CN106884309B - Fiber hybrid particle and polymer-based composite material - Google Patents
Fiber hybrid particle and polymer-based composite material Download PDFInfo
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Abstract
The invention provides a fiber hybrid particle and a polymer matrix composite. The fiber hybrid particles consist of nanofibers and nanoparticles loaded on the surfaces of the nanofibers; the coverage rate of the nano particles on the surface of the nano fiber is 5% -100%; the diameter of the nano fiber is 50nm-300nm, and the length is 1 μm-100 μm; the particle size of the nano particles is equal to or less than the diameter of the nano fibers; the interface connection between the nanofiber and the nanoparticle is physical adsorption or/and chemical bond combination. The polymer-based composite material of the present invention comprises a polymer and the above-described fiber hybrid particles filled in the polymer. The fiber hybrid particle solves the problem of agglomeration and winding of granular and fibrous nano materials, and endows the fibrous hybrid nano material with multiple functions, so that the polymer-based composite material with controllable and multifunctional performance is obtained in a more convenient and effective manner.
Description
Technical Field
The invention relates to fiber hybrid particles and a polymer matrix composite material formed by the fiber hybrid particles, belonging to the field of nanofiber materials.
Background
Nanomaterials are broadly defined as materials that have at least one dimension in three-dimensional space in the nanoscale range (0.1nm-100nm) or that are composed of them as the basic unit. The nano material has extremely fine particles and extremely large surface area, and the atomic percentage of disordered arrangement on the surface of the particles is far more than the atomic percentage of the surface of a large-scale material, so that the nano material has the characteristics which are not possessed by the traditional solid material, such as volume effect, surface effect, quantum size effect, macroscopic quantum tunneling effect, dielectric confinement effect and the like, and the nano material has microwave absorption performance, high surface activity, strong oxidizing property, superparamagnetism and the like. Besides the above basic characteristics, the nano material also has special optical, catalytic, chemical reaction kinetics and special physical and mechanical properties. The use of nanomaterials greatly enriches the development and application of materials.
The nano material has various excellent characteristics, and the high molecular polymer material also has unique performances in the aspects of mechanics, physics, chemistry and electricity. The nano material is compounded with the high molecular polymer material, and the prepared composite material not only has the special performance of the nano material, but also can keep the excellent characteristics of the high molecular polymer material.
With the development of science and technology, materials are required to have various composite properties or more specific properties. Therefore, the application of a single nanomaterial has not been able to meet the technical requirements in some fields. To achieve this goal, the compounding of nanomaterials is becoming a necessity.
The conventional technique of compounding nanomaterials is to mix several nanomaterials with other substances (polymers or nanomaterials). However, due to the high specific surface area and the high surface activity of the nanomaterial, particles are very easily adsorbed together by van der waals force to form agglomerates and are not easily dispersed again, so that it is not easy to effectively control the properties of the material in the process of developing a new material.
The nanofiber material has the advantages of large specific surface area, high transverse-longitudinal ratio, strong mutual permeability with other substances, fine structure of nanofiber fabric, excellent flexibility, adsorbability, filterability and the like. The unique performance of the nano-fiber enables the nano-fiber to have great market potential in the fields of membrane materials, filter media, catalysts, electronic products, biological products, composite reinforced materials and the like. However, the nanofiber material has extremely high aspect ratio and specific surface area, so that the nanofiber material is easy to wind when being prepared into a composite material with a polymer, and particularly when being compounded with nanoparticles by a mechanical method, the composite material with uniform dispersion is difficult to obtain, and the performance is difficult to control.
Disclosure of Invention
In order to solve the above-described problems, an object of the present invention is to provide a fibrous hybrid particle and a polymer-based composite material composed of the fibrous hybrid particle. The fiber hybrid particle solves the problem of agglomeration and winding of granular and fibrous nano materials, and endows the fibrous hybrid nano material with multiple functions, so that the polymer-based composite material with controllable and multifunctional performance is obtained in a more convenient and effective manner.
In order to achieve the above technical objects, the present invention first provides a fibrous hybrid particle, which is composed of nanofibers and nanoparticles supported on the surfaces of the nanofibers;
wherein the coverage rate of the nano particles on the surface of the nano fiber is 5% -100%;
the diameter of the nano fiber is 50nm-300nm, and the length of the nano fiber is 1 mu m-100 mu m;
the particle size of the nano particles is equal to or less than the diameter of the nano fibers;
the interface connection between the nano fiber and the nano particle is physical adsorption or/and chemical bond combination.
