CN104608430A - Wave-absorbing composite material - Google Patents

Wave-absorbing composite material Download PDF

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CN104608430A
CN104608430A CN201510016271.0A CN201510016271A CN104608430A CN 104608430 A CN104608430 A CN 104608430A CN 201510016271 A CN201510016271 A CN 201510016271A CN 104608430 A CN104608430 A CN 104608430A
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冯丹
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/08—Ferroso-ferric oxide (Fe3O4)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Abstract

The invention discloses a wave-absorbing composite material. A method for preparing the wave-absorbing composite material comprises the following steps: preparing oxidized graphite, dispersing the prepared oxidized graphite, and the like, so that hollow FeO4 nanometer particles are successfully supported onto the surfaces of graphene slices. The method is convenient and quick, and the graphene/hollow Fe3O4/polyaniline nanometer composite materials with excellent wave-absorbing performance can be prepared.

Description

A kind of Wave suction composite material
Technical field
The present invention relates to absorbing material field, in particular a kind of Wave suction composite material.
Background technology
Along with science and technology and the development of electronics industry, increasing electromagenetic wave radiation is present in around us, show through research, excessive electromagenetic wave radiation occurs, except obstacle, even may bring out the serious disease comprising all kinds of cancer except causing nervous system, immune system, reproductive system and blood circulation system etc.Be in for a long time in electromagnetic wave environment, damaged by electromagnetic wave in human body and the damage of the tissue of the self-regeneration that is not able to do in time and organ can become dynamic disease becomes because of long term accumulation, can threat to life time serious.
Graphene, the single layer structure due to its uniqueness makes it have the features such as ultralight density, large specific area, dielectric constant that electric conductivity is excellent and high, becomes a kind of novel wave-absorbing material.In addition, the chemical bond that oxidized graphenic surface exposes in a large number more easily produces the dielectric relaxor of outer-shell electron and attenuates electromagnetic waves under the effect of electromagnetic field, for Graphene is inhaling the applications expanding prospect in ripple field, at the hollow ferriferrous oxide nano-particle of graphenic surface carried magnetic, not only can improve magnetism of material energy, the magnetic loss of reinforced composite, be conducive to the impedance matching of composite, and ferriferrous oxide particles is again stacking in three-dimensional graphite structure in dry run as spacer medium minimizing Graphene, considerable effect is played to stable graphene film Rotating fields.
Technical problem to be solved by this invention is for the deficiencies in the prior art, provides a kind of Wave suction composite material.
Technical scheme of the present invention is as follows:
A kind of Wave suction composite material, it is characterized in that, this Wave suction composite material is laminar nano composite wave-suction material, the ferroferric oxide nano granules homoepitaxial of hollow hemisphere structure is on two surfaces up and down of redox graphene sheet, the absorbing material of the multi-layer compound structure of a kind of nano thickness formed, on graphene sheet layer, load particle diameter is about hollow four iron oxide three particles of 20-50nm, and polyaniline-coated has the graphene sheet layer surface of hollow nano ferriferrous oxide in load, the preparation method of this absorbing material comprises the following steps:
Step one, made by graphite and be of a size of 50-200 order and obtain graphite powder, being added to mass fraction is afterwards in the hydrochloric acid solution of 35%, stirs 30min, adopts deionized water repeatedly to rinse afterwards and makes pH value be neutral, dry stand-by;
By graphite powder, potassium peroxydisulfate and P 2o 5add in the concentrated sulfuric acid, form mixture, the pH value of the mixture formed is 1.5, and this mixture is stirred 1-2h at 60 DEG C, then 2-4h is stirred with at the ramp to 80 of 5 DEG C/min DEG C, finally be warming up to 87 DEG C with 2 DEG C/min and stir 1-2h, then adopt this mixture of distilled water diluting, the pH value of this mixture is diluted to 3.6, distilled water is adopted to filter after placing 36h, make mixture pH value be 6-7, after carry out drying at room temperature, described graphite powder, potassium peroxydisulfate, P 2o 5be 1-3: 1-2: 1-2: 5-10 with the mass ratio of the concentrated sulfuric acid;
