CN105950112B - A kind of nano combined absorbing material and preparation method thereof - Google Patents
A kind of nano combined absorbing material and preparation method thereof Download PDFInfo
- Publication number
- CN105950112B CN105950112B CN201610361468.2A CN201610361468A CN105950112B CN 105950112 B CN105950112 B CN 105950112B CN 201610361468 A CN201610361468 A CN 201610361468A CN 105950112 B CN105950112 B CN 105950112B
- Authority
- CN
- China
- Prior art keywords
- modification
- magnetic nanoparticle
- preparation
- alkynyl
- azide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
Abstract
The invention discloses a kind of preparation method of nano combined absorbing material, belong to electromagnetism field, the present invention first prepares the magnetic nanoparticle of alkynyl modification, it is again the graphene oxide matrix that raw material prepares that Azide is modified with graphite, then the magnetic nanoparticle modified the alkynyl by cycloaddition reaction is covalently sequestered in the surface of graphene oxide of the Azide modification, hydrazine hydrate reduction is finally used, forms nano combined absorbing material；Magnetic nanoparticle is covalently sequestered on graphenic surface by the present invention by clicking on coupling process, the nano particle of chelating is not easy to come off from graphenic surface, therefore the graphene ferrite composite material has good electric conductivity, magnetic property, and has the advantages that acid resistance is strong, stability is good, practical；Improve the impedance matching performance of absorbing material simultaneously, material prepared by the present invention all has preferably microwave-absorbing in C-band and Ku wave bands, has significant application value in electromagnetic shielding field.
Description
Technical field
The present invention relates to electromagnetism field, more particularly to a kind of nano combined absorbing material and preparation method thereof.
Background technology
With the development of modern science and technology, electric power（Power transmission and transformation, household electrical appliance etc.）, microwave（Micro-wave oven, microwave signal hair
Penetrate tower etc.）, radio wave（Handset mobile communications, radio and television launching tower etc.）Use Deng electronics, electrical equipment is quite general
And the complicated electromagnetic environment of formation also getting worse.Caused electromagnetic radiation and electromagnetic interference to human body, electronic equipment all
Produce greatly harm, be the generally acknowledged the fourth-largest pollution after atmosphere pollution, noise pollution and water pollution, turn into society and
The hot issue of scientific circles' concern.As electromagnetic radiation can influence the circulatory system, immune, reproduction and the metabolic function of human body, seriously
Can also induce cancer, and the cancer cell multiplication of human body can be accelerated；Electromagnetic Interference broadcast, TV signal and communication signal, make
The robot control system(RCS) failure of equipment instrument, aircraft flight indication signal error etc..Therefore, how electromagnetic radiation is reduced, prevents electromagnetism
Interference, effective environmental protection, health is protected, it is extremely urgent.
Mutual supplement with each other's advantages can be formed to support or carry magnetic material using graphene as substrate, on the one hand light graphene
Material can reduce the density of material, and on the other hand two kinds of the compound of material can make material have multi-form electromagnetic consumable.
But prepare magnetic nanoparticle at present and typically use coprecipitation, solvent-thermal method with the compound absorbing material of graphene, these
Composite wave-suction material prepared by method is all that magnetic nanoparticle is deposited on into graphene table by physical absorption or electrostatic interaction
On face, the composite that these methods are formed is unstable, acidproof, oxidation resistance is not strong, and nano particle is easily reunited, and is made
The shortcomings of easily being come off during from graphenic surface.
Therefore, existing absorbing material can not reach stable, acidproof, resistance to oxidation and the requirement to the effective absorption of electromagnetic wave.
The content of the invention
An object of the present invention, in that a kind of preparation method of new nano combined absorbing material is provided, to solve
Above mentioned problem.