In the fibrous hybrid particles provided by the present invention, preferably, the nanoparticles used have a particle size of 5nm to 50 nm.
In the fiber hybrid particle provided by the invention, preferably, the adopted nano-fiber is a nano-conductor fiber, and the adopted nano-particle is an insulating oxide nano-particle or a semiconductor oxide nano-particle. The structure of the fiber hybrid particle with the surface of the nano-conductor fiber loaded with insulating oxide or semiconductor oxide nano-particles is shown in fig. 1.
In the fibrous hybrid particle provided by the present invention, preferably, the nano conductor fiber used includes an inorganic nano conductor fiber and/or an organic nano conductor fiber.
In the fiber hybrid particle provided by the invention, preferably, the adopted inorganic nano conductor fiber comprises one or more of carbon nano tube, nano gold, nano silver, nano copper, nano nickel, nano titanium, nano cobalt, nano aluminum, nano iron, nano indium, nano tin and nano zinc.
In the fibrous hybrid particles provided by the present invention, preferably, the organic nano conductor fiber used includes a nano conductor fiber composed of at least one of polyacetylene, polythiophene (manufactured by shanghai heiji chemical industries, ltd.), polypyrrole (manufactured by Carlit, japan), polyaniline (manufactured by shijiazhu Jianhia new material science and technology ltd.), p-polyphenylenes, polyphenylenevinylenes and polydiacetylenes.
In the fiber hybrid particle provided by the present invention, preferably, the insulating oxide nanoparticles used include at least one of barium titanate nanoparticles, barium strontium titanate nanoparticles, lead titanate nanoparticles, copper calcium titanate nanoparticles, boron nitride nanoparticles, aluminum nitride nanoparticles, alumina nanoparticles, silica nanoparticles, titanium dioxide nanoparticles, calcium titanate nanoparticles, and calcium sulfate nanoparticles.
In the fiber hybrid particle provided by the invention, preferably, the semiconductor oxide nanoparticles used include at least one of silver oxide nanoparticles, zinc oxide nanoparticles, cuprous oxide nanoparticles, copper oxide nanoparticles, manganese oxide nanoparticles, iron oxide nanoparticles and titanium oxide nanoparticles.
In the fiber hybrid particle provided by the invention, preferably, the adopted nano-fiber is insulating oxide nano-fiber or semiconductor oxide nano-fiber, and the adopted nano-particle is conductive particle. The structure of the fiber hybrid particle with the surface of the insulating oxide nanofiber or the semiconductor oxide nanofiber loaded with the conductive particles is shown in fig. 2.
In the fiber hybrid particle provided by the present invention, preferably, the insulating oxide nanofiber or semiconductor oxide nanofiber used comprises an insulating oxide nanofiber or semiconductor oxide nanofiber composed of at least one of barium titanate, barium strontium titanate, lead titanate, calcium copper titanate, boron nitride, aluminum nitride, alumina, silica, titanium dioxide, calcium titanate, calcium sulfate, silver oxide, zinc oxide, cuprous oxide, copper oxide, manganese oxide, and iron oxide.
In the fibrous hybrid particle provided by the present invention, preferably, the conductive particles used include at least one of gold particles, silver particles, copper particles, nickel particles, titanium particles, cobalt particles, aluminum particles, iron particles, and manganese particles; or
The adopted conductive particles are conductive carbon particles, and more preferably, the adopted conductive carbon particles comprise at least one of graphite, graphite oxide, graphene, carbon nanotubes and carbon black; or
The conductive particles used are conductive polymer particles, and more preferably, the conductive polymer particles used include conductive polymer particles composed of at least one of polyacetylene, polythiophene, polypyrrole, polyaniline, polyparaphenylene, polyphenylenevinylene, and polydiyne.
The fiber hybrid particles provided by the invention are prepared by physical adsorption or/and chemical bond bonding between the nano-fibers and the nano-particles, and the specific preparation method is shown in the embodiment of the invention, but not limited to the preparation method in the embodiment.
