CN109548393A - A kind of narrow frequency range responding microwave material and preparation method thereof - Google Patents
A kind of narrow frequency range responding microwave material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052709 silver Inorganic materials 0.000 claims abstract description 23
- 239000004332 silver Substances 0.000 claims abstract description 23
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011258 core-shell material Substances 0.000 claims abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- 230000001698 pyrogenic effect Effects 0.000 claims abstract 6
- -1 glyoxaline compound Chemical class 0.000 claims abstract 4
- 229920001577 copolymer Polymers 0.000 claims abstract 2
- 239000003446 ligand Substances 0.000 claims abstract 2
- 229910021645 metal ion Inorganic materials 0.000 claims abstract 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000002086 nanomaterial Substances 0.000 claims description 17
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- YZEUHQHUFTYLPH-UHFFFAOYSA-N 2-nitroimidazole Chemical compound [O-][N+](=O)C1=NC=CN1 YZEUHQHUFTYLPH-UHFFFAOYSA-N 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 22
- 230000035699 permeability Effects 0.000 description 15
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000002121 nanofiber Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 229910021404 metallic carbon Inorganic materials 0.000 description 3
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- AJAVMTJTPWMHAE-UHFFFAOYSA-N 1h-imidazole;methanol Chemical compound OC.C1=CNC=N1 AJAVMTJTPWMHAE-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- NYGZKMXIYAFNRM-UHFFFAOYSA-N methanol;zinc Chemical compound [Zn].OC NYGZKMXIYAFNRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Catalysts (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention discloses a kind of narrow frequency range responding microwave material and preparation method thereof, it is the core-shell structure copolymer nanofibrous structures being made of kernel silver nanoparticle fiber and shell pyrogenic metal organic frame, wherein, pyrogenic metal organic frame is the thermal decomposition product of metal organic frame, metal organic frame with one or more of cobalt, iron, zinc, nickel for metal ion, using glyoxaline compound as ligand.The responding microwave material has narrow frequency range microwave resonance response characteristic, and resonant frequency is adjustable, can be widely applied to the fields such as electro-magnetic wave absorption, energy augmentor, electromagnetism accelerator, microwave antenna, electromagnetic sensing.
Description
Technical field
The present invention relates to a kind of narrow frequency range responding microwave materials and preparation method thereof, belong to electromagnetic response material technology neck
Domain.
Background technique
In recent years, the nano material with electromagnetic response characteristic presents huge potentiality in terms of microwave defense material,
And receive domestic and international extensive concern.These materials based on Debye relaxation loss mechanism caused by interfacial polarization, are pursued mostly
Wide-band electromagnetic response characteristic.However, some microwave electronic devices such as power amplifier, particle accelerator, antenna etc. require ratio
The narrower frequency range of Debye relaxation, faster change in dielectric constant, to realize narrow frequency range electromagnetic response.Currently, based on molecule or
The Lorentz plasmon resonance of electronics shows as narrow frequency range electromagnetic response, and frequency concentrates on Terahertz to ultraviolet frequencies range.Gold
The narrow frequency range plasma resonance of metal surface typically occurs in optics frequency range.So far, narrow frequency range responding microwave material is designed still
It is a big difficulty in industry, there is very big challenge.
Summary of the invention
The object of the present invention is to provide a kind of narrow frequency range responding microwave material and preparation method thereof, which has unique
Narrow frequency range electromagnetic response characteristic.
The technical scheme adopted by the invention is as follows:
A kind of narrow frequency range responding microwave material, the narrow frequency range responding microwave material are by silver nanoparticle fiber and metal carbon/oxidation
The core-shell nanostructure material that object is constituted, wherein shell metallic carbon/oxide is to be pyrolyzed to be formed by metal organic frame temperature control.
Further, shell metallic carbon/oxide component includes carbon, nitrogen, oxygen and cobalt, iron, zinc, one in nickel
Kind is several.
Preferably, shell metallic carbon/oxide is with a thickness of 10 ~ 1000 nanometers.
The preparation method of above-mentioned narrow frequency range responding microwave material, comprising the following steps:
Step 1, the metal salt methanol solution stirring 30 of 1 mol/L is added into the silver nanoparticle fiber methanol dispersion liquid of 1 grams per liter
Minute or more, the glyoxaline compound methanol solution that 1 mol/L is then added stirs 12 hours or more, through filtering, cleaning, very
Sky is dried to obtain silver/metal organic frame precursor；
Step 2, silver/metal organic frame precursor is placed in temperature control under inert atmosphere to calcine, obtains powdered silver/metal oxidation of coal
Object core-shell nanostructure.