Joined in red fuming nitric acid (RFNA) by dried mixture and stir 45-60min, make pH value be 2-4, the mass ratio of described dried mixture and red fuming nitric acid (RFNA) is 1-4: 50-100, and after stirring, at-8 DEG C, first time adds KMnO 4, stir 30min, at being cooled to-12 DEG C afterwards, second time adds KMnO 4, stir 30min, at being finally cooled to-15 DEG C, third time adds KMnO 4, stir 20min, obtain the graphite mixture of pre-oxidation, described first time adds KMnO 4, second time adds KMnO 4kMnO is added with third time 4mass ratio be 1: 2: 3, described dried mixture and total KMnO 4ratio be 1-2: 10-15;
After the graphite mixture obtaining pre-oxidation is filtered also drying, be positioned in Muffle furnace and heat, heat treated temperature, for process 10-20s at 1100 DEG C, processes 15-20s at 1150 DEG C, processes 20-30s, obtain expanded graphite at 1180 DEG C;
Step 2, puts into incubator by expanded graphite made for step one and is warmed up to 40 DEG C, reaction 3h, subsequently, add the first distilled water with the consistent amount of graphite mixture volume of pre-oxidation, then react 2.5h, by incubator temperature to 40 DEG C, again add after-fractionating water and H 2o 2reaction 10-60min, the amount of described after-fractionating water is 1-1.5 times of the first distilled water, after-fractionating water and H 2o 2volume ratio be 4-20: 1, carry out centrifugation 10min, rotating speed 8000 ~ 10000r/min after reaction terminates, centrifugation afterproduct hydrochloric acid solution washs, the volume of this hydrochloric acid solution is 10-50 times of centrifugation afterproduct volume, and finally dialysis obtains graphite oxide in 7-8 days; Add N-hydroxysuccinimide after graphite oxide being adopted methyl-sulfoxide ultrasonic dissolution and make surface conditioning agent by oneself and stir 2h at 35 DEG C, product carries out suction filtration, washing, oven dry, namely obtains surface-treated graphite oxide.
Step 3,
Under normal temperature, the graphite oxide obtained in 1g step 2 is joined in the reactor that 500g deionized water is housed, and reactor is placed in ultrasonic dispersers stirs, stir 10-15min, ammoniacal liquor is adopted to regulate the aqueous solution that the pH value of system is adjusted to 11, and be warming up to 70 DEG C, 5-10g sodium borohydride aqueous solution is added again in reactor, after keeping sonic oscillation reaction 30 ~ 60min, the temperature of system is down to 15 DEG C, add 25g sulfanilic acid again, keep sonic oscillation reaction 2 ~ 4 hours, leave standstill reaction 3 hours again, then suction filtration is carried out to remove desolventizing to mixed liquor, and spend deionized water more than 2 times, filtrate is dispersed in again in 400 ~ 1600g deionized water, and add 1 ~ 4g hydrazine hydrate, react 12 ~ 24 hours at 80 DEG C, product passes through suction filtration, and spend deionized water more than 2 times, finally filtrate drying is obtained sulfonated graphite in 24 ~ 48 hours,
Step 4, the ethylene glycol ultrasonic disperse putting into 500ml after sulfonated graphite 1-2g step 3 obtained carries out lyophilization at-10-30 DEG C with 1-10g PEO-PPOX-PEO triblock copolymer in the lump forms uniform first dispersion liquid; Simultaneously by 4-15g by FeCl 36H 2o, FeCl 24H 2the mixture of O and acetyl acetone iron composition, 6 ~ 25g polyvinylpyrrolidone and 10 ~ 50g NH 4ac is dissolved in the ethylene glycol of 500-1000mL and forms the second dispersion liquid, by the first dispersion liquid and the second dispersion liquid mix and blend, and regulates with ammoniacal liquor, makes it to become the settled solution that pH value is 8-10, described FeCl 36H 2o, FeCl 24H 2the mass ratio of O and acetyl acetone iron is 1: 1: 0.5;
Step 5, the settled solution that 100ml step 3 obtains is put into reactor, after sealing, be heated to 150 DEG C, insulation 2h, 200 DEG C are warming up to afterwards with the heating rate of 2-4 DEG C/min, insulation 4h, 235 DEG C are warming up to afterwards with the heating rate of 3-6 DEG C/min, insulation 3h, then 200 DEG C of insulation 2h are cooled to the cooling rate of 5-7 DEG C/min, finally be warming up to 235 DEG C with the heating rate of 3-6 DEG C/min again, insulation 7h, after question response completes, reactor is taken out, make it cool to room temperature, described cooling rate is 3-6 DEG C/min, by the black powder centrifugation 10min of gained, rotating speed 8000 ~ 10000r/min, absolute ethyl alcohol and deionized water is adopted respectively to wash three times, at 50 ~ 70 DEG C of vacuum drying 24h, obtain the first product,
Be added in the solution of DBSA by 5g first product and 5-10g aniline monomer, ultrasonic disperse 65min, form the second product, the mass ratio of described first product and DBSA is 1-1.5: 8-15;
3g ammonium persulfate is dissolved in 80-120ml distilled water, is slowly added drop-wise in the second product, stirring reaction 15h, after reaction terminates, suction filtration, uses distilled water, ethanol washed product colourless to filtrate respectively, 50 ~ 70 DEG C of vacuum drying 24 ~ 36h, obtain Wave suction composite material.