The invention also provides a polymer matrix composite material, which comprises a polymer and fiber hybrid particles filled in the polymer; wherein, the fiber hybrid particles are the fiber hybrid particles, and the adopted fiber hybrid particles account for 10 to 80 percent of the total mass of the polymer matrix composite material.
In the polymer-based composite material provided by the present invention, preferably, the polymer used includes at least one of an epoxy resin (produced by jinan saint spring group ltd), a polyimide resin (produced by seiyang kun-kuiyi chemical ltd), a polyester resin (produced by guangzhou-xiong-co-polymer ltd), a phenol resin (produced by jinan saint spring group ltd), and a bismaleimide triazine resin (produced by sanyang seiko chemical trade ltd).
The preparation method of the polymer-based composite material provided by the invention comprises the following specific steps:
dispersing fiber hybrid particles into a butanone solution, stirring and ultrasonically dispersing for 1 hour, and adding a polymer solution dissolved in the butanone solution;
stirring and ultrasonically dispersing for 2 hours, and adding a curing agent, a curing accelerator, a defoaming agent and a rheological agent; wherein, the curing agent, the curing accelerator, the defoaming agent and the rheological agent are selected from the reagents commonly used in the field, and the addition amount of each substance can be determined according to the conventional mode in the field;
performing ultrasonic stirring for 0.5 hour to obtain resin slurry containing hybrid particles;
coating the film by a bar coater, heating, crosslinking and curing to obtain the polymer-based composite material.
According to the invention, through constructing a reasonable nano structure, the granular nano particles are loaded on the surface of the nano fiber through electrostatic adsorption or chemical bond action, so that the problems of agglomeration and winding of granular and fibrous nano materials are solved, and meanwhile, the fibrous hybrid nano material is endowed with multiple functions, and the polymer-based composite material with controllable performance and multiple functions is prepared in a more convenient and effective manner.
Drawings
Fig. 1 is a schematic structural diagram of a fiber hybrid particle with insulating oxide or semiconductor oxide nanoparticles loaded on the surface of a nano conductor fiber.
Fig. 2 is a schematic structural diagram of a fiber hybrid particle with conductive particles loaded on the surface of insulating oxide nanofibers or semiconductor oxide nanofibers.
Fig. 3 is an SEM image of CNT-ZnO fiber hybrid particles with ZnO particles supported on the CNT surface.
FIG. 4 shows BaTiO3SEM image of Ag fiber hybrid particles, Ag particles supported on BaTiO3The surface of the fiber.
FIG. 5 shows CNT-TiO2TEM image of fiber hybrid particles, TiO2The particles are loaded on the surface of the CNT fiber.
FIG. 6 is a graph of the conductivity of a CNT-ZnO/epoxy composite.
FIG. 7 is an I-V characteristic curve of a CNT-ZnO/epoxy composite.
FIG. 8 shows BaTiO3The dielectric constant curve of the Ag/epsoy composite.
FIG. 9 shows BaTiO3Dielectric loss curves of Ag/epsoy composites.
FIG. 10 shows BaTiO3Resistivity versus frequency curve of Ag/epsoy composite.
Description of the main figures
11 nano-conductor fiber 12 insulating oxide or semiconductor oxide nano-particle 21 insulating oxide nano-fiber or semiconductor oxide nano-fiber 22 conductive particle
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a fiber hybrid particle with nano zinc oxide loaded on the surface of CNT, which is prepared by the following steps:
putting 1g of Carbon Nano Tube (CNT) into 200mL of mixed solution of concentrated nitric acid and concentrated sulfuric acid (3:1 volume ratio), and stirring for 4 hours at 65 ℃;
after the mixed solution is cooled, diluting with deionized water, after the carbon nano tube is settled, pouring the supernatant, then diluting the carbon nano tube for multiple times to be neutral, and drying the carbon nano tube to obtain acidified CNT;
dispersing the acidified CNT into 300mL of ZnO sol, treating for 12 hours by using a ball milling method, and then slowly heating the solution into a three-neck flask to 180 ℃ and keeping the temperature for 24 hours;
and cooling to room temperature, washing with absolute ethyl alcohol and deionized water for multiple times, and drying at 100 ℃ for at least 12 hours to obtain the CNT-ZnO fiber hybrid particles.