Preferably, the quality molar ratio of silver nanoparticle fiber and metal salt is 1:0.01 ~ 1:0.5, metal salt and imidazoles
The molar ratio of class compound is 1: 5.
Preferably, metal salt is the nitrate or hydrochloride of cobalt, iron, zinc, nickel.
Preferably, calcination temperature is 600 DEG C, and heating rate is 1 ~ 10 degree/min, and inert atmosphere is nitrogen or argon gas.
Compared with prior art, the present invention has the following obvious advantages:
(1) present invention can give full play to its narrow frequency range plasmon resonance characteristic using highly conductive silver nanoparticle fiber as core.
(2) present invention has thickness controllable, element species are adjustable, to make institute using metal organic frame as shell precursor
The design that silver/metal carbon oxide core-shell nanostructure performance has height is formed, promotes resonant frequency red shift to microwave
Frequency range.
(3) it is raw that scale high-volume may be implemented without complicated synthesis device in preparation method simple process of the present invention
It produces.
(4) narrow frequency range responding microwave material prepared by the present invention is presented powdered, generally with macromolecule resin, binder etc.
It is mixed and made into composite material use, arbitrary shape can be processed into according to actual needs, can also be used as coating use.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of sample 1 made from the embodiment of the present invention 1.
Fig. 2 is the transmission electron microscope picture of sample 1 made from the embodiment of the present invention 1.
Fig. 3 is the complex dielectric permittivity of sample 1 made from the embodiment of the present invention 1.
Fig. 4 is the complex permeability of sample 1 made from the embodiment of the present invention 1.
Fig. 5 is the scanning electron microscope (SEM) photograph of sample 2 made from the embodiment of the present invention 2.
Fig. 6 is the transmission electron microscope picture of sample 2 made from the embodiment of the present invention 2.
Fig. 7 is the complex dielectric permittivity of sample 2 made from the embodiment of the present invention 2.
Fig. 8 is the complex permeability of sample 2 made from the embodiment of the present invention 2.
Fig. 9 is the scanning electron microscope (SEM) photograph of sample 3 made from the embodiment of the present invention 3.
Figure 10 is the transmission electron microscope picture of sample 3 made from the embodiment of the present invention 3.
Figure 11 is the complex dielectric permittivity of sample 3 made from the embodiment of the present invention 3.
Figure 12 is the complex permeability of sample 3 made from the embodiment of the present invention 3.
Figure 13 is the complex dielectric permittivity of sample 5 made from the embodiment of the present invention 5.
Figure 14 is the complex permeability of sample 7 made from the embodiment of the present invention 7.
Specific embodiment
Below in conjunction with attached drawing, technical scheme is described further, but the scope of protection of present invention is simultaneously
It is not limited to this.
The present invention is inspired in the narrow frequency range plasma resonance characteristic of metal nano material, we can using a kind of size
Adjust, the silver nanoparticle fiber of technology of preparing maturation is core, pass through surface controllable growth nano level metal organic frame (MOFs) thin layer
With temperature control pyrolytic technique under inert atmosphere, a kind of metal/metal oxycarbide core-shell nanostructure is successfully prepared.This kind of nanometer
Material had both maintained the narrow frequency range electromagnetic response characteristic of metal nano fiber, be also successfully realized resonant frequency from optics frequency range to
The large-scale red shift of microwave frequency band is expected to be used widely on New-generation microwave electronic device.
Embodiment 1
The preparation method of responding microwave material sample 1 of the present invention the following steps are included:
Step 1, it disperses silver nanoparticle fiber in methanol under ultrasonic wave added and prepares 1 grams per liter dispersion liquid；Prepare the nitre of 1 mol/L
Sour zinc methanol solution；Prepare the imidazolemethanol solution of 1 mol/L.20 milliliters are added into 80 milliliters of silver nanoparticle fiber dispersions
Zinc nitrate solution stirring 30 minutes or more, 100 milliliters of methyl imidazole solutions are then added and stir 12 hours, through filtering, methanol
It the processes such as washes, be dried in vacuo and obtaining silver/metal organic frame precursor.
Step 2, silver/metal organic frame precursor is placed under argon gas to heat up 600 degree and then keeps 600 degree of calcinings 4 hours,
Obtain sample 1.Wherein, heating rate is 5 degrees/min.
Fig. 1 and Fig. 2 is respectively the scanning electron microscope (SEM) photograph and transmission electron microscope picture of sample 1 in embodiment 1, it can be seen that sample 1 is micro-
Uniform core-shell nanostructure is presented in sight, belongs to one-dimensional axial core-shell nano fiber, there is high draw ratio, shell thickness is about
It is 100 nanometers.Fig. 3 and Fig. 4 is the complex dielectric permittivity figure and complex permeability figure of 1 microwave frequency band of sample in embodiment 1, can be seen
Sample 1 shows strong narrow frequency range dielectric resonance and magnetic resonance characteristics in 12.48 GHz out.
Embodiment 2
The zinc nitrate solution of step 1 in embodiment 1 is changed to cobalt chloride solution, other implementation conditions obtain sample with embodiment 1
2。
Fig. 5 and Fig. 6 is respectively the scanning electron microscope (SEM) photograph and transmission electron microscope picture of sample 2 in embodiment 2, it can be seen that sample 2 is micro-
Uniform core-shell nano fibre structure is presented in sight, there is high draw ratio, shell thickness is about 60 nanometers.Fig. 7 and Fig. 8 is real
Apply the complex dielectric permittivity figure and complex permeability figure of 2 microwave frequency band of sample in example 2, it can be seen that sample 2 is in 10.35,11.00 Hes
Multiple frequency ranges such as 16.57 GHz show weak dielectric resonance phenomenon, and present in 10.52 and 16.27 GHz, two frequencies
Weak magnetic resonance characteristics.
Embodiment 3
The zinc nitrate solution of step 1 in embodiment 1 is changed to the mixed solution of zinc nitrate and cobalt chloride that molar ratio is 1:1,
Its implementation condition obtains sample 3 with embodiment 1.
Fig. 9 and Figure 10 is respectively the scanning electron microscope (SEM) photograph and transmission electron microscope picture of sample 3 in embodiment 3, it can be seen that sample 3 is micro-
Uniform rough surface nanofiber is presented in sight, there is high draw ratio and core-shell nanostructure, shell thickness is about 50 to receive
Rice.Figure 11 and Figure 12 is the complex dielectric permittivity figure and complex permeability figure of 3 microwave frequency band of sample in embodiment 3, it can be seen that sample
3 show the narrow frequency range dielectric resonance phenomenon enhanced than sample 1 in 14.48 GHz, and show 14.52 than the enhancing of sample 1
Narrow frequency range electromagnetic induction phenomenon, absolutely prove that cobalt element doping effectively while can adjust resonant frequency and the strength of resonance.
Embodiment 4
The zinc nitrate solution of step 1 in embodiment 1 is changed to solution of ferrous chloride, other implementation conditions obtain sample with embodiment 1
Product 4.By test, sample 4 is rendered as one-dimensional nucleocapsid nanostructure on microcosmic, and shell thickness is about 70 nanometers, answers dielectric
There is strong covibration, resonant frequency shift to 9.28 GHz in microwave frequency band in constant and complex permeability constant.
Embodiment 5
The zinc nitrate solution of step 1 in embodiment 1 is changed to nickel nitrate solution, other implementation conditions obtain sample with embodiment 1
5.By test, sample 5 is rendered as one-dimensional nucleocapsid nanostructure on microcosmic, and shell thickness is about 80 nanometers, and it is normal to answer dielectric
For several and complex permeability constant in microwave frequency band there are strong covibration, resonant frequency shift is shown in Figure 12 to 12.47 GHz.
Embodiment 6
The methyl imidazole solution of step 1 in embodiment 1 is changed to imidazole solution, other implementation conditions obtain sample with embodiment 1
6.By test, sample 6 is rendered as one-dimensional nucleocapsid nanostructure on microcosmic, and shell thickness is about 30 nanometers, and it is normal to answer dielectric
In microwave frequency band, there are strong covibration, resonant frequency shifts to 14.26 GHz with complex permeability constant for number.
Embodiment 7
The methyl imidazole solution of step 1 in embodiment 1 is changed to benzimidazole solution, other implementation conditions are obtained with embodiment 1
Sample 7.By test, sample 7 is rendered as one-dimensional nucleocapsid nanostructure on microcosmic, and shell thickness is about 200 nanometers, multiple to be situated between
In microwave frequency band there are apparent covibration, resonant frequency shift is shown in figure to 11.85 GHz for electric constant and complex permeability constant
14。
Embodiment 8
20 milliliters of zinc nitrate solutions of step 1 in embodiment 1 are changed to 4 milliliters of zinc nitrate solutions, 100 milliliters of methyl imidazole solutions
20 milliliters of methyl imidazole solutions are changed to, other implementation conditions obtain sample 8 with embodiment 1.By test, sample 8 is on microcosmic
It is rendered as one-dimensional nucleocapsid nanostructure, shell thickness is about 10 nanometers, and complex dielectric permittivity and complex permeability constant are in Microwave Frequency
There are significant covibration, resonant frequency shifts to 8.24 GHz for section.