The ratio of the g of graphite oxide described in step 2, methyl-sulfoxide ml, N-hydroxysuccinimide g and self-control surface conditioning agent g is 0.2-0.5: 20-25: 2-5: 0.1-05, described self-control surface conditioning agent is made up of dicyclohexylcarbodiimide, dodecyl sodium sulfate, kayexalate and polyacrylic acid, and described dicyclohexylcarbodiimide, dodecyl sodium sulfate, kayexalate and polyacrylic mass ratio are 1: 1: 2: 3.
In described described step 2, the concentration of hydrochloric acid is the hydrochloric acid solution of volume ratio 1: 10.
This absorbing material is laminar nano composite wave-suction material, the ferroferric oxide nano granules homoepitaxial of hollow hemisphere structure is on two surfaces up and down of redox graphene sheet, the absorbing material of the multi-layer compound structure of a kind of nano thickness formed, on graphene sheet layer, load particle diameter is about hollow four iron oxide three particles of 20-50nm, and polyaniline-coated has the graphene sheet layer surface of hollow nano ferriferrous oxide in load.
The coupling part weak in graphite after ball milling when graphite is broken up, and does not need through ultrasonic disperse, through colding and heat succeed each other and Small molecular effect in preparation process, both atom can have been made to peel off, reduce energy consumption, and the production cycle, make the production cycle shorten 5-15h.
The preparation method of absorbing material of the present invention is by the growth in situ of tri-iron tetroxide on graphene sheet layer and the in-situ polymerization of polyaniline on Graphene/ferriferrous oxide composite material surface, thus realize the wave-absorbing effect of material excellence, be 4.8-5.1GHz at the Absorber Bandwidth of below reflection loss-10dB;
Applicant prepares pre-oxidation graphite through large quantity research step one of the present invention and adopts different heating rates to be warming up to required whipping temp, stirring stage by stage under different whipping temps, and adds KMnO at different temperature stage by stage 4contribute to the preparation of pre-oxidation graphite, make oxidation more thoroughly be higher than common disposable stirring and add KMnO 410-15%, and be conducive to the formation of later stage Graphene;
In step 2, further surface treatment is done for graphite oxide, adopt homemade surface conditioning agent, the surperficial shortcoming low for metallic iron ion affinity of graphite oxide enough can be made up after adding, increase the load capacity of surperficial Fe ion, also make Fe ion below more even in the dispersion of graphite surface, the specific area of its graphite reaches 35-37m simultaneously 2/ g;
Graphite through oversulfonate process just has fabulous dissolubility in the later stage, and be more easy to be added in high molecular polymer matrix, the associativity of the nano composite material formed is more outstanding.
