.036mol Fe(NO3)3·9H2O、0.0015mol La
(NO3)3·6H2O is dissolved with water, is sequentially added containing 0.0468mol citric acids C6H8O7·H2In the O aqueous solution, under stirring, then
NH is added dropwise thereto3·H2O, adjust pH value of solution=7.Then, add 0.05g is attapulgite modified in above-mentioned solution, then by its
Ultrasonic 0.5h, then the stirring reaction 5h under 80 DEG C of constant temperature, forms it into wet gel；Then, then by wet gel done at 160 DEG C
Dry 12h, grey black xerogel is obtained, then it is lighted in atmosphere, brought it about self-propagating combustion reaction, obtain fluffy coral
The brown ceramic powder of shape.It is calcined into 1h at 1000 DEG C again, then, it naturally cools to room temperature, obtains attapulgite modified multiple
Close rear-earth-doped level barium ferrite magnetic material（ATP/Ba1-xRexFe12O19）.Finally, by the attapulgite modified compound rare-earths of 0.1g
Adulterate level barium ferrite magnetic material（ATP/Ba1-xRexFe12O19）The ultrasonic disperse 0.5h in the mol/L hydrochloric acid solutions of 20 mL 1,
Sequentially add the mixed solution of 0.011mol aniline monomer, 0.011mol sulfamic acid and citric acid thereto again（Mole
Than for 1:1）, stir mixture 0.5h, then the hydrochloric acid solution by 0.0044mol oxidant ammonium persulfates（Concentration of hydrochloric acid is 1mol/
L）It is added drop-wise in said mixture.6h is reacted at 0 ~ 5 DEG C, mixture solution is changed into blackish green, then, then the mixture is taken out
Filter, washing, 60 DEG C of vacuum drying, ATP/Ba is obtained after crushing1-xRexFe12O19/ PANI composites.
Fig. 1 show the ATP/Ba of embodiment 61-xRexFe12O19The TEM figures of/PANI composites, can from figure
Go out：In the original location in polymerization process, polyaniline film is covered in ATP/Ba1-xRexFe12O19The surface of material coats it well,
And then ATP/Ba is made1-xRexFe12O19/ PANI composites.
Fig. 2 is the ATP/Ba of embodiment 61-xRexFe12O19The hysteresis curve figure of/PANI composites, the saturation magnetic of material
It is respectively 7.816 emu/g, 4.598 kOe, 4.554 to change intensity (Ms), coercivity (Hc) and remanent magnetization (Mr)
emu/g.For this explanation during aniline in-situ polymerization, polyaniline is deposited on ATP/Ba1-xRexFe12O19The surface of material and crystal grain
On border, its surface defect is covered, causes the magnetic anisotropy of ferrite surfaces to reduce.
Fig. 3 show the ATP/Ba of embodiment 61-xRexFe12O19/ PANI composites are 1-5mm inhaling ripple thickness degree, frequency
Rate is the reflection loss curve map in the range of 0.5-18GHz, and with the increase for inhaling ripple thickness degree, the minimal reflection loss of material is in
Now first increase the trend reduced afterwards；Simultaneously it can also be seen that with material inhale ripple thickness degree increase, its minimum reflection loss by
Gradually moved to low frequency.It is 3.0 mm inhaling ripple thickness degree, when frequency is 7.02 GHz, the minimal reflection loss of material reaches
12.37 dB.It is respectively 2.0 mm when inhaling ripple thickness degree, when 4.0 mm, 5.0 mm, the minimal reflection loss of material is respectively
11.89 dB（10.65 GHz）、−11.61 dB（5.53 GHz）、−10.02 dB （4.26 GHz）, this shows multiple by regulating and controlling
The composition and coating layer thickness of condensation material, and then carry out the absorption frequency scope of controlled material.
Comparative example：
According to the solid-liquid mass ratio of attapulgite and water（g）1:10, by attapulgite in H2Mix, natural subsidence 2h, remove in O
Calcining and activating 2h, grinding at 350 DEG C are placed in after the impurity of upper strata, after suction filtration, drying to weigh；Above-mentioned attapulgite is scattered in afterwards
Filtered after 300 mL 1mol/L HCl, mechanical agitation 4h, it is 7 to be washed to pH, after being dried in vacuo 12h, grinding, it is recessed to produce modification
Convex rod soil（ATP）.Then by 0.0027mol Ba (NO3)2、0.036mol Fe(NO3)3·9H2O、0.0003mol La
(NO3)3·6H2O is dissolved with water, is sequentially added containing 0.0468mol citric acids C6H8O7·H2In the O aqueous solution, under stirring, then
NH is added dropwise thereto3·H2O, adjust pH value of solution=7.Then, add 0.05g is attapulgite modified in above-mentioned solution, then by its
Ultrasonic 0.5h, then the stirring reaction 5h under 80 DEG C of constant temperature, forms it into wet gel；Then, then by wet gel done at 160 DEG C
Dry 12h, grey black xerogel is obtained, then it is lighted in atmosphere, brought it about self-propagating combustion reaction, obtain fluffy coral
The brown ceramic powder of shape.It is calcined into 1h at 1000 DEG C again, then, it naturally cools to room temperature, obtains attapulgite modified multiple
Close rear-earth-doped level barium ferrite magnetic material（ATP/Ba1-xRexFe12O19）.Finally, by the attapulgite modified compound rare-earths of 0.1g
Adulterate level barium ferrite magnetic material（ATP/Ba1-xRexFe12O19）The ultrasonic disperse 0.5h in the mol/L hydrochloric acid solutions of 20 mL 1,
Sequentially add 0.011mol aniline monomer, 0.011mol sulfamic acid thereto again, stir mixture 0.5h, then will
The hydrochloric acid solution of 0.0044mol oxidant ammonium persulfates（Concentration of hydrochloric acid is 1mol/L）It is added drop-wise in said mixture.At 0 ~ 5 DEG C
Lower reaction 6h, mixture solution are changed into blackish green, then, then by the mixture filter, washing, 60 DEG C vacuum drying, after crushing
Obtain ATP/Ba1-xRexFe12O19/ PANI composites.
Claims (3)
1. rear-earth-doped barium ferrite magnetoelectric composites preparation method, it is characterised in that its step is：
（1）Surface modification treatment is carried out to attapulgite, first attapulgite is dispersed in water, makes the solid-liquid of attapulgite and water
Mass ratio g/L is 1:10 ~ 20, mechanical agitation 2h, natural subsidence 2h, after removing upper strata impurity, suction filtration, it is placed in 350 DEG C after drying
Lower calcining and activating 2h, is ground into powder；It is 1 that above-mentioned activation attapulgite is scattered in into hydrochloric acid and citric acid mol ratio afterwards:1~3
Mixed acid solution in, make the solid-liquid mass ratio g/L of activation attapulgite and mixed acid solution be 1:After 6,2 ~ 4h of mechanical agitation
Filter, it is 7 to be washed to pH, after drying, is ground into powder, produces attapulgite modified；
（2）Prepare attapulgite modified composite rare earth doping level barium ferrite magnetic material ATP/Ba1-xRexFe12O19, first by Ba
(NO3)2、Fe(NO3)3·9H2O、Re(NO3)3·6H2O, wherein Re=La or Ce, are dissolved with water, are added containing citric acid
C6H8O7·H2In the O aqueous solution, Ba is controlled2+、Fe3+Mol ratio with citric acid is 1.0:12.0:15.6；Under stirring, then to its
Middle dropwise addition NH3·H2O, adjust pH value of solution=7；Then add in above-mentioned solution, make attapulgite modified by attapulgite modified
Quality g and Ba2+Material amount mol than g/mol be 100 ~ 200:1, successively by its first room temperature ultrasound 0.5h, then in 80 DEG C of perseverances
The lower stirring reaction 5h of temperature, forms it into wet gel；Then, 8 ~ 12h then by wet gel is dried at 160 DEG C, grey black is obtained and does
Gel, then it is lighted in atmosphere, self-propagating combustion reaction is brought it about, obtains fluffy coralloid brown ceramic powder；By its
1h is calcined at 900 ~ 1200 DEG C, then, it naturally cools to room temperature, that is, obtains attapulgite modified composite rare earth doping barium iron
Oxysome magnetic material ATP/Ba1-xRexFe12O19；
（3）Prepare the attapulgite clay compounded rear-earth-doped level barium ferrite magnetic material ATP/Ba of polyaniline-coated1-xRexFe12O19/
PANI, first by attapulgite modified composite rare earth doping level barium ferrite magnetic material ATP/Ba1-xRexFe12O19It is 1 in concentration
Ultrasonic disperse 0.5h, makes ATP/Ba in mol/L hydrochloric acid solutions1-xRexFe12O19Quality g and aniline monomer material amount mol
Than for 10 ~ 60:1, then thereto successively by aniline monomer, sulfamic acid and citric acid mol ratio be 1:1 mixed acid solution adds
Enter, it is 0.9 ~ 5 to make mixed acid solution and aniline monomer mol ratio:1, mixture 0.5h is stirred, then will to be dissolved in 1mol/L hydrochloric acid molten
Oxidant ammonium persulfate in liquid, is added drop-wise in said mixture, and it is 0.4 ~ 1.2 to make ammonium persulfate and aniline monomer mol ratio:
1；2h ~ 8h is reacted at 0 ~ 40 DEG C, mixture solution is changed into blackish green, then, then the mixture filtered, washing, 60 DEG C it is true
Sky obtains ATP/Ba after dry, pulverize1-xRexFe12O19/ PANI composites.
2. rear-earth-doped barium ferrite magnetoelectric composites preparation method according to claim 1, it is characterised in that step
（1）Acid in mixed acid solution is hydrochloric acid and citric acid, mol ratio 1:1~3.
3. rear-earth-doped barium ferrite magnetoelectric composites preparation method according to claim 1, it is characterised in that step
（3）Mixed acid solution in acid be sulfamic acid and citric acid, mol ratio 1:1.
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