CN103436013B - A kind of preparation method of polyaniline/sliver-cferriteobalt ferriteobalt composite material - Google Patents

A kind of preparation method of polyaniline/sliver-cferriteobalt ferriteobalt composite material Download PDF

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CN103436013B
CN103436013B CN201310388264.4A CN201310388264A CN103436013B CN 103436013 B CN103436013 B CN 103436013B CN 201310388264 A CN201310388264 A CN 201310388264A CN 103436013 B CN103436013 B CN 103436013B
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cofe
solution
polyaniline
ferriteobalt
cferriteobalt
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CN103436013A (en
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齐暑华
张欣欣
钟晓兰
何征
邱华
黄英
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Northwestern Polytechnical University
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Abstract

The preparation method of a kind of polyaniline/sliver-cferriteobalt ferriteobalt composite material that the present invention proposes is that 1:2:4 takes three kinds of materials respectively according to the stoichiometric ratio of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, iron nitrate, citric acid, adopts sol-gel method to prepare vectolite (CoFe 2o 4), to obtained CoFe 2o 4carry out chemical silvering, thus obtain the suction ripple filler of electromagnetic performance excellence.Final with aniline monomer, Ag/CoFe 2o 4for raw material, adopt chemistry polymerizing in situ legal system for PANI/Ag/CoFe 2o 4matrix material.Change electrical property, CoFe that matrix material combines metal simple-substance Ag excellence 2o 4good magnetic property and good processibility, stability and the electrical property of conduction high polymer polyaniline, be a kind of well microwave absorbing material, have important using value in field of microwave absorption.The Ag/CoFe that the inventive method obtains 2o 4compounded mix combines electrical property and the CoFe of Ag excellence 2o 4good magnetic property, is a kind of well magnetoelectric composites, it can be used as the PANI/Ag/CoFe that filler is obtained 2o 4matrix material has good microwave absorbing property.