During adopting different heating rates to be warming up to required temperature in step 5 of the present invention, through insulation of once lowering the temperature, more contribute to the formation of Graphene/hollow tri-iron tetroxide, make the absorbing property of the final absorbing material formed stronger, be better than the performance 5-15% of the absorbing material that commonsense method is formed, and the tri compound absorbing material performance formed is more stable;
The present invention without the need to using nitrogen or oxygen protection, without the need to hot conditions, can effectively reduce synthesis cost, and effectively raising the dispersing uniformity of nano particle in graphite, improve the performance of product in preparation process.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
A kind of Wave suction composite material, it is characterized in that, this Wave suction composite material is laminar nano composite wave-suction material, the ferroferric oxide nano granules homoepitaxial of hollow hemisphere structure is on two surfaces up and down of redox graphene sheet, the absorbing material of the multi-layer compound structure of a kind of nano thickness formed, on graphene sheet layer, load particle diameter is about hollow four iron oxide three particles of 20-50nm, and polyaniline-coated has the graphene sheet layer surface of hollow nano ferriferrous oxide in load, the preparation method of this absorbing material comprises the following steps:
Step one, made by graphite and be of a size of 50-200 order and obtain graphite powder, being added to mass fraction is afterwards in the hydrochloric acid solution of 35%, stirs 30min, adopts deionized water repeatedly to rinse afterwards and makes pH value be neutral, dry stand-by;
By graphite powder, potassium peroxydisulfate and P 2o 5add in the concentrated sulfuric acid, form mixture, the pH value of the mixture formed is 1.5, and this mixture is stirred 1-2h at 60 DEG C, then 2-4h is stirred with at the ramp to 80 of 5 DEG C/min DEG C, finally be warming up to 87 DEG C with 2 DEG C/min and stir 1-2h, then adopt this mixture of distilled water diluting, the pH value of this mixture is diluted to 3.6, distilled water is adopted to filter after placing 36h, make mixture pH value be 6-7, after carry out drying at room temperature, described graphite powder, potassium peroxydisulfate, P 2o 5be 1-3: 1-2: 1-2: 5-10 with the mass ratio of the concentrated sulfuric acid;
Joined in red fuming nitric acid (RFNA) by dried mixture and stir 45-60min, make pH value be 2-4, the mass ratio of described dried mixture and red fuming nitric acid (RFNA) is 1-4: 50-100, and after stirring, at-8 DEG C, first time adds KMnO 4, stir 30min, at being cooled to-12 DEG C afterwards, second time adds KMnO 4, stir 30min, at being finally cooled to-15 DEG C, third time adds KMnO 4, stir 20min, obtain the graphite mixture of pre-oxidation, described first time adds KMnO 4, second time adds KMnO 4kMnO is added with third time 4mass ratio be 1: 2: 3, described dried mixture and total KMnO 4ratio be 1-2: 10-15;
After the graphite mixture obtaining pre-oxidation is filtered also drying, be positioned in Muffle furnace and heat, heat treated temperature, for process 10-20s at 1100 DEG C, processes 15-20s at 1150 DEG C, processes 20-30s, obtain expanded graphite at 1180 DEG C;
Step 2, puts into incubator by expanded graphite made for step one and is warmed up to 40 DEG C, reaction 3h, subsequently, add the first distilled water with the consistent amount of graphite mixture volume of pre-oxidation, then react 2.5h, by incubator temperature to 40 DEG C, again add after-fractionating water and H 2o 2reaction 10-60min, the amount of described after-fractionating water is 1-1.5 times of the first distilled water, after-fractionating water and H 2o 2volume ratio be 4-20: 1, carry out centrifugation 10min, rotating speed 8000 ~ 10000r/min after reaction terminates, centrifugation afterproduct hydrochloric acid solution washs, the volume of this hydrochloric acid solution is 10-50 times of centrifugation afterproduct volume, and finally dialysis obtains graphite oxide in 7-8 days; Add N-hydroxysuccinimide after graphite oxide being adopted methyl-sulfoxide ultrasonic dissolution and make surface conditioning agent by oneself and stir 2h at 35 DEG C, product carries out suction filtration, washing, oven dry, namely obtains surface-treated graphite oxide.