To achieve these goals, the technical solution adopted by the present invention is such：A kind of nano combined absorbing material
Preparation method, the magnetic nanoparticle of alkynyl modification and graphene oxide matrix that Azide is modified is compound；Alkynyl is repaiied
The proportioning for the graphene oxide matrix that the magnetic nanoparticle of decorations is modified with Azide is by weight（5-10）：1 is well mixed,
Then the magnetic nanoparticle modified the alkynyl by cycloaddition reaction is covalently sequestered in the oxygen of the Azide modification
On graphite alkene surface, finally with hydrazine hydrate reduction, ferrite-graphene nano composite wave-suction material is formed.
As preferable technical scheme：The magnetic nanoparticle general molecular formula is MFe2O4, wherein M is Co2+, Ni2+,
Mg2+, Fe2+One or more in.
As preferable technical scheme：The preparation technology of the magnetic nanoparticle of the alkynyl modification is as follows：
（1）Weigh Fe (NO3)3· 9H2O and M (NO3)2· 6H2O, dissolved, and stirred with water, and adjust the pH of solution
>7, presoma pours into and is incubated 4 ~ 24h in reactor at 160 ~ 240 DEG C, then scrubbed, dry, obtains ferrite nano powder
Body；
（2）By step（1）The ferrite nano powder of gained is scattered in the aqueous solution of polyacrylic acid, then 80 ~ 95
40 ~ 90min, magnetic nanoparticle that is then acidified, washing, be dried to obtain surface carboxyl groups are stirred at DEG C；
（3）By step（2）The magnetic nanoparticle of the carboxylated of gained is scattered in dimethyl formamide solution, Ran Houyi
Acid amides reaction occurs at normal temperatures for secondary addition carbodiimide hydrochloride, n-hydroxysuccinimide and propargylamine, most afterwards through washing
Wash, be dried to obtain the magnetic nanoparticle of alkynyl modification.
As preferable technical scheme：The graphene oxide preparation method of Azide modification is：Stone will be aoxidized first
Ink, which is scattered in dimethylformamide or tetrahydrofuran solution, obtains graphene oxide dispersion, then add sodium azide 30 ~
Stirred 2 ~ 3 days at 60 DEG C, finally wash, be dried to obtain the graphene oxide of Azide modification（GO-N3）.
As preferable technical scheme：The method that covalently chelates is：Example weighs alkynyl modification by mass percentage
Magnetic nanoparticle and Azide modification graphene oxide be scattered in dimethyl formamide solution, by evenly mixing after,
Catalyst is added into mixed solution, Dipolar Cycloaddition occurs, most obtains the ferrite-stone through hydrazine hydrate reduction afterwards
The black nano combined absorbing material of alkene（MFe2O4/RGO）.
As preferable technical scheme：The process for dispersing uses ultrasonic disperse.
Present invention also offers a kind of nano combined absorbing material being prepared using above-mentioned preparation method.
Compared with prior art, the advantage of the invention is that：By clicking on coupling nano particle can be made preferably to be sequestered in
On graphenic surface, the composite has good electric conductivity, magnetic property, and compared to Electrostatic Absorption, this is multiple in the application
The nano particle of conjunction mode is not easy to come off from graphenic surface, and has practicality after the coated modification in magnetic nanoparticle surface
By force, the features such as acid resistance is strong, stability is good；Furthermore graphene is set to exist in graphenic surface magnetic nanoparticle growth in situ
Electric charge transfer is produced at covalent coupling and forms strong dielectric relaxor, improves the impedance matching of graphene and magnetic nanoparticle
Can, there is excellent absorbing property, therefore have good application value in absorbing material field.
Brief description of the drawings
Fig. 1 is the course of reaction figure of the embodiment of the present invention 1；
Fig. 2 is the average grain diameter figure of the cobalt ferrite nanoparticles of the embodiment of the present invention 1；
Fig. 3 is the infrared spectrogram that the embodiment of the present invention 1 clicks on composite；
Fig. 4 is the reflection loss figure of 1 Conjugate ferrite of the embodiment of the present invention/reduced graphene composite.