Description

A kind of preparation method of polyaniline/sliver-cferriteobalt ferriteobalt composite material
Technical field
The present invention relates to a kind of preparation method of polyaniline/sliver-cferriteobalt ferriteobalt composite material, obtained matrix material can be used for field of microwave absorption.
Background technology
Conventional microwave absorbing material comprises ferrite, conduction high polymer, carbon nanomaterial etc.Ferrite has higher saturation magnetization and magnetic loss, and being the most frequently used suction ripple filler, having the vectolite of spinel structure to have higher saturation magnetization and coercive force, is the magneticsubstance of excellent performance.Conduction high polymer is primarily of polyaniline, polypyrrole, Polythiophene etc., and polyaniline is because cost is low, it is easy to synthesize, specific conductivity is high, the physics of environmental stability one collection uniqueness, chemistry, electromagnetic performance receive much concern.
The basic demand of absorbing material is " thin, light, wide, high ", and namely thickness is thin, quality is light, frequency range is wide, intensity is high.But often absorption mechanism is single, microwave absorbing frequency range is narrow to use single filler, in order to address these problems, above-mentioned multiple suction ripple filler is complex as a whole, collect each the chief, be beneficial to preparation and there is light weight, wideband, high-strength microwave absorbing composite material.
Summary of the invention
The technical problem solved
In order to avoid the deficiencies in the prior art part, the present invention proposes a kind of preparation method of polyaniline/sliver-cferriteobalt ferriteobalt composite material, by polyaniline, vectolite and metal simple-substance silver compound, prepare the microwave absorbing composite material having good electrical properties and magnetic property concurrently.
Technical scheme
A preparation method for polyaniline/sliver-cferriteobalt ferriteobalt composite material, is characterized in that step is as follows:
Step 1: take three kinds of materials respectively for 1:2:4 with the stoichiometric ratio of Xiao Suan Gu ﹕ Xiao Suan Tie ﹕ citric acid, adds distilled water respectively and dissolves, mix afterwards; Drip ammoniacal liquor regulator solution pH value again to neutral, in 80 ~ 120 DEG C of water-baths, be heated to solution is colloidal, taken out by colloid and put into 100 ~ 150 DEG C, baking oven oven dry, 2 ~ 4h, take out afterwards at putting into retort furnace 850 DEG C and calcine 2 ~ 4h, naturally cooling obtains vectolite CoFe 2o 4;
Step 2: to CoFe 2o 4carry out pre-treatment, comprise alligatoring, sensitization and activation treatment;
Step 3: by pretreated CoFe 2o 4join in silver ammino solution, after dispersed with stirring, drip formaldehyde solution, after reacting 40 ~ 90min under room temperature, product suction filtration is washed, and vacuum-drying 24h obtains Ag/CoFe at 50 ~ 100 DEG C 2o 4; Described CoFe 2o 4and AgNO 3mass ratio be m coFe2O4: m agNO3=1:0.8 ~ 3; The volume ratio of described formaldehyde solution and silver ammino solution is V formaldehyde solution﹕ V silver ammino solution=1 ﹕ 3 ~ 8;
Step 4, employing chemistry polymerizing in situ method synthesis PANI/Ag/CoFe 2o 4: aniline monomer is joined and fills in the there-necked flask of hydrochloric acid soln, after stirring, add Ag/CoFe 2o 4with ultrasonic disperse after cetyl trimethylammonium bromide CTAB; The hydrochloric acid soln of ammonium persulphate APS is slowly dripped under condition of ice bath, dropping terminates rear reaction 6h, by product successively with acetone, water washing, then use hydrochloric acid soln secondary doping, under 80 DEG C of conditions, vacuum-drying 24h obtains polyaniline/sliver-cferriteobalt ferriteobalt composite material; The volume ratio of described aniline monomer and HCl solution is V aniline﹕ V hCl solution=1 ﹕ 30 ~ 50; Described aniline monomer and Ag/CoFe 2o 4mass ratio be m aniline﹕ m ag/CoFe2O4=1 ﹕ 0.2 ~ 1; The mass ratio of described aniline monomer and CTAB is 1 ﹕ 0.2; The mass ratio of described aniline monomer and APS is m aniline﹕ m aPS=1 ﹕ 2 ~ 4, the volume ratio of the hydrochloric acid soln of aniline and APS is V aniline﹕ V aPS solution=1 ﹕ 20 ~ 30.
Alligatoring in described step 2 is the HNO of 5 ~ 20% by volume fraction 3solution supersound process 10 ~ 30min.
Sensitization in described step 2 is the SnCl with 10 ~ 50g/L 2solution supersound process 10 ~ 30min.
Activation in described step 2 is the PdCl with 0.2 ~ 1g/L 2solution supersound process 30 ~ 60min.
Silver ammino solution in described step 3 requires now to join.
Described AgNO 3the concentration of solution is 0.01 ~ 0.5mol/L.
The concentration of described formaldehyde solution is 40 ~ 100g/L.
In described step 4, the concentration of HCl solution is 0.1mol/L.
Be 15min with acetone, deionized water wash time in described step 4.
In described step 4, HCl strength of solution is 0.1mol/L.
Beneficial effect