Step 3,
Under normal temperature, the graphite oxide obtained in 1g step 2 is joined in the reactor that 500g deionized water is housed, and reactor is placed in ultrasonic dispersers stirs, stir 10-15min, ammoniacal liquor is adopted to regulate the aqueous solution that the pH value of system is adjusted to 11, and be warming up to 70 DEG C, 5-10g sodium borohydride aqueous solution is added again in reactor, after keeping sonic oscillation reaction 30 ~ 60min, the temperature of system is down to 15 DEG C, add 25g sulfanilic acid again, keep sonic oscillation reaction 2 ~ 4 hours, leave standstill reaction 3 hours again, then suction filtration is carried out to remove desolventizing to mixed liquor, and spend deionized water more than 2 times, filtrate is dispersed in again in 400 ~ 1600g deionized water, and add 1 ~ 4g hydrazine hydrate, react 12 ~ 24 hours at 80 DEG C, product passes through suction filtration, and spend deionized water more than 2 times, finally filtrate drying is obtained sulfonated graphite in 24 ~ 48 hours,
Step 4, the ethylene glycol ultrasonic disperse putting into 500ml after sulfonated graphite 1-2g step 3 obtained carries out lyophilization at-10-30 DEG C with 1-10g PEO-PPOX-PEO triblock copolymer in the lump forms uniform first dispersion liquid; Simultaneously by 4-15g by FeCl 36H 2o, FeCl 24H 2the mixture of O and acetyl acetone iron composition, 6 ~ 25g polyvinylpyrrolidone and 10 ~ 50g NH 4ac is dissolved in the ethylene glycol of 500-1000mL and forms the second dispersion liquid, by the first dispersion liquid and the second dispersion liquid mix and blend, and regulates with ammoniacal liquor, makes it to become the settled solution that pH value is 8-10, described FeCl 36H 2o, FeCl 24H 2the mass ratio of O and acetyl acetone iron is 1: 1: 0.5;
Step 5, the settled solution that 100ml step 3 obtains is put into reactor, after sealing, be heated to 150 DEG C, insulation 2h, 200 DEG C are warming up to afterwards with the heating rate of 2-4 DEG C/min, insulation 4h, 235 DEG C are warming up to afterwards with the heating rate of 3-6 DEG C/min, insulation 3h, then 200 DEG C of insulation 2h are cooled to the cooling rate of 5-7 DEG C/min, finally be warming up to 235 DEG C with the heating rate of 3-6 DEG C/min again, insulation 7h, after question response completes, reactor is taken out, make it cool to room temperature, described cooling rate is 3-6 DEG C/min, by the black powder centrifugation 10min of gained, rotating speed 8000 ~ 10000r/min, absolute ethyl alcohol and deionized water is adopted respectively to wash three times, at 50 ~ 70 DEG C of vacuum drying 24h, obtain the first product,
Be added in the solution of DBSA by 5g first product and 5-10g aniline monomer, ultrasonic disperse 65min, form the second product, the mass ratio of described first product and DBSA is 1-1.5: 8-15;
3g ammonium persulfate is dissolved in 80-120ml distilled water, is slowly added drop-wise in the second product, stirring reaction 15h, after reaction terminates, suction filtration, uses distilled water, ethanol washed product colourless to filtrate respectively, 50 ~ 70 DEG C of vacuum drying 24 ~ 36h, obtain Wave suction composite material.
The ratio of the g of graphite oxide described in step 2, methyl-sulfoxide ml, N-hydroxysuccinimide g and self-control surface conditioning agent g is 0.2-0.5: 20-25: 2-5: 0.1-05, described self-control surface conditioning agent is made up of dicyclohexylcarbodiimide, dodecyl sodium sulfate, kayexalate and polyacrylic acid, and described dicyclohexylcarbodiimide, dodecyl sodium sulfate, kayexalate and polyacrylic mass ratio are 1: 1: 2: 3.
In described described step 2, the concentration of hydrochloric acid is the hydrochloric acid solution of volume ratio 1: 10.
This absorbing material is laminar nano composite wave-suction material, the ferroferric oxide nano granules homoepitaxial of hollow hemisphere structure is on two surfaces up and down of redox graphene sheet, the absorbing material of the multi-layer compound structure of a kind of nano thickness formed, on graphene sheet layer, load particle diameter is about hollow four iron oxide three particles of 20-50nm, and polyaniline-coated has the graphene sheet layer surface of hollow nano ferriferrous oxide in load.
The preparation method of absorbing material of the present invention is by the growth in situ of tri-iron tetroxide on graphene sheet layer and the in-situ polymerization of polyaniline on Graphene/ferriferrous oxide composite material surface, thus realize the wave-absorbing effect of material excellence, be 4.8-5.1GHz at the Absorber Bandwidth of below reflection loss-10dB;
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.

Claims (3)

1. a Wave suction composite material, it is characterized in that, this Wave suction composite material is laminar nano composite wave-suction material, the ferroferric oxide nano granules homoepitaxial of hollow hemisphere structure is on two surfaces up and down of redox graphene sheet, the absorbing material of the multi-layer compound structure of a kind of nano thickness formed, on graphene sheet layer, load particle diameter is about hollow four iron oxide three particles of 20-50nm, and polyaniline-coated has the graphene sheet layer surface of hollow nano ferriferrous oxide in load, the preparation method of this absorbing material comprises the following steps:
Step one, made by graphite and be of a size of 50-200 order and obtain graphite powder, being added to mass fraction is afterwards in the hydrochloric acid solution of 35%, stirs 30min, adopts deionized water repeatedly to rinse afterwards and makes pH value be neutral, dry stand-by;
By graphite powder stand-by for aforementioned oven dry, potassium peroxydisulfate and P 2o 5add in the concentrated sulfuric acid, form mixture, the pH value of the mixture formed is 1.5, and this mixture is stirred 1-2h at 60 DEG C, then 2-4h is stirred with at the ramp to 80 of 5 DEG C/min DEG C, finally be warming up to 87 DEG C with 2 DEG C/min and stir 1-2h, then adopt this mixture of distilled water diluting, the pH value of this mixture is diluted to 3.6, distilled water is adopted to filter after placing 36h, make mixture pH value be 6-7, after carry out drying at room temperature, described graphite powder, potassium peroxydisulfate, P 2o 5be 1-3: 1-2: 1-2: 5-10 with the mass ratio of the concentrated sulfuric acid;
Joined in red fuming nitric acid (RFNA) by dried mixture and stir 45-60min, make pH value be 2-4, the mass ratio of described dried mixture and red fuming nitric acid (RFNA) is 1-4: 50-100, and after stirring, at-8 DEG C, first time adds KMnO 4, stir 30min, at being cooled to-12 DEG C afterwards, second time adds KMnO 4, stir 30min, at being finally cooled to-15 DEG C, third time adds KMnO 4, stir 20min, obtain the graphite mixture of pre-oxidation, described first time adds KMnO 4, second time adds KMnO 4kMnO is added with third time 4mass ratio be 1: 2: 3, described dried mixture and total KMnO 4ratio be 1-2: 10-15;
After the graphite mixture obtaining pre-oxidation is filtered also drying, be positioned in Muffle furnace and heat, heat treated temperature, for process 10-20s at 1100 DEG C, processes 15-20s at 1150 DEG C, processes 20-30s, obtain expanded graphite at 1180 DEG C;
Step 2, puts into incubator by expanded graphite made for step one and is warmed up to 40 DEG C, reaction 3h, subsequently, add the first distilled water with the consistent amount of graphite mixture volume of pre-oxidation, then react 2.5h, by incubator temperature to 40 DEG C, again add after-fractionating water and H 2o 2reaction 10-60min, the amount of described after-fractionating water is 1-1.5 times of the first distilled water, after-fractionating water and H 2o 2volume ratio be 4-20: 1, carry out centrifugation 10min, rotating speed 8000 ~ 10000r/min after reaction terminates, centrifugation afterproduct hydrochloric acid solution washs, the volume of this hydrochloric acid solution is 10-50 times of centrifugation afterproduct volume, and finally dialysis obtains graphite oxide in 7-8 days; Add N-hydroxysuccinimide after graphite oxide being adopted methyl-sulfoxide ultrasonic dissolution and make surface conditioning agent by oneself and stir 2h at 35 DEG C, product carries out suction filtration, washing, oven dry, namely obtains surface-treated graphite oxide.
Step 3,
Under normal temperature, the graphite oxide obtained in 1g step 2 is joined in the reactor that 500g deionized water is housed, and reactor is placed in ultrasonic dispersers stirs, stir 10-15min, ammoniacal liquor is adopted to regulate the aqueous solution that the pH value of system is adjusted to 11, and be warming up to 70 DEG C, 5-10g sodium borohydride aqueous solution is added again in reactor, after keeping sonic oscillation reaction 30 ~ 60min, the temperature of system is down to 15 DEG C, add 25g sulfanilic acid again, keep sonic oscillation reaction 2 ~ 4 hours, leave standstill reaction 3 hours again, then suction filtration is carried out to remove desolventizing to mixed liquor, and spend deionized water more than 2 times, filtrate is dispersed in again in 400 ~ 1600g deionized water, and add 1 ~ 4g hydrazine hydrate, react 12 ~ 24 hours at 80 DEG C, product passes through suction filtration, and spend deionized water more than 2 times, finally filtrate drying is obtained sulfonated graphite in 24 ~ 48 hours,
Step 4, the ethylene glycol ultrasonic disperse putting into 500ml after sulfonated graphite 1-2g step 3 obtained carries out lyophilization at-10-30 DEG C with 1-10g PEO-PPOX-PEO triblock copolymer in the lump forms uniform first dispersion liquid; Simultaneously by 4-15g by FeCl 36H 2o, FeCl 24H 2the mixture of O and acetyl acetone iron composition, 6 ~ 25g polyvinylpyrrolidone and 10 ~ 50g NH 4ac is dissolved in the ethylene glycol of 500-1000mL and forms the second dispersion liquid, by the first dispersion liquid and the second dispersion liquid mix and blend, and regulates with ammoniacal liquor, makes it to become the settled solution that pH value is 8-10, described FeCl 36H 2o, FeCl 24H 2the mass ratio of O and acetyl acetone iron is 1: 1: 0.5;
Step 5, the settled solution that 100ml step 3 obtains is put into reactor, after sealing, be heated to 150 DEG C, insulation 2h, 200 DEG C are warming up to afterwards with the heating rate of 2-4 DEG C/min, insulation 4h, 235 DEG C are warming up to afterwards with the heating rate of 3-6 DEG C/min, insulation 3h, then 200 DEG C of insulation 2h are cooled to the cooling rate of 5-7 DEG C/min, finally be warming up to 235 DEG C with the heating rate of 3-6 DEG C/min again, insulation 7h, after question response completes, reactor is taken out, make it cool to room temperature, described cooling rate is 3-6 DEG C/min, by the black powder centrifugation 10min of gained, rotating speed 8000 ~ 10000r/min, absolute ethyl alcohol and deionized water is adopted respectively to wash three times, at 50 ~ 70 DEG C of vacuum drying 24h, obtain the first product,
Be added in the solution of DBSA by 5g first product and 5-10g aniline monomer, ultrasonic disperse 65min, form the second product, the mass ratio of described first product and DBSA is 1-1.5: 8-15;
3g ammonium persulfate is dissolved in 80-120ml distilled water, is slowly added drop-wise in the second product, stirring reaction 15h, after reaction terminates, suction filtration, uses distilled water, ethanol washed product colourless to filtrate respectively, 50 ~ 70 DEG C of vacuum drying 24 ~ 36h, obtain Wave suction composite material.
2. preparation method according to claim 1, it is characterized in that, the ratio of the g of graphite oxide described in step 2, methyl-sulfoxide ml, N-hydroxysuccinimide g and self-control surface conditioning agent g is 0.2-0.5: 20-25: 2-5: 0.1-05, described self-control surface conditioning agent is made up of dicyclohexylcarbodiimide, dodecyl sodium sulfate, kayexalate and polyacrylic acid, and described dicyclohexylcarbodiimide, dodecyl sodium sulfate, kayexalate and polyacrylic mass ratio are 1: 1: 2: 3.
3. preparation method according to claim 1, is characterized in that, in described described step 2, the concentration of hydrochloric acid is the hydrochloric acid solution of volume ratio 1: 10.
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CN115746362A (en) * 2022-09-09 2023-03-07 东莞市零度导热材料有限公司 Wave-absorbing heat-conducting fin and preparation method thereof

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CN109835010A (en) * 2017-11-29 2019-06-04 深圳光启岗达创新科技有限公司 A kind of Wave suction composite material and preparation method thereof
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