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described.
Embodiment 1：CoFe2O4The preparation method of/RGO composite wave-suction materials
As shown in figure 1, comprise the following steps：
Step（1）：The preparation of alkynyl Conjugate ferrite
In molar ratio 2:1 weighs Fe (NO3)3· 9H2O and Co (NO3)2· 6H2O dispensings, are dissolved in deionized water
Beaker in, and stir, after it is completely dissolved, ammonification water and pH=9 for adjusting solution, solution be transferred to liner poly- four
In PVF reactor, 10h is incubated at 180 DEG C, through washing, being freeze-dried after normal temperature cooling, obtains Conjugate ferrite nano powder
Body, as shown in Fig. 2 its average grain diameter of cobalt ferrite nanoparticles is in 10 ~ 20nm；By mass ratio of the Conjugate ferrite than polyacrylic acid
3:1, by cobalt ferrite nanoparticles ultrasonic disperse in the aqueous solution of polyacrylic acid, 1h is then quickly stirred at 95 DEG C, so
By acidifying, washing, freeze-drying；The cobalt ferrite nanoparticles ultrasonic disperse of a certain amount of carboxylated is weighed in 30ml dimethyl
In formamide solution, then sequentially add carbodiimide hydrochloride, n-hydroxysuccinimide and propargylamine and stir at room temperature
Mix overnight generation acid amides reaction, last cobalt ferrite nanoparticles that are scrubbed, being dried to obtain terminal alkynyl.
Step（2）：Azide graphene oxide（GO-N3）Preparation
Graphite oxide is prepared first with Hummers methods, takes 0.2g graphite oxides ultrasonic disperse in 200ml dimethyl formyls
Graphene oxide dispersion is obtained in amine aqueous solution, 0.2g sodium azide insulated and stirred 2 days at 40 DEG C are then added, most afterwards through washing
Wash, centrifuge, be freeze-dried obtain azido modification graphene oxide（RO-N3）；
Step（3）：Conjugate ferrite/graphene clicks on compound preparation
The cobalt ferrite nanoparticles for the alkynyl that step 1 is obtained and Azide graphene oxide（Mass ratio 10:1）It is super
Sound is scattered in 30ml dimethyl formamide solutions, ferrite is well mixed with graphene oxide after ultrasound, then to solution
Middle addition sodium ascorbate and copper sulphate make ethynylation magnetic nanoparticle occur with Azide graphene oxide even as catalyst
Polar ring addition reaction, even if magnetic nanoparticle is covalently sequestered in surface of graphene oxide, infared spectrum such as Fig. 3 after chelating, fold
The peak value appearance that nitrogen base disappears new；Product Magneto separate, after distilling water washing, add hydrazine hydrate（M graphene oxides：M hydrazine hydrates=
10：7）Reduction, obtain clicking on the CoFe prepared after scrubbed, dry2O4/ RGO composite wave-suction materials A.
After tested, prepared composite wave-suction material A is found in 2 ~ 18GHz, minimum -40 dB of reflection loss
(6.8GHz)；Reflection loss can reach -25dB at Ku wave bands 15.2GHz, and effective Absorber Bandwidth less than -10dB is
5.2GHz.With reference to example it can be seen that the composite wave-suction material of the invention prepared is in C-band（That is 4-8 GHz）With Ku wave bands（I.e.
12-18 GHz）All there is excellent microwave absorbing property, referring to Fig. 4.
Embodiment 2：
NiFe2O4, graphene preparation method respectively with the step of embodiment 1（1）, step（2）, in mass ratio 5:1 weighs
Alkynyl NiFe2O4With Azide graphene, preparation method is the same as the step of embodiment 1（3）, obtain NiFe2O4/ RGO composite wave-absorbings
Material B.Prepared composite B reaches 4.8GHz in frequency bandwidth of 2 ~ 18GHz internal reflection rates penalty values less than -10dB, most
Small reachable-the 44dB of loss of reflectivity value (5.6GHz).