The preparation method of a kind of polyaniline/sliver-cferriteobalt ferriteobalt composite material that the present invention proposes is that 1:2:4 takes three kinds of materials respectively according to the stoichiometric ratio of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, iron nitrate, citric acid, adopts sol-gel method to prepare vectolite (CoFe 2o 4), to obtained CoFe 2o 4carry out chemical silvering, thus obtain the suction ripple filler of electromagnetic performance excellence.Final with aniline monomer, Ag/CoFe 2o 4for raw material, adopt chemistry polymerizing in situ legal system for PANI/Ag/CoFe 2o 4matrix material.Change electrical property, CoFe that matrix material combines metal simple-substance Ag excellence 2o 4good magnetic property and good processibility, stability and the electrical property of conduction high polymer polyaniline, be a kind of well microwave absorbing material, have important using value in field of microwave absorption.The Ag/CoFe that the inventive method obtains 2o 4compounded mix combines electrical property and the CoFe of Ag excellence 2o 4good magnetic property, is a kind of well magnetoelectric composites, it can be used as the PANI/Ag/CoFe that filler is obtained 2o 4matrix material has good microwave absorbing property.
Embodiment
Now the invention will be further described in conjunction with the embodiments:
Embodiment 1:
Preparation CoFe 2o 4: take 5.8210g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, 16.16g iron nitrate, 16.8112g citric acid, add in distilled water respectively and dissolve, mix afterwards, adding ammoniacal liquor regulator solution pH value is 7, at 90 DEG C, heating in water bath to solution is colloidal, colloidal product is put into baking oven 130 DEG C of dry 5h afterwards, take out product and put into retort furnace 850 DEG C calcining 3h, naturally cooling can obtain CoFe 2o 4.
To CoFe 2o 4carry out chemical silvering: by CoFe 2o 4add the HNO that volume fraction is 10% 3solution supersound process 5min, suction filtration is washed to neutrality; Concentration is adopted to be the SnCl of 45g/L 2+ HCl solution supersound process 5min, suction filtration is washed to neutrality; Adopt the PdCl of 0.5g/L 2solution supersound process 15min, suction filtration is washed to neutrality.Take 0.01mol AgNO 3, add deionized water and be made into the AgNO that concentration is 0.05mol/L 3solution, constantly stirs the lower ammoniacal liquor that slowly drips and obtains silver ammino solution.Solution is put into beaker, adds the CoFe that 1g pre-treatment completes 2o 4, continue electric stirring, slowly dripping 50ml concentration is afterwards the formaldehyde solution of 80g/L, and reaction 60min, washes product suction filtration, and carry out vacuum-drying 24h at 80 DEG C.
PANI/Ag/CoFe 2o 4preparation: 3ml aniline monomer is joined in the there-necked flask of the HCl solution filling 100ml0.1mol/L, stirs.Add 0.6g Ag/CoFe 2o 4and 0.2gCTAB, ultrasonic disperse 30min, afterwards under condition of ice bath, slow dropping 50ml contains the HCl(0.1mol/L of 9gAPS) solution, ice bath reaction 6h, reaction terminates to use each 15min of acetone, deionized water wash respectively afterwards, then uses the HCl solution secondary doping 1.5h of 0.1mol/L.Finally vacuum-drying 24h under 80 DEG C of conditions.
Embodiment 2:
CoFe 2o 4preparation and chemical silvering process with embodiment 1.
PANI/Ag/CoFe 2o 4preparation: 3ml aniline monomer is joined in the there-necked flask of the HCl solution filling 100ml0.1mol/L, stirs.Add 1.2g Ag/CoFe 2o 4and 0.2gCTAB, ultrasonic disperse 30min, afterwards under condition of ice bath, slow dropping 50ml contains the HCl(0.1mol/L of 9gAPS) solution, ice bath reaction 6h, reaction terminates to use each 15min of acetone, deionized water wash respectively afterwards, then uses the HCl solution secondary doping 1.5h of 0.1mol/L.Finally vacuum-drying 24h under 80 DEG C of conditions.
Embodiment 3:
CoFe 2o 4preparation and chemical silvering process with embodiment 1.
PANI/Ag/CoFe 2o 4preparation: 3ml aniline monomer is joined in the there-necked flask of the HCl solution filling 100ml0.1mol/L, stirs.Add 1.8g Ag/CoFe 2o 4and 0.2gCTAB, ultrasonic disperse 30min, afterwards under condition of ice bath, slow dropping 50ml contains the HCl(0.1mol/L of 9gAPS) solution, ice bath reaction 6h, reaction terminates to use each 15min of acetone, deionized water wash respectively afterwards, then uses the HCl solution secondary doping 1.5h of 0.1mol/L.Finally vacuum-drying 24h under 80 DEG C of conditions.
Embodiment 4:
CoFe 2o 4preparation and chemical silvering process with embodiment 1.
PANI/Ag/CoFe 2o 4preparation: 3ml aniline monomer is joined in the there-necked flask of the HCl solution filling 100ml0.1mol/L, stirs.Add 2.4g Ag/CoFe 2o 4and 0.2gCTAB, ultrasonic disperse 30min, afterwards under condition of ice bath, slow dropping 50ml contains the HCl(0.1mol/L of 9gAPS) solution, ice bath reaction 6h, reaction terminates to use each 15min of acetone, deionized water wash respectively afterwards, then uses the HCl solution secondary doping 1.5h of 0.1mol/L.Finally vacuum-drying 24h under 80 DEG C of conditions.
Embodiment 5:
CoFe 2o 4preparation and chemical silvering process with embodiment 1.
PANI/Ag/CoFe 2o 4preparation: 3ml aniline monomer is joined in the there-necked flask of the HCl solution filling 100ml0.1mol/L, stirs.Add 3g Ag/CoFe 2o 4and 0.2gCTAB, ultrasonic disperse 30min, afterwards under condition of ice bath, slow dropping 50ml contains the HCl(0.1mol/L of 9gAPS) solution, ice bath reaction 6h, reaction terminates to use each 15min of acetone, deionized water wash respectively afterwards, then uses the HCl solution secondary doping 1.5h of 0.1mol/L.Finally vacuum-drying 24h under 80 DEG C of conditions.

Claims (9)

1. a preparation method for polyaniline/sliver-cferriteobalt ferriteobalt composite material, is characterized in that step is as follows:
Step 1: take three kinds of materials respectively for 1:2:4 with the stoichiometric ratio of Xiao Suan Gu ﹕ Xiao Suan Tie ﹕ citric acid, adds distilled water respectively and dissolves, mix afterwards; Drip ammoniacal liquor regulator solution pH value again to neutral, in 80 ~ 120 DEG C of water-baths, be heated to solution is colloidal, taken out by colloid and put into 100 ~ 150 DEG C, baking oven oven dry, 2 ~ 4h, take out afterwards at putting into retort furnace 850 DEG C and calcine 2 ~ 4h, naturally cooling obtains vectolite CoFe 2o 4;
Step 2: to CoFe 2o 4carry out pre-treatment, comprise alligatoring, sensitization and activation treatment;
Step 3: by pretreated CoFe 2o 4join in silver ammino solution, after dispersed with stirring, drip formaldehyde solution, after reacting 40 ~ 90min under room temperature, product suction filtration is washed, and vacuum-drying 24h obtains Ag/CoFe at 50 ~ 100 DEG C 2o 4; Described CoFe 2o 4and AgNO 3mass ratio be m coFe2O4: m agNO3=1:0.8 ~ 3; The volume ratio of described formaldehyde solution and silver ammino solution is V formaldehyde solution﹕ V silver ammino solution=1 ﹕ 3 ~ 8;
Step 4, employing chemistry polymerizing in situ method synthesis PANI/Ag/CoFe 2o 4: aniline monomer is joined and fills in the there-necked flask of hydrochloric acid soln, after stirring, add Ag/CoFe 2o 4with ultrasonic disperse after cetyl trimethylammonium bromide CTAB; The hydrochloric acid soln of ammonium persulphate APS is slowly dripped under condition of ice bath, dropping terminates rear reaction 6h, by product successively with acetone, water washing, then use hydrochloric acid soln secondary doping, under 80 DEG C of conditions, vacuum-drying 24h obtains polyaniline/sliver-cferriteobalt ferriteobalt composite material; The volume ratio of described aniline monomer and HCl solution is V aniline﹕ V hCl solution=1 ﹕ 30 ~ 50; Described aniline monomer and Ag/CoFe 2o 4mass ratio be m aniline﹕ m ag/CoFe2O4=1 ﹕ 0.2 ~ 1; The mass ratio of described aniline monomer and CTAB is 1 ﹕ 0.2; The mass ratio of described aniline monomer and APS is m aniline﹕ m aPS=1 ﹕ 2 ~ 4, the volume ratio of the hydrochloric acid soln of aniline and APS is V aniline﹕ V aPS solution=1 ﹕ 20 ~ 30.
2. the preparation method of polyaniline/sliver-cferriteobalt ferriteobalt composite material according to claim 1, is characterized in that: the alligatoring in described step 2 is the HNO of 5 ~ 20% by volume fraction 3solution supersound process 10 ~ 30min.
3. the preparation method of polyaniline/sliver-cferriteobalt ferriteobalt composite material according to claim 1, is characterized in that: the sensitization in described step 2 is the SnCl with 10 ~ 50g/L 2solution supersound process 10 ~ 30min.
4. the preparation method of polyaniline/sliver-cferriteobalt ferriteobalt composite material according to claim 1, is characterized in that: the activation in described step 2 is the PdCl with 0.2 ~ 1g/L 2solution supersound process 30 ~ 60min.
5. the preparation method of polyaniline/sliver-cferriteobalt ferriteobalt composite material according to claim 1, is characterized in that: the silver ammino solution in described step 3 requires now to join.
6. the preparation method of polyaniline/sliver-cferriteobalt ferriteobalt composite material according to claim 1, is characterized in that: described AgNO 3the concentration of solution is 0.01 ~ 0.5mol/L.
7. the preparation method of polyaniline/sliver-cferriteobalt ferriteobalt composite material according to claim 1, is characterized in that: the concentration of described formaldehyde solution is 40 ~ 100g/L.
8. the preparation method of polyaniline/sliver-cferriteobalt ferriteobalt composite material according to claim 1, is characterized in that: in described step 4, the concentration of HCl solution is 0.1mol/L.
9. the preparation method of polyaniline/sliver-cferriteobalt ferriteobalt composite material according to claim 1, is characterized in that: be 15min with acetone, deionized water wash time in described step 4.
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CN103848988B (en) * 2014-02-27 2017-02-15 南京理工大学 Nitrogen-doped graphene/nickel ferrite/polyaniline nanometer composite material and preparation method for same
CN104673185A (en) * 2014-07-21 2015-06-03 西北工业大学 Method for preparing reduced graphene oxide/CoFe2O4/Ag composite wave-absorbing material
CN104356646B (en) * 2014-11-24 2017-07-04 扬州大学 The preparation method of ferrite/conducting polymer multiphase composite wave-suction material
CN104672446A (en) * 2015-03-06 2015-06-03 苏州欢颜电气有限公司 Preparation method of SiO2 coated CoFe2O4 particle/PANI (polyaniline) composite material serving as conductive and wave absorbing material
CN105482110B (en) * 2015-12-29 2017-11-10 陕西科技大学 A kind of PANI/CoFe2O4/ PVDF absorbing materials and preparation method
CN106830100B (en) * 2017-02-27 2018-11-02 陕西科技大学 A kind of rodlike cobalt ferrite powder and preparation method thereof
CN109317147A (en) * 2018-10-29 2019-02-12 华侨大学 A kind of preparation method of magnetism oxygen vacancy cobalt ferrite bimetallic oxide composite catalyst
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CN110028932B (en) * 2019-05-21 2022-02-22 沈阳师范大学 High microwave absorption spinel type ferrite and silver composite material and preparation method thereof
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