The CNT-ZnO hybrid particle of this example is prepared by acidifying CNT with carboxyl on surface and hydrolyzing to alkaline Zn (OH)2The hydroxyl groups of (a) are combined to prepare the fiber hybrid particles. The structure of the fiber hybrid particle in which the surface of the nano-conductor fiber 11 is supported by the insulating oxide or semiconductor oxide nanoparticles 12 is shown in fig. 1.
The diameter of the CNT in the fiber hybrid particle prepared in this example is 10nm-20nm, the length is more than 10 μm, the diameter of the ZnO nanoparticle is less than 10nm, and the SEM of the CNT-ZnO hybrid particle is shown in fig. 3.
Example 2
This example provides a CNT surface loaded BaTiO3The fiber hybrid particle of (1), which is prepared by the following steps:
dispersing 0.25g of CNT in 100mL of absolute ethyl alcohol, mixing with 0.3mL of 28 wt% concentrated ammonia water, and ultrasonically dispersing for 15 min;
slowly dripping 0.75mL of tetrabutyl titanate for about 5min, and stirring for 24h at 45 ℃;
washing with deionized water and anhydrous ethanol for 3 times, and drying at 100 deg.C for 12 hr;
sintering at 500 deg.C for 2h in air atmosphere to obtain CNT-TiO2Hybrid particles;
adding CNT-TiO sintered for 2 hours at 500 ℃ into aqueous solution of barium source2Heating at 200 deg.C for 12 hr in reaction kettle to obtain CNT-BaTiO3Fibrous hybrid particles.
CNT-BaTiO of this example3The fiber hybrid particles, CNT are not treated, have no chemical bond with titanium dioxide/barium titanate, and are electrostatically adsorbed by means of electronegativity difference of respective positions in a reaction system, so that the fiber hybrid particles are formed.
The hybrid particles prepared in this example have CNTs with diameters of 10nm-20nm and lengths greater than 10 μm, BaTiO3The particle size of the (B) can be controlled within 5nm-15 nm.
CNT-BaTiO of this example3The composite material prepared from the fiber hybrid particles and the epoxy resin can ensure the insulativity of the composite material and can obtain higher dielectric constant and lower dielectric loss.
Example 3
The embodiment provides a copper nanowire surface loaded TiO2Fibrous hybrid particles prepared by the steps of:
taking 0.1M Cu (NO)3)210mL of 15M NaOH 200mL and 1.5mL of ethylenediamine are put into a 500mL round-bottom flask, the temperature is raised to 50 ℃, and the stirring is carried out at 700 rpm;
after 5min 0.25mL of 35 wt% N was taken2H4Rapidly adding into the above solution;
after 2min, 150mL of an aqueous solution containing 3 wt% of polyvinylpyrrolidone (MW: 10000) and 1 wt% of diethylhydroxylamine was added and reacted for 1 hour;
obtaining copper nanowires (CuNWs) through centrifugal separation, finally dispersing the CuNWs into ethanol solution, slowly dripping 0.5mL of tetrabutyl titanate into the ethanol solution for about 5min, and stirring the solution for 24h at the temperature of 45 ℃;
washing with deionized water and anhydrous ethanol for 3 times, drying at 100 deg.C for 12 hr,then sintering the obtained product for 2h to CuNW-TiO in air atmosphere at 500 DEG C2Fibrous hybrid particles.
CuNW-TiO obtained in this example2The diameter of the Cu nanowire of the fiber hybrid particle is 50nm, the length of the Cu nanowire is 10-20 mu m, and TiO2Has a particle diameter of 20 nm.