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (6)
- A kind of 1. preparation method of nano combined absorbing material, it is characterised in that：By alkynyl modification magnetic nanoparticle with The graphene oxide matrix of Azide modification is compound；The magnetic nanoparticle of alkynyl modification and the graphite oxide of Azide modification The proportioning of alkenyl body is by weight (5-10)：1 is well mixed, the magnetic for then being modified the alkynyl by cycloaddition reaction Property nano particle be covalently sequestered in the surface of graphene oxide of Azide modification, finally with hydrazine hydrate reduction, form iron Oxysome-graphene nano composite wave-suction material.
- 2. preparation method according to claim 1, it is characterised in that the magnetic Nano being sequestered on graphenic surface Granulin molecule formula is MFe2O4, wherein M is divalent transition metal ion Co2+、Ni2+And Zn2+In one or more.
- 3. preparation method according to claim 2, it is characterised in that the system of the magnetic nanoparticle of the alkynyl modification Standby technique is as follows：(1) Fe (NO are weighed3)3·9H2O and M (NO3)2·6H2O, dissolved, and stirred with water, and adjust the pH of solution>7, so 4~24h is incubated at 16~240 DEG C afterwards, it is then scrubbed, dry, obtain ferrite nano powder；(2) the ferrite nano powder obtained by step (1) is scattered in the aqueous solution of polyacrylic acid, then at 80~95 DEG C Stir 40~90min, magnetic nanoparticle that is then acidified, washing, be dried to obtain surface carboxyl groups；(3) magnetic nanoparticle of the carboxylated obtained by step (2) is scattered in dimethylformamide or tetrahydrofuran solution, Then carbodiimide hydrochloride, n-hydroxysuccinimide and propargylamine are sequentially added acid amides reaction occurs at normal temperatures, most By the magnetic nanoparticle for washing, being dried to obtain alkynyl modification.
- 4. preparation method according to claim 1, it is characterised in that the graphene oxide preparation side of the Azide modification Method is：Graphite oxide GO is prepared by raw material of graphite first with Hummers methods, by gained graphite oxide ultrasonic disperse in diformazan Graphene oxide dispersion is obtained in base formamide or tetrahydrofuran solution, sodium azide is then added and is stirred at 30~80 DEG C 2~7 days, finally wash, be dried to obtain the graphene oxide GO-N of Azide modification3。
- 5. preparation method according to claim 1, it is characterised in that the method that covalently chelates is：By quality percentage Dimethylformamide or four are scattered in than weighing the magnetic nanoparticle of alkynyl modification and the graphene oxide of Azide modification In hydrogen tetrahydrofuran solution, by evenly mixing after, add catalyst into mixed solution, Dipolar Cycloaddition occur, most afterwards through water Hydrazine reduction is closed, obtains described ferrite-graphene nano composite wave-suction material MFe2O4/RGO。
- 6. according to the preparation method described in claim 3-5 any one, it is characterised in that：The process for dispersing is using ultrasound point Dissipate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610361468.2A CN105950112B (en) | 2016-05-27 | 2016-05-27 | A kind of nano combined absorbing material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610361468.2A CN105950112B (en) | 2016-05-27 | 2016-05-27 | A kind of nano combined absorbing material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105950112A CN105950112A (en) | 2016-09-21 |
| CN105950112B true CN105950112B (en) | 2018-02-23 |
Family