Embodiment 9
20 milliliters of zinc nitrate solutions of step 1 in embodiment 1 are changed to 200 milliliters of zinc nitrate solutions, 100 milliliters of methylimidazoles are molten
Liquid is changed to 1 liter of methyl imidazole solution, and other implementation conditions obtain sample 9 with embodiment 1.By test, sample 9 is on microcosmic
It is rendered as one-dimensional nucleocapsid nanostructure, shell thickness is about 1000 nanometers, and complex dielectric permittivity and complex permeability constant are in microwave
There are medium covibration, resonant frequency shifts to 6.68 GHz for frequency range.
Comparative example 1
The zinc nitrate solution of step 1 in embodiment 1 is changed to copper nitrate solution, other implementation conditions obtain sample with embodiment 1
10.By test, sample 10 is mixed and disorderly in microcosmic upper structure, cannot be rendered as one-dimensional nucleocapsid nanostructure, complex dielectric permittivity and
Covibration is not observed in microwave frequency band in complex permeability constant.
Comparative example 2
The methyl imidazole solution of step 1 in embodiment 1 is changed to benzenetricarboxylic acid solution, other implementation conditions are passed through with embodiment 1
It is existing there is no resonating in microwave frequency band to cannot get one-dimensional nucleocapsid nanostructure, complex dielectric permittivity and complex permeability constant for test
As.
The present invention is core using silver nanoparticle fiber, is pyrolyzed to form metal oxide shell as template using metal organic frame,
The uniform core-shell nano fiber of microscopic appearance is constructed, the narrow frequency range resonance characteristics of silver nanoparticle fiber had not only been maintained, but also keeps it total
Vibration frequency success red shift presents strong narrow frequency range microwave resonance characteristic to microwave frequency band.Preparation method technique of the present invention
Simply, at low cost, it is suitable for industrialized production.
The above embodiment is merely an example for clearly illustrating the present invention, and is not to embodiment party of the invention
The restriction of formula.For those of ordinary skill in the art, other differences can also be made on the basis of the above description
The variation or variation of form.There is no necessity and possibility to exhaust all the enbodiments.And these belong to essence of the invention
The obvious changes or variations that mind is extended out are still in the protection scope of this invention.
Claims (10)
1. a kind of narrow frequency range responding microwave material, it is characterised in that: it is that had by kernel silver nanoparticle fiber and shell pyrogenic metal
The core-shell structure copolymer nanofibrous structures that machine frame is constituted, wherein pyrogenic metal organic frame is the thermal decomposition product of metal organic frame,
Metal organic frame with one or more of cobalt, iron, zinc, nickel for metal ion, using glyoxaline compound as ligand.
2. narrow frequency range responding microwave material according to claim 1, it is characterised in that: glyoxaline compound be selected from imidazoles,
One or more of 2-methylimidazole, benzimidazole, 2- nitroimidazole.
3. narrow frequency range responding microwave material according to claim 1, it is characterised in that: the composition of pyrogenic metal organic frame
Element includes one or more of cobalt, iron, zinc, nickel and carbon, nitrogen, oxygen element.
4. narrow frequency range responding microwave material according to claim 1, it is characterised in that: the thickness of pyrogenic metal organic frame
It is 10 ~ 1000 nanometers.
5. the preparation method of -5 any narrow frequency range responding microwave materials according to claim 1, which is characterized in that including such as
Lower step:
Step 1, it is added into silver nanoparticle fiber methanol dispersion liquid the stirring of metal salt methanol solution 30 minutes or more, miaow is then added
The stirring of azole compounds methanol solution 12 hours or more, silver/metal organic frame precursor was obtained through filtering, cleaning, vacuum drying；
Step 2, silver/metal organic frame precursor is placed in temperature control under inert atmosphere to calcine, obtains powdered silver/metal oxidation of coal
Object core-shell nanostructure.
6. preparation method according to claim 5, it is characterised in that: the concentration of silver nanoparticle fiber methanol dispersion liquid be 1 gram/
It rises；The concentration of metal salt methanol solution is 1 mol/L；The concentration of glyoxaline compound methanol solution is 1 mol/L.
7. preparation method according to claim 5, it is characterised in that: the quality of silver nanoparticle fiber and metal salt mole it
Than for 1:0.01 ~ 1:0.5, the molar ratio of metal salt and glyoxaline compound is 1: 5.
8. preparation method according to claim 5, it is characterised in that: metal salt be cobalt, iron, zinc, any one in nickel or
Several nitrate or hydrochloride.
9. preparation method according to claim 5, it is characterised in that: calcination temperature is 600 ± 10 DEG C, heating rate 1
~ 10 degrees/min, inert atmosphere is nitrogen or argon gas.
10. application of -5 any materials in narrow frequency range responding microwave electronic device according to claim 1.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104028181A (en) * | 2014-04-24 | 2014-09-10 | 温州大学 | Precious metal/paramagnetic metal composite nanoparticle with core-shell structure and application thereof |
| CN104827029A (en) * | 2015-05-29 | 2015-08-12 | 厦门大学 | Method for synthesizing shell isolation silver nanoparticles |
| CN105152281A (en) * | 2015-09-10 | 2015-12-16 | 上海大学 | Preparation method of capacitive type desalination electrode prepared from hierarchical porous carbon material with core-shell structure |
| CN105885784A (en) * | 2016-04-18 | 2016-08-24 | 青岛大学 | Preparation method of wave-absorbing material adopting core-shell structure |
| CN106041121A (en) * | 2016-06-30 | 2016-10-26 | 青岛科技大学 | Preparation method of carbon nanomaterial loaded nanometer ferrite hollow sphere |
| CN107887592A (en) * | 2017-11-17 | 2018-04-06 | 武汉理工大学 | Carbon coating ZnO nano-wire and its preparation method and application |
| CN108067250A (en) * | 2017-09-27 | 2018-05-25 | 东北师范大学 | A kind of Ag nano wires/Cu2O nucleocapsids and preparation method thereof |
| CN108237222A (en) * | 2018-01-05 | 2018-07-03 | 广东工业大学 | A kind of nuclear shell structure nano metal interconnection process |
| CN108579758A (en) * | 2018-03-23 | 2018-09-28 | 中国科学院宁波材料技术与工程研究所 | A kind of controllable bimetallic nanometer nuclear shell nano-structure, catalyst, its preparation method and application |
| CN108752905A (en) * | 2018-05-04 | 2018-11-06 | 南京恒新新材料有限公司 | A kind of composite wave-suction material and preparation method thereof based on silver-colored@polypyrroles core-shell nano fiber |
-
2018
- 2018-11-09 CN CN201811332063.1A patent/CN109548393B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104028181A (en) * | 2014-04-24 | 2014-09-10 | 温州大学 | Precious metal/paramagnetic metal composite nanoparticle with core-shell structure and application thereof |
| CN104827029A (en) * | 2015-05-29 | 2015-08-12 | 厦门大学 | Method for synthesizing shell isolation silver nanoparticles |
| CN105152281A (en) * | 2015-09-10 | 2015-12-16 | 上海大学 | Preparation method of capacitive type desalination electrode prepared from hierarchical porous carbon material with core-shell structure |
| CN105885784A (en) * | 2016-04-18 | 2016-08-24 | 青岛大学 | Preparation method of wave-absorbing material adopting core-shell structure |
| CN106041121A (en) * | 2016-06-30 | 2016-10-26 | 青岛科技大学 | Preparation method of carbon nanomaterial loaded nanometer ferrite hollow sphere |
| CN108067250A (en) * | 2017-09-27 | 2018-05-25 | 东北师范大学 | A kind of Ag nano wires/Cu2O nucleocapsids and preparation method thereof |
| CN107887592A (en) * | 2017-11-17 | 2018-04-06 | 武汉理工大学 | Carbon coating ZnO nano-wire and its preparation method and application |
| CN108237222A (en) * | 2018-01-05 | 2018-07-03 | 广东工业大学 | A kind of nuclear shell structure nano metal interconnection process |
| CN108579758A (en) * | 2018-03-23 | 2018-09-28 | 中国科学院宁波材料技术与工程研究所 | A kind of controllable bimetallic nanometer nuclear shell nano-structure, catalyst, its preparation method and application |
| CN108752905A (en) * | 2018-05-04 | 2018-11-06 | 南京恒新新材料有限公司 | A kind of composite wave-suction material and preparation method thereof based on silver-colored@polypyrroles core-shell nano fiber |
Non-Patent Citations (1)
| Title |
|---|
| 张坤: "基于管状纳米材料复合物的设计及其吸波性能研究", 《中国优秀硕士学位论文全文数据库（电子期刊）》 * |
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