Example 4
This example provides a BaTiO3The fiber hybrid particles with the fiber surface loaded with the nano Ag are prepared by the following steps:
2.5541g of barium acetate powder was added to 4mL of glacial acetic acid and stirred at room temperature until completely dissolved;
adding 4.6mL of tetrabutyl titanate into 3.5mL of ethanol, and magnetically stirring for 30 min;
mixing the two solutions at room temperature, stirring for 8h, adding 0.2g of PVP, and stirring for 8h to obtain yellow transparent precursor sol;
transferring the precursor sol into an injection device for continuous spinning to obtain BaTiO3Gel fiber of BaTiO3Drying gel fiber in oven at 85 deg.C for 3 hr to volatilize solvent on fiber surface, fixing fiber shape, placing the fiber in crucible, placing in muffle furnace for heat treatment, and making into BaTiO fiber3The fiber heat treatment is divided into two steps of pre-burning and sintering, wherein the pre-burning aims to fully remove a large amount of organic matters in the fiber so as to avoid causing excessive holes and cracks, so that the temperature rise rate is controlled to be slow; firstly heating to 180 ℃ at the speed of 2 ℃/min, preserving heat for 1h at 180 ℃, then heating to 400 ℃ at the speed of 5 ℃/min, preserving heat for 60min, and finally heating to 600 ℃ at the speed of 5 ℃/min, preserving heat for 2 h; sintering the pre-sintered fiber at 800 ℃ for 1h at the speed of 5 ℃/min to obtain BaTiO3Ceramic fibers. Then weighing 1g of silver nitrate powder, adding the silver nitrate powder into 100mL of ethylene glycol solution, and stirring for 30min to obtain a light yellow solution;
weighing 1g of barium titanate fiber, adding the barium titanate fiber into a 300mL three-neck flask, adding 100mL of ethylene glycol solution, magnetically stirring for 1h, slowly adding a light yellow solution into the three-neck flask, stirring for 2h, slowly heating to 140 ℃, keeping the temperature for 30 minutes, and cooling at room temperature to obtain a light gray solution;
and standing the light gray solution, pouring out supernatant, washing the lower precipitate with alcohol for 3-5 times, and drying at 80 ℃ for 2h to obtain the fiber hybrid particles of the barium titanate fiber surface loaded with the silver nanoparticles.
The fiber hybrid particle of the barium titanate fiber surface loaded with the silver nanoparticles in this embodiment relies on the principle that the (1,1,1) interplanar spacing of barium titanate is close to the (1,1,1) interplanar spacing of silver nanoparticles, and the silver nanoparticles can perform nucleation growth preferentially on the barium titanate surface, thereby forming the fiber hybrid particle. The structure of the fiber hybrid particle in which the conductive fine particles 22 are supported on the surface of the insulating oxide nanofiber or the semiconductor oxide nanofiber 21 is shown in fig. 2.
The barium titanate nanofiber of the fiber hybrid particle of which the surface of the barium titanate fiber is loaded with the silver nanoparticles obtained in the embodiment has the diameter of 500nm and the length of 15 μm, and the particle size of the nano Ag loaded on the surface of the barium titanate nanofiber is 70nm-80 nm. The BaTiO3SEM of-Ag fiber hybrid particle is shown in FIG. 4.
Example 5
The embodiment provides a fiber hybrid particle with nano-Cu loaded on the surface of ZnO fiber, which is prepared by the following steps:
ZnAc is reacted with a catalyst2·2H2Dissolving O (1.1g), PEG400(7.5mL) and NaOH (4.0g) in 30mL of absolute ethyl alcohol, adding the mixture into a 50mL polytetrafluoroethylene reaction kettle, sealing the reaction kettle in a stainless steel container, keeping the temperature at 120 ℃ for 12 hours, naturally cooling to room temperature, separating out white precipitate, washing for 3 times by using absolute ethyl alcohol and deionized water in sequence, and drying at 100 ℃ for 4 hours to obtain ZnO nanowires (ZnONW);
ultrasonically dispersing a certain amount of ZnO nanowire (0.1g) in 5mL of distilled water, and adding 2mL of 0.05mol/L CuCl2Adding the solution into a ZnO nanowire suspension system, magnetically stirring for 1h, centrifuging, washing for 3 times with deionized water, re-dispersing in 5mL of distilled water, and adding 5mL of 0.05mol/L NaBH4And magnetically stirring the solution at room temperature for 1h, aging for 24h, and performing centrifugal separation to obtain ZnONW-Cu fiber hybrid particles.
The ZnO nanofibers of the fiber hybrid particles in which the nanocu was supported on the surface of the ZnO fibers obtained in this example had a diameter of 40nm and a length of 10 μm, and the diameter of the nanocu supported thereon was 20 nm.