ID=56909898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610361468.2A Active CN105950112B (en) | 2016-05-27 | 2016-05-27 | A kind of nano combined absorbing material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105950112B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107936525A (en) * | 2017-11-21 | 2018-04-20 | 南京理工大学 | Polymeric material of graphene oxide composite material filling being covalently attached layer by layer and preparation method thereof |
| CN110104635A (en) * | 2018-04-04 | 2019-08-09 | 朱晶晶 | Utilize the preparation method of the composite Nano electromagnetic wave absorbent material of graphene preparation |
| CN109174039A (en) * | 2018-10-09 | 2019-01-11 | 李忠 | A kind of composite nano materials and preparation method thereof for air cleaning |
| CN110054869B (en) * | 2019-05-13 | 2021-05-25 | 青岛碳智新材料科技有限公司 | Preparation method of graphene oxide/nano silicon dioxide/epoxy resin composite material |
| CN110272243B (en) * | 2019-06-21 | 2021-11-05 | 中国人民解放***箭军工程大学 | Double-layer cement-based wave-absorbing material and preparation method thereof |
| CN110724493B (en) * | 2019-09-29 | 2022-11-18 | 安徽理工大学 | Multi-walled carbon nanotube/ferroferric oxide/nano oxide hybrid wave-absorbing material and preparation method thereof |
| CN110724492B (en) * | 2019-09-29 | 2022-11-18 | 安徽理工大学 | Ferroferric oxide/nano oxide hybrid wave-absorbing material and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157809A (en) * | 2013-02-05 | 2013-06-19 | 西南科技大学 | Preparation method of graphene/metal nanoparticle composite material with sandwich structure |
| CN103191699A (en) * | 2013-04-23 | 2013-07-10 | 北京化工大学 | Ferrite/graphene composite adsorbent and preparation and using methods thereof |
| CN103341346A (en) * | 2013-06-26 | 2013-10-09 | 江苏省环境科学研究院 | Preparation method of manganese ferrite nanoparticle-graphene compound |
| CN103467079A (en) * | 2013-08-28 | 2013-12-25 | 西北工业大学 | Preparation method for grapheme/Ni0.8Zn0.2Ce0.06Fe1.94O4 nano wave-absorbing material |
| CN103965250A (en) * | 2013-12-24 | 2014-08-06 | 中国科学院上海应用物理研究所 | Technetium-99m-labeledgraphene oxide nanoparticle and preparation method thereof |
| CN104984740A (en) * | 2015-06-19 | 2015-10-21 | 西北师范大学 | Preparation and application of cobalt ferrite-quasi-graphene carbon nano-composite magnetic adsorption material |
| CN105111913A (en) * | 2015-10-08 | 2015-12-02 | 北京理工大学 | Graphene/nano ferrite based water electromagnetic shielding paint and preparation method thereof |
| CN105199667A (en) * | 2015-10-21 | 2015-12-30 | 李同乐 | Continuous synthesis method of graphene/ferrite nanocomposite |
| KR20160047266A (en) * | 2014-10-22 | 2016-05-02 | 엘지이노텍 주식회사 | Electromagnetic wave shielding sheet, wireless power transmitting apparatus and wireless power receiving apparatus comprising the same |
-
2016
- 2016-05-27 CN CN201610361468.2A patent/CN105950112B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157809A (en) * | 2013-02-05 | 2013-06-19 | 西南科技大学 | Preparation method of graphene/metal nanoparticle composite material with sandwich structure |
| CN103191699A (en) * | 2013-04-23 | 2013-07-10 | 北京化工大学 | Ferrite/graphene composite adsorbent and preparation and using methods thereof |
| CN103341346A (en) * | 2013-06-26 | 2013-10-09 | 江苏省环境科学研究院 | Preparation method of manganese ferrite nanoparticle-graphene compound |
| CN103467079A (en) * | 2013-08-28 | 2013-12-25 | 西北工业大学 | Preparation method for grapheme/Ni0.8Zn0.2Ce0.06Fe1.94O4 nano wave-absorbing material |
| CN103965250A (en) * | 2013-12-24 | 2014-08-06 | 中国科学院上海应用物理研究所 | Technetium-99m-labeledgraphene oxide nanoparticle and preparation method thereof |
| KR20160047266A (en) * | 2014-10-22 | 2016-05-02 | 엘지이노텍 주식회사 | Electromagnetic wave shielding sheet, wireless power transmitting apparatus and wireless power receiving apparatus comprising the same |