Example 6
This example provides a BaTiO3The fiber hybrid particles with conductive polyaniline loaded on the surface of the fiber are prepared by the following steps:
2.5541g of barium acetate powder was added to 4mL of glacial acetic acid and stirred at room temperature until completely dissolved;
adding 4.6mL of tetrabutyl titanate into 3.5mL of ethanol, and magnetically stirring for 30 min;
mixing the two solutions at room temperature, stirring for 8h, adding 0.2g of PVP, and stirring for 8h to obtain yellow transparent precursor sol;
transferring the precursor sol into an injection device for continuous spinning to obtain BaTiO3Gel fiber of BaTiO3Drying the gel fiber in an oven at 85 ℃ for 3h to volatilize the solvent on the surface of the fiber, and fixing the shape of the fiber;
placing the fiber in a crucible, placing the crucible in a muffle furnace for heat treatment, and BaTiO3The fiber heat treatment is divided into two steps of pre-burning and sintering, wherein the pre-burning aims to fully remove a large amount of organic matters in the fiber so as to avoid causing excessive holes and cracks, so that the temperature rise rate is controlled to be slow; firstly heating to 180 ℃ at the speed of 2 ℃/min, preserving heat for 1h at 180 ℃, then heating to 400 ℃ at the speed of 5 ℃/min, preserving heat for 60min, and finally heating to 600 ℃ at the speed of 5 ℃/min, preserving heat for 2 h; sintering the pre-sintered fiber at 800 ℃ for 1h at the speed of 5 ℃/min to obtain BaTiO3Ceramic fiber, BaTiO3Ceramic fiber 1g, 20mL of a 1 wt% aqueous solution of KH550 in alcohol was placed in a 100mL three-necked flask and mechanically stirred for 30 min. Preparing 70mL of 2M hydrochloric acid solution from 2mL (0.02mol) of aniline monomer, pouring the hydrochloric acid solution into a three-neck flask, and continuously mechanically stirring for 1 h; 4.564g of APS (0.02mol) were weighed out and dissolved in 20mL of deionized water; dropwise adding an aqueous solution of an initiator APS into a three-neck flask, gradually changing the liquid in the flask from colorless to light blue along with the dropwise addition of the APS, finally changing the liquid into dark green, and continuously stirring for reaction for 3 hours;
and after the reaction is finished, carrying out suction filtration on the liquid in the flask, washing the liquid with absolute ethyl alcohol and deionized water until the filtrate is colorless, and carrying out vacuum drying on the powder obtained by suction filtration at 80 ℃ for 24 hours to obtain the hybrid particles of the barium titanate fiber surface loaded with the conductive polyaniline.
Example 7
The embodiment provides a fiber hybrid particle with nano titanium dioxide loaded on the surface of CNT, which is prepared by the following steps:
dispersing 0.25g of CNT in 100mL of absolute ethyl alcohol, mixing with 0.3mL of 8 wt% concentrated ammonia water, and ultrasonically dispersing for 15 min;
slowly dripping 0.75mL of tetrabutyl titanate for about 5min, stirring at 45 ℃ for 24h, respectively cleaning with deionized water and absolute ethyl alcohol for 3 times, drying at 100 ℃ for 12h, sintering at 500 ℃ for 2h in air atmosphere, removing organic matters and improving crystallinity to obtain CNT-TiO2Fibre hybrid particles, CNT-TiO2The TEM of the fibrous hybrid particles is shown in fig. 5.
Example 8
This example provides a polymer matrix composite containing the fibrous hybrid particles of example 1, prepared by the following steps:
dispersing 10g of the CNT-ZnO fiber hybrid particles prepared in example 1 in 20mL of butanone solution, stirring and ultrasonically dispersing for 1 hour, and adding 10g of epoxy resin Epon828 dissolved in 20mL of butanone;
stirring and ultrasonically dispersing for 2 hours, adding a mixed solution of 0.8g of dicyandiamide and 0.1g of 2-methyl-4-ethylimidazole dissolved in 5mL of N, N-dimethylformamide, and ultrasonically stirring for 0.5 hour to obtain epoxy resin slurry containing hybrid particles;
coating the film by a bar coater, and thermally curing the film for 2 hours at 180 ℃ to obtain the CNT-ZnO/epoxy composite material. Wherein the mass content of the fiber hybrid particles in the composite material is 48 percent.
FIG. 6 is a graph of conductivity of a CNT-ZnO/epoxy composite and FIG. 7 is a graph of I-V characteristics of a CNT-ZnO/epoxy composite. As can be seen from fig. 6 and 7, the composite material can ensure the insulation property of the composite material and has an antistatic function.
Example 9
This example provides a polymer matrix composite containing the fibrous hybrid particles of example 4, prepared by the following steps:
10g of BaTiO obtained in example 4 were taken3Dispersing Ag fiber hybrid particles in 20mL butanone solution, stirring and ultrasonically dispersing for 1 hour, and adding 10g epoxy resin Epon828 dissolved in 20mL butanone;
stirring and ultrasonically dispersing for 2 hours, adding a mixed solution of 0.8g of dicyandiamide and 0.1g of 2-methyl-4-ethylimidazole dissolved in 5mL of N, N-dimethylformamide, and ultrasonically stirring for 0.5 hour to obtain epoxy resin slurry containing hybrid particles;
coating with a bar coater, and heat curing at 180 deg.C for 2 hr to obtain BaTiO3-Ag/epsoy composite material. Wherein the mass content of the fiber hybrid particles in the composite material is 48%.
FIG. 8 shows BaTiO3Dielectric constant curve of-Ag/epsoy composite, FIG. 9 is BaTiO3Dielectric loss curve of-Ag/epsoy composite, FIG. 10 is BaTiO3Resistivity versus frequency curve of Ag/epsoy composite. As can be seen from fig. 8, 9 and 10, the composite material can not only obtain a higher dielectric constant and a lower dielectric loss, but also ensure the insulation and frequency stability, and in addition, the application thereof in the field of catalysis can not only ensure the chemical stability, but also improve the catalytic performance.
The above examples illustrate that the fiber hybrid particles and the polymer-based composite material of the present invention solve the problem of agglomeration and entanglement of the particulate and fibrous nanomaterials, and simultaneously, provide multiple functions to the fibrous hybrid nanomaterials, so that the polymer-based composite material containing the fiber hybrid particles can be prepared in a more convenient and efficient manner, and the properties of the composite-based composite material can be controlled.
Claims (4)
1. The fiber hybrid particle is characterized by consisting of nanofibers and nanoparticles loaded on the surfaces of the nanofibers;
wherein the coverage rate of the nano particles on the surface of the nano fiber is 5% -100%;
the diameter of the nano fiber is 50nm-300nm, and the length of the nano fiber is 1 mu m-100 mu m;
the particle size of the nano particles is equal to or less than the diameter of the nano fibers;
the interface connection between the nano fiber and the nano particle is physical adsorption or/and chemical bond combination;
the nano-fibers are nano-conductor fibers, and the nano-particles are semiconductor oxide nano-particles; or
The nano-fiber is an insulating oxide nano-fiber, and the nano-particle is a conductive particle;
the nano conductor fiber is a carbon nano tube, and the semiconductor oxide nano particles are at least one of zinc oxide nano particles or titanium oxide nano particles;
the insulating oxide nano-fiber is barium titanate, and the conductive particles are silver particles.
2. The fibrous hybrid particle according to claim 1, wherein the nanoparticle has a particle size of 5nm to 50 nm.
3. A polymer-based composite material, characterized in that it comprises a polymer and fibrous hybrid particles filled in said polymer;
the fibrous hybrid particle is the fibrous hybrid particle of any one of claims 1-2;
the fiber hybrid particles account for 10-80% of the total mass of the polymer-based composite material.
4. The polymer-matrix composite of claim 3, wherein the polymer comprises at least one of an epoxy resin, a polyimide resin, a polyester resin, a phenolic resin, and a bismaleimide triazine resin.
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| PCT/CN2016/075838 WO2017101223A1 (en) | 2015-12-15 | 2016-03-08 | Fibre-hybridised particle and polymer-based composite |
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| DE102018214834B4 (en) | 2018-08-31 | 2024-02-22 | Airbus Defence and Space GmbH | Method for nanostructuring carbon fiber surfaces in fiber composite plastics based on sulfur and aromatic hydrocarbons as well as a fiber composite plastic produced according to the method and a method for repairing at least one fiber in a fiber composite plastic |
| CN110655846A (en) * | 2019-10-14 | 2020-01-07 | 李道勤 | Toughened epoxy resin coating with enhanced corrosion resistance |
| CN113754925B (en) * | 2021-09-28 | 2023-04-07 | 浙江荣泰科技企业有限公司 | Insulating base material-carbon nano tube hybrid material and preparation method and application thereof |
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| CN101413210B (en) * | 2008-11-12 | 2011-08-31 | 东华大学 | Method for carbon fiber surface modification of plasma coated with silicon dioxide by plasma treatment |
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