| CN104984740A (en) * | 2015-06-19 | 2015-10-21 | 西北师范大学 | Preparation and application of cobalt ferrite-quasi-graphene carbon nano-composite magnetic adsorption material |
| CN105111913A (en) * | 2015-10-08 | 2015-12-02 | 北京理工大学 | Graphene/nano ferrite based water electromagnetic shielding paint and preparation method thereof |
| CN105199667A (en) * | 2015-10-21 | 2015-12-30 | 李同乐 | Continuous synthesis method of graphene/ferrite nanocomposite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105950112A (en) | 2016-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105950112B (en) | A kind of nano combined absorbing material and preparation method thereof | |
| CN107399735B (en) | Preparation method and application of graphene composite aerogel wave-absorbing material | |
| Lei et al. | Tunable dielectric loss to enhance microwave absorption properties of flakey FeSiAl/ferrite composites | |
| CN108690556B (en) | Preparation method of reduced graphene oxide/multiwalled carbon nanotube/nickel ferrite ternary nano composite wave-absorbing material | |
| CN112839500B (en) | Yolk shell hollow ferroferric oxide @ air @ carbon nano composite wave-absorbing material and preparation method thereof | |
| CN107626931B (en) | Preparation and application of cobalt-graphene composite material for absorbing electromagnetic waves | |
| CN107949266B (en) | A kind of three-dimensional porous flower-like structure cobalt/carbon nano composite electromagnetic wave absorption material and preparation method thereof | |
| Chen et al. | PANI/BaFe12O19@ Halloysite ternary composites as novel microwave absorbent | |
| CN105219345B (en) | Preparation method of ferroferric oxide @ iron core shell structure-graphene composite absorbing material | |
| Wang et al. | Construction of core-shell structured Co7Fe3@ C nanocapsules with strong wideband microwave absorption at ultra-thin thickness | |
| CN105647468A (en) | Wave-absorbing material based on grapheme and preparation method thereof | |
| CN109207123A (en) | A kind of double shell structurre carbonyl iron composite absorbers and preparation method | |
| CN109005660B (en) | Cobalt nano-particle and redox graphene electromagnetic wave absorbent material preparation method | |
| Zubair et al. | Effect of barium hexaferrites and thermally reduced graphene oxide on EMI shielding properties in polymer composites | |
| CN108795379A (en) | A kind of preparation method of three-dimensional netted multi-walled carbon nanotube/Ni ferrite composite wave-suction material | |
| CN110342531B (en) | Iron powder coated silicon dioxide material and preparation method thereof | |
| CN107286907B (en) | Molybdenum disulfide/carbonyl iron composite microwave absorbent with core-shell structure and preparation method thereof | |
| CN107011540A (en) | A kind of carbonyl iron/graphene/polyvinylpyrrolidone composite wave-suction material, its preparation method and its prepared suction wave plate | |
| CN108559445A (en) | A kind of preparation method of the nano combined absorbing material of redox graphene/Mn ferrite | |
| CN108587159A (en) | One type graphene carbonitride/ferroso-ferric oxide/polyaniline nano composite wave-suction material and preparation method thereof | |
| CN109451715B (en) | Graphene-carbonyl iron powder @ ferroferric oxide electromagnetic wave absorption composite material | |
| CN107434857B (en) | Graphene-loaded cerium oxide and rubber composite material and preparation method thereof | |
| CN113316379B (en) | Nano composite structure wave absorber material, preparation method and application | |
| CN107338023A (en) | A kind of nano combined microwave absorption and preparation method thereof | |
| Hou et al. | Achieving high-efficiency and broad bandwidth with low filler loading for hierarchical Fe3O4/Co-MOF absorbers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |