WO2017101223A1 - 一种纤维杂化颗粒及聚合物基复合材料 - Google Patents

一种纤维杂化颗粒及聚合物基复合材料 Download PDF

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WO2017101223A1
WO2017101223A1 PCT/CN2016/075838 CN2016075838W WO2017101223A1 WO 2017101223 A1 WO2017101223 A1 WO 2017101223A1 CN 2016075838 W CN2016075838 W CN 2016075838W WO 2017101223 A1 WO2017101223 A1 WO 2017101223A1
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nanoparticles
fiber
particles
oxide
nano
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French (fr)
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于淑会
罗遂斌
孙蓉
王健
刘鸿昌
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Shenzhen Institute of Advanced Technology of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/10—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
    • H01F1/11—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles
    • H01F1/113—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles in a bonding agent
    • H01F1/117—Flexible bodies
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to a fiber hybrid particle and a polymer matrix composite material composed of the fiber hybrid particle, belonging to the field of nano fiber materials.
  • Nanomaterials are broadly defined as materials that have at least one dimension in the three-dimensional space in the nanoscale range (0.1 nm-100 nm) or are composed of them as basic units.
  • the nano-material particles are extremely fine and have a large surface area.
  • the atomic percentage of the disordered arrangement on the surface of the particles is much larger than the percentage of the atoms on the surface of the large-scale material, resulting in nano-materials having characteristics not possessed by conventional solid materials, such as volume effect, surface effect. , quantum size effect, macroscopic quantum tunneling effect and dielectric confinement effect, etc., so that the nano material has microwave absorption performance, high surface activity, strong oxidation, superparamagnetism and the like.
  • nanomaterials have special optical, catalytic, chemical reaction kinetics and special physical and mechanical properties. The use of nanomaterials greatly enriches the development and application of materials.
  • Nanomaterials have a variety of excellent properties, while high molecular polymer materials have unique properties in mechanics, physics, chemistry, and electricity.
  • the composite material is compounded with the high molecular polymer material, and the composite material has the special properties of the nano material and maintains the excellent properties of the polymer material.
  • the composite technology of nanomaterials was to mix several nanomaterials with other materials (polymer or nanomaterial).
  • the surface activity is very large, and the particles and the particles are easily adsorbed together by van der Waals force to form agglomerates, and are not easily dispersed again, thereby making it difficult to develop new materials. Effectively control the properties of the material.
  • the nanofiber material has a large specific surface area, a high aspect ratio, and a strong interpenetrating force with other substances.
  • the nanofiber fabric has a fine structure and excellent flexibility, adsorption, and filtration properties.
  • the unique properties of nanofibers make it a huge market potential in membrane materials, filter media, catalysts, electronics, biologics, composite reinforcements and more.
  • it is precisely because of the great aspect ratio and specific surface area of the nanofiber material that it is easy to entangle when it is prepared into a composite material with a polymer, and in particular, when the nanoparticle is composited by a mechanical method, it is difficult to obtain a uniformly dispersed composite material. Performance is difficult to control.
  • an object of the present invention is to provide a fiber hybrid particle and a polymer matrix composite material composed of the fiber hybrid particle.
  • the fiber hybridized particle solves the problem of agglomeration and entanglement of the granular and fibrous nanomaterials, and imparts multiple functions to the fibrous hybrid nanomaterial, thereby obtaining a controllable and multifunctional polymer matrix composite in a more convenient and efficient manner. material.
  • the present invention first provides a fiber hybrid particle composed of nanofibers and nanoparticles supported on the surface of the nanofiber;
  • the surface coverage of the nanoparticles on the nanofibers is 5%-100%
  • the nanofibers have a diameter of 50 nm to 300 nm and a length of 1 ⁇ m to 100 ⁇ m;
  • the particle diameter of the nanoparticles is equal to or smaller than the diameter of the nanofibers
  • the interfacial connection of the nanofibers to the nanoparticles is physical adsorption or/and chemical bonding.
  • the nanoparticles used have a particle diameter of from 1 nm to 50 nm.
  • the nanofibers used are nano-conductor fibers, and the nanoparticles used are insulating oxide nanoparticles or semiconductor oxide nanoparticles.
  • the structure of the fiber hybrid particles in which the surface of the nanoconductor fiber is loaded with an insulating oxide or a semiconductor oxide nanoparticle is shown in FIG.
  • the nanoconductor fibers used include inorganic nanoconductor fibers and/or organic nanoconductor fibers.
  • the inorganic nano conductor fibers used include carbon nanotubes, nano gold, nano silver, nano copper, nano nickel, nano titanium, nano cobalt, nano aluminum, nano iron, nano An alloy of one or several of indium, nano tin, and nano zinc.
  • the organic nanoconductor fibers used include polyacetylene, polythiophene (produced by Shanghai Huiping Chemical Co., Ltd.), polypyrrole (produced by Japan Carlit Co., Ltd.), and polyaniline (Shijiazhuang). Nano-conductor fiber composed of at least one of para-polyphenylene, polyphenylene vinylene and polydiacetylene produced by Pan'an Yada New Material Technology Co., Ltd.).
  • the insulating oxide nanoparticles used include barium titanate nanoparticles, barium titanate nanoparticles, lead titanate nanoparticles, copper calcium titanate nanoparticles, and nitriding. At least one of boron nanoparticles, aluminum nitride nanoparticles, alumina nanoparticles, silica nanoparticles, titanium dioxide nanoparticles, calcium titanate nanoparticles, and calcium sulfate nanoparticles.
  • the semiconductor oxide nanoparticles used include silver oxide nanoparticles, zinc oxide nanoparticles, cuprous oxide nanoparticles, copper oxide nanoparticles, manganese oxide nanoparticles, At least one of iron oxide nanoparticles and titanium oxide nanoparticles.
  • the nanofibers used are insulating oxide nanofibers or semiconductor oxide nanofibers
  • the nanoparticles used are conductive particles.
  • the structure of the fiber hybrid particles in which the insulating oxide nanofiber or the semiconductor oxide nanofiber surface is loaded with the conductive particles is as shown in FIG.
  • the insulating oxide nanofiber or the semiconductor oxide nanofiber used includes barium titanate, barium titanate, lead titanate, copper calcium titanate, boron nitride.
  • Insulating oxide nanometer composed of at least one of aluminum nitride, aluminum oxide, silicon dioxide, titanium dioxide, calcium titanate, calcium sulfate, silver oxide, zinc oxide, cuprous oxide, copper oxide, manganese oxide and iron oxide Fiber or semiconducting oxide nanofibers.
  • 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 conductive particles used are conductive carbon particles, and more preferably, the conductive carbon particles used include at least one of graphite, graphite oxide, graphene, carbon nanotubes, and carbon black;
  • the conductive particles used are conductive polymer particles, and more preferably, the conductive polymer particles used include at least at least one of polyacetylene, polythiophene, polypyrrole, polyaniline, para-polyphenylene, polyphenylene vinylene, and polydiacetylene.
  • a composition of conductive polymer particles are conductive polymer particles.
  • the above-mentioned fiber hybridized particles provided by the present invention are prepared by physical adsorption or/and chemical bonding between the nanofibers and the nanoparticles, and the specific preparation method is as shown in the embodiment of the present invention, but is not limited to the embodiment. Preparation method.
  • the present invention also provides a polymer-based composite material comprising a polymer and fiber hybrid particles filled in the polymer; wherein the fiber hybrid particles are the fiber hybrid particles described above;
  • the fiber hybrid particles used comprise from 10% to 80% of the total mass of the polymer matrix composite.
  • the polymer used includes epoxy resin (manufactured by Jinan Shengquan Group Co., Ltd.) and polyimide resin (produced by Fuyang Tianyi Chemical Co., Ltd.) , polyester resin (produced by Guangzhou Produce Polymer Co., Ltd.), phenolic resin (produced by Jinan Shengquan Group Co., Ltd.) and bismaleimide triazine resin (produced by Xianyang Sanjingke Industry and Trade Co., Ltd.) At least one.
  • epoxy resin manufactured by Jinan Shengquan Group Co., Ltd.
  • polyimide resin produced by Fuyang Tianyi Chemical Co., Ltd.
  • polyester resin produced by Guangzhou Produce Polymer Co., Ltd.
  • phenolic resin produced by Jinan Shengquan Group Co., Ltd.
  • bismaleimide triazine resin produced by Xianyang Sanjingke Industry and Trade Co., Ltd.
  • the above polymer-based composite material provided by the present invention is specifically prepared as follows:
  • the film is coated by a bar coater, and crosslinked and cured by heating to obtain a polymer-based composite material.
  • the granular nanoparticles are supported on the surface of the nanofiber by electrostatic adsorption or chemical bonding, and the fibrous hybrid nanomaterial is imparted while solving the problem of agglomeration and entanglement of the granular and fibrous nanomaterials.
  • FIG. 1 is a schematic view showing the structure of a fiber hybrid particle in which an insulating oxide or a semiconductor oxide nanoparticle is supported on a surface of a nanoconductor fiber.
  • FIG. 2 is a schematic view showing the structure of fiber hybrid particles in which insulating oxide nanofibers or semiconductor oxide nanofibers are loaded with conductive particles.
  • Figure 3 is an SEM image of CNT-ZnO fiber hybrid particles loaded on the surface of the CNT.
  • Figure 5 is a TEM image of CNT-TiO 2 fiber hybrid particles loaded with TiO 2 particles on the surface of CNT fibers.
  • Figure 6 is a graph showing the conductivity of a CNT-ZnO/epoxy composite.
  • Figure 7 is an I-V characteristic curve of a CNT-ZnO/epoxy composite.
  • Figure 8 is a graph showing the dielectric constant of a BaTiO 3 -Ag/epxoy composite.
  • Figure 9 is a graph showing the dielectric loss of a BaTiO 3 -Ag/epxoy composite.
  • Figure 10 is a plot of resistivity versus frequency for a BaTiO 3 -Ag/epxoy composite.
  • insulation oxide or semiconductor oxide nanoparticles insulation oxide nanofiber or semiconductor oxide nanofiber 22 conductive particles
  • the present embodiment provides a fiber hybrid nanoparticle of CNT surface loaded with nano zinc oxide, which is prepared by the following steps:
  • CNT carbon nanotubes
  • the acidified CNTs were dispersed into 300 mL of ZnO sol and treated by ball milling for 12 hours, after which the solution was placed in a three-necked flask and slowly heated to 180 ° C for 24 hours;
  • the CNT-ZnO fiber hybrid particles of the present embodiment are fiber hybrid particles prepared by combining the carboxyl group on the surface of the CNT after acidification and the hydroxyl group of Zn(OH) 2 which is basic after hydrolysis.
  • the structure of the fiber hybrid particles in which the surface of the nanoconductor fiber 11 is loaded with the insulating oxide or the semiconductor oxide nanoparticle 12 is as shown in FIG.
  • the CNTs in the fiber hybrid particles prepared in this example have a diameter of 10 nm to 20 nm, a length of more than 10 ⁇ m, and a diameter of the ZnO nanoparticles of less than 10 nm.
  • the SEM of the CNT-ZnO hybrid particles is shown in FIG. 3 .
  • This embodiment provides a fiber hybrid particle of BaTiO 3 supported on a CNT surface, which is prepared by the following steps:
  • CNT-TiO 2 sintered at 500 ° C for 2 hours was added to an aqueous solution of lanthanum, and CNT-BaTiO 3 fiber hybrid particles were obtained by heating at 200 ° C for 12 hours in a reaction vessel.
  • the CNT-BaTiO 3 fiber hybrid particles of the present embodiment are not treated, and have no chemical bond with the titanium dioxide/barium titanate, and rely on the electronegativity difference of the respective positions in the reaction system to perform electrostatic adsorption, thereby forming fiber miscellaneous. Granules.
  • the diameter of the CNTs in the hybrid particles prepared in this embodiment is 10 nm to 20 nm, the length is more than 10 ⁇ m, and the particle diameter of BaTiO 3 can be controlled to be 5 nm to 15 nm.
  • the composite material prepared by the CNT-BaTiO 3 fiber hybrid particle and the epoxy resin of the embodiment can ensure the insulation property of the composite material and obtain a high dielectric constant and a low dielectric loss.
  • This embodiment provides a copper nanowire surface-loaded TiO 2 fiber hybrid particle which is prepared by the following steps:
  • CuNW copper nanowires
  • the Cu nanowires of the CuNW-TiO 2 fiber hybrid particles obtained in the present example have a diameter of 50 nm, a length of 10 ⁇ m to 20 ⁇ m, and a particle diameter of TiO 2 of 20 nm.
  • This embodiment provides a fiber hybrid particle of nano-Ag loaded on the surface of BaTiO 3 fiber, which is prepared by the following steps:
  • the precursor sol was transferred to an injection device for continuous spinning to obtain BaTiO 3 gel fiber.
  • the BaTiO 3 gel fiber was dried in an oven at 85 ° C for 3 h, so that the solvent on the surface of the fiber was volatilized, the fiber shape was fixed, and the fiber was placed in the crucible.
  • BaTiO 3 fiber heat treatment is divided into two steps of calcination and sintering. The purpose of calcination is to completely remove a large amount of organic matter in the fiber to avoid excessive pores and cracks, so the temperature is raised.
  • the rate should be controlled slowly; firstly heat to 180 ° C at 2 ° C / min, heat at 180 ° C for 1 h, then heat to 400 ° C at 5 ° C / min and keep warm for 60 min, and finally rise to 600 ° at 5 ° C / min
  • the temperature was kept at ° C for 2 h; the pre-fired fibers were sintered at 800 ° C for 1 h at a rate of 5 ° C/min to obtain BaTiO 3 ceramic fibers.
  • 1 g of silver nitrate powder was weighed and added to 100 mL of an ethylene glycol solution and stirred for 30 minutes to obtain a pale yellow solution;
  • the light gray solution was allowed to stand, the supernatant liquid was poured off, and the lower layer precipitate was washed with alcohol for 3-5 times and dried at 80 ° C for 2 hours to obtain fiber hybrid particles in which silver nanoparticles were supported on the surface of the barium titanate fiber.
  • the fiber hybrid particles supporting the silver nanoparticles on the surface of the barium titanate fiber of the present embodiment rely on the (1,1,1) interplanar spacing of barium titanate and the (1,1,1) interplanar spacing of the silver nanoparticles. Close to the principle, silver nanoparticles can preferentially grow on the surface of barium titanate to form fiber hybrid particles.
  • the structure of the fiber hybrid particles in which the insulating oxide nanofibers or the semiconductor oxide nanofibers 21 are supported on the surface of the conductive particles 22 is as shown in FIG.
  • the barium titanate nanofibers of the fiber nanoparticle-loaded fiber hybrid particles having the surface of the barium titanate fiber obtained in the present embodiment have a diameter of 500 nm and a length of 15 ⁇ m, and the particle size of the nano-Ag supported on the surface thereof is 70 nm to 80 nm.
  • the SEM of the BaTiO 3 -Ag fiber hybrid particles is shown in Fig. 4 .
  • This embodiment provides a fiber hybrid particle of nano-Cu loaded on the surface of a ZnO fiber, which is prepared by the following steps:
  • ZnAc 2 ⁇ 2H 2 O (1.1g), PEG400 (7.5mL), NaOH (4.0g) were dissolved in 30mL of absolute ethanol, added to 50mL of polytetrafluoroethylene reactor, and then sealed in stainless steel container After being heated at 120 ° C for 12 h, it was naturally cooled to room temperature, and a white precipitate was separated, washed three times with absolute ethanol and deionized water, and dried at 100 ° C for 4 h to obtain ZnO nanowires (ZnONW);
  • ZnO nanowires (0.1g) were ultrasonically dispersed in 5mL of distilled water, 2mL of 0.05mol/L CuCl 2 solution was added to the ZnO nanowire suspension system, magnetically stirred for 1h, centrifuged and washed 3 times with deionized water. Then, it was redispersed in 5 mL of distilled water, and 5 mL of a 0.05 mol/L NaBH 4 solution was added thereto, and magnetically stirred at room temperature for 1 hour, aged for 24 hours, and centrifuged to obtain ZnONW-Cu fiber hybrid particles.
  • the ZnO nanofibers of the fiber hybrid particles loaded with nano-Cu on the surface of the ZnO fiber obtained in the present embodiment have a diameter of 40 nm and a length of 10 ⁇ m, and the particle diameter of the nano-Cu supported thereon is 20 nm.
  • the present embodiment provides a fiber hybrid particle of a conductive polyaniline supported on a surface of a BaTiO 3 fiber, which is prepared by the following steps:
  • the precursor sol was transferred to an injection device for continuous spinning to obtain BaTiO 3 gel fiber, and the BaTiO 3 gel fiber was dried in an oven at 85 ° C for 3 hours, so that the solvent on the surface of the fiber was volatilized and the fiber shape was fixed;
  • the fiber is placed in a crucible and placed in a muffle furnace for heat treatment.
  • the heat treatment of BaTiO 3 fiber is divided into two steps of calcination and sintering.
  • the purpose of calcination is to completely remove a large amount of organic matter in the fiber to avoid excessive pores and cracks.
  • the heating rate should be controlled slowly; firstly heat to 180 ° C at 2 ° C / min, heat at 180 ° C for 1 h, then 5 ° C / min to 400 ° C and keep warm for 60 min, and finally 5 ° C / Min was raised to 600 ° C for 2 h; the calcined fiber was sintered at 800 ° C for 1 h at a rate of 5 ° C / min to obtain BaTiO 3 ceramic fiber, 1 g of BaTiO 3 ceramic fiber, 20 mL of KH550 1 wt% aqueous alcohol solution, and placed. Among the 100 mL three-necked bottles, mechanical stirring was carried out for 30 min.
  • the liquid in the flask was suction filtered, washed with absolute ethanol and deionized water until the filtrate was colorless, and the powder obtained by suction filtration was vacuum dried at 80 ° C for 24 h to obtain a surface-loaded conductive polyaniline of barium titanate fiber. Hybrid particles.
  • This embodiment provides a fiber hybrid particle of nano surface titanium dioxide loaded on a CNT surface, which is prepared by the following steps:
  • This example provides a polymer-based composite material comprising the fiber hybrid particles of Example 1, which is prepared by the following steps:
  • the film was coated by a bar coater and thermally cured at 180 ° C for 2 hours to obtain a CNT-ZnO/epoxy composite.
  • the mass content of the fiber hybrid particles in the composite material is 48%.
  • Figure 6 is the conductivity curve of the CNT-ZnO/epoxy composite
  • Figure 7 is the I-V characteristic of the CNT-ZnO/epoxy composite. It can be seen from FIG. 6 and FIG. 7 that the composite material can not only ensure the insulation of the composite material, but also have the antistatic function of the composite material.
  • This example provides a polymer-based composite material comprising the fiber hybrid particles of Example 4, which is prepared by the following steps:
  • the film was coated by a bar coater and thermally cured at 180 ° C for 2 hours to obtain a BaTiO 3 -Ag/epxoy composite.
  • the mass content of the fiber hybrid particles in the composite material is 48%.
  • FIG. 8 is BaTiO 3 -Ag / epxoy change in dielectric constant composite curve
  • FIG. 9 is a BaTiO 3 -Ag / dielectric loss curves epxoy composite material
  • FIG. 10 is a BaTiO 3 -Ag / resistivity of the composite epxoy Curve with frequency. It can be seen from FIG. 8, FIG. 9 and FIG. 10 that the composite material can obtain both a high dielectric constant and a low dielectric loss, while at the same time ensuring its insulation and frequency stability, and in addition, it is in the field of catalysis. The application not only ensures its chemical stability, but also improves its catalytic performance.
  • the above examples illustrate that the fiber hybrid particles and the polymer matrix composite material of the present invention solve the problem of agglomeration and entanglement of the granular and fibrous nanomaterials, and impart multiple functions to the fibrous hybrid nanomaterial, which can be more convenient and effective.
  • the method comprises preparing a polymer-based composite material comprising the fiber hybridized particles, and the properties of the composite-based composite material are controllable.

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Abstract

本发明提供了一种纤维杂化颗粒及聚合物基复合材料。该纤维杂化颗粒由纳米纤维和负载在纳米纤维表面的纳米颗粒组成；纳米颗粒在纳米纤维的表面覆盖率为5％-100％；纳米纤维的直径为50nm-300nm，长度为1μm-100μm；纳米颗粒的粒径等于或小于纳米纤维的直径；纳米纤维与纳米颗粒的界面连接作用为物理吸附或/和化学键结合。本发明的聚合物基复合材料包括聚合物和填充于聚合物中的上述纤维杂化颗粒。该纤维杂化颗粒解决了颗粒状和纤维状纳米材料团聚和缠绕问题的同时，赋予纤维状杂化纳米材料多重功能，以更加方便、有效的方式得到性能可控、多功能的聚合物基复合材料。

Description

一种纤维杂化颗粒及聚合物基复合材料 技术领域
本发明涉及一种纤维杂化颗粒及由该纤维杂化颗粒构成的聚合物基复合材料，属于纳米纤维材料领域。
背景技术
纳米材料在广义上定义为在三维空间中至少有一维处在纳米尺度范围(0.1nm-100nm)或由他们作为基本单元构成的材料。纳米材料颗粒极细，表面积极大，在颗粒表面无序排列的原子百分数远大于大尺度材料表面原子所占的百分数，导致纳米材料具有传统固体材料所不具备的特性，如体积效应，表面效应，量子尺寸效应，宏观量子隧道效应和介电限域效应等，从而使纳米材料具有微波吸收性能、高表面活性、强氧化性、超顺磁性等。除以上基本特性，纳米材料还具有特殊的光学、催化、化学反应动力学和特殊的物理机械性质等。纳米材料的使用极大地丰富了材料的开发和应用。
纳米材料具有各种优异的特性，而高分子聚合物材料在力学、物理、化学、电学方面也拥有其独特的性能。将纳米材料与高分子聚合物材料进行复合，制备的复合材料既拥有纳米材料的特殊性能又能保持高分子聚合物材料的优异特性。
随着科学技术的发展，要求材料具有多种复合性能或更为特殊的性能。因此，单种纳米材料的应用在某些领域已不能满足技术要求。为了达到此目标，纳米材料的复合，成为了一种必然。
以往的纳米材料的复合技术是将几种纳米材料与其他物质(聚合物或纳米材料)进行混合。但是，由于纳米材料的高比表面积，表面活性很大，颗粒与颗粒之间极易通过范德华力吸附在一起，形成团聚体，并且不易再次分散开，从而使得在开发新材料的过程中不容易有效地控制材料的性能。
纳米纤维材料具有极大的比表面积、高横纵比、极强的与其他物质的互相渗透力，纳米纤维织物结构精细，具有极好的柔韧性、吸附性、过滤性等。纳米纤维独特的性能使其在膜材料、过滤介质、催化剂、电子产品、生物制品、复合增强材料等领域拥有巨大的市场潜力。但是，正是由于纳米纤维材料具有极大的纵横比和比表面积，将其与聚合物制备成复合材料时易缠绕，特别是与纳米颗粒通过机械方法复合时，难以得到分散均匀的复合材料，性能难以控制。
发明内容
为了解决上述技术问题，本发明的目的在于提供一种纤维杂化颗粒及由该纤维杂化颗粒构成的聚合物基复合材料。该纤维杂化颗粒解决了颗粒状和纤维状纳米材料团聚和缠绕问题的同时，赋予纤维状杂化纳米材料多重功能，以更加方便、有效的方式得到性能可控、多功能的聚合物基复合材料。
为了实现上述技术目的，本发明首先提供了一种纤维杂化颗粒，该纤维杂化颗粒由纳米纤维和负载在纳米纤维表面的纳米颗粒组成；
其中，所述纳米颗粒在所述纳米纤维的表面覆盖率为5％-100％；
所述纳米纤维的直径为50nm-300nm，长度为1μm-100μm；
所述纳米颗粒的粒径等于或小于所述纳米纤维的直径；
所述纳米纤维与所述纳米颗粒的界面连接作用为物理吸附或/和化学键结合。
在本发明提供的纤维杂化颗粒中，优选地，采用的纳米颗粒的粒径为1nm-50nm。
在本发明提供的纤维杂化颗粒中，优选地，采用的纳米纤维为纳米导体纤维，采用的纳米颗粒为绝缘氧化物纳米颗粒或半导体氧化物纳米颗粒。纳米导体纤维表面负载绝缘氧化物或半导体氧化物纳米颗粒的纤维杂化颗粒的结构如图1所示。
在本发明提供的纤维杂化颗粒中，优选地，采用的纳米导体纤维包括无机纳米导体纤维和/或有机纳米导体纤维。
在本发明提供的纤维杂化颗粒中，优选地，采用的无机纳米导体纤维包括碳纳米管、纳米金、纳米银、纳米铜、纳米镍、纳米钛、纳米钴、纳米铝、纳米铁、纳米铟、纳米锡和纳米锌中的一种或几种组合的合金。
在本发明提供的纤维杂化颗粒中，优选地，采用的有机纳米导体纤维包括由聚乙炔、聚噻吩(上海汇平化工有限公司生产)、聚吡咯(日本Carlit公司生产)、聚苯胺(石家庄冀安亚大新材料科技有限公司生产)、对位聚苯、聚苯撑乙烯和聚双炔中的至少一种组成的纳米导体纤维。
在本发明提供的纤维杂化颗粒中，优选地，采用的绝缘氧化物纳米颗粒包括钛酸钡纳米颗粒、钛酸锶钡纳米颗粒、钛酸铅纳米颗粒、钛酸铜钙纳米颗粒、氮化硼纳米颗粒、氮化铝纳米颗粒、氧化铝纳米颗粒、二氧化硅纳米颗粒、二氧化钛纳米颗粒、钛酸钙纳米颗粒和硫酸钙纳米颗粒中的至少一种。
在本发明提供的纤维杂化颗粒中，优选地，采用的半导体氧化物纳米颗粒包括氧化银纳米颗粒、氧化锌纳米颗粒、氧化亚铜纳米颗粒、氧化铜纳米颗粒、氧化锰纳米颗粒、 氧化铁纳米颗粒和氧化钛纳米颗粒中的至少一种。
在本发明提供的纤维杂化颗粒中，优选地，采用的纳米纤维为绝缘氧化物纳米纤维或半导体氧化物纳米纤维，采用的纳米颗粒为导电微粒。绝缘氧化物纳米纤维或半导体氧化物纳米纤维表面负载导电微粒的纤维杂化颗粒的结构如图2所示。
在本发明提供的纤维杂化颗粒中，优选地，采用的绝缘氧化物纳米纤维或半导体氧化物纳米纤维包括由钛酸钡、钛酸锶钡、钛酸铅、钛酸铜钙、氮化硼、氮化铝、氧化铝、二氧化硅、二氧化钛、钛酸钙、硫酸钙、氧化银、氧化锌、氧化亚铜、氧化铜、氧化锰和氧化铁中的至少一种构成的绝缘氧化物纳米纤维或半导体氧化物纳米纤维。
在本发明提供的纤维杂化颗粒中，优选地，采用的导电微粒包括金微粒、银微粒、铜微粒、镍微粒、钛微粒、钴微粒、铝微粒、铁微粒和锰微粒中的至少一种；或
采用的导电微粒为导电碳微粒，更优选地，采用的导电碳微粒包括石墨、氧化石墨、石墨烯、纳米炭管和炭黑中的至少一种；或
采用的导电微粒为导电聚合物微粒，更优选地，采用的导电聚合物微粒包括由聚乙炔、聚噻吩、聚吡咯、聚苯胺、对位聚苯、聚苯撑乙烯和聚双炔中的至少一种组成的导电聚合物微粒。
本发明提供的上述纤维杂化颗粒是通过纳米纤维与纳米颗粒之间物理吸附或/和化学键结合作用制备得到的，具体的制备方法如本发明的实施例所示，但不局限于实施例中的制备方法。
本发明还提供了一种聚合物基复合材料，该聚合物基复合材料包括聚合物和填充于所述聚合物中的纤维杂化颗粒；其中，纤维杂化颗粒是上述的纤维杂化颗粒；采用的纤维杂化颗粒占该聚合物基复合材料总质量的10％-80％。
在本发明提供的聚合物基复合材料中，优选地，采用的聚合物包括环氧树脂(济南圣泉集团股份有限公司生产)、聚酰亚胺树脂(沁阳市天益化工有限公司生产)、聚酯树脂(广州产协高分子有限公司生产)、酚醛树脂(济南圣泉集团股份有限公司生产)和双马来酰亚胺三嗪树脂(咸阳三精科工贸有限公司生产)中的至少一种。
本发明提供的上述聚合物基复合材料，具体的制备方法如下：
将纤维杂化颗粒分散与丁酮溶液中，经过搅拌和超声分散处理1小时后，加入溶解于丁酮溶液的聚合物溶液；
搅拌和超声分散2小时，加入固化剂、固化促进剂、消泡剂、流变剂；其中，固化剂、固化促进剂、消泡剂、流变剂选择本领域中常用的试剂即可，各物质的添加量可以 按本领域的常规方式确定；
超声搅拌0.5小时后得到含有杂化颗粒的树脂浆料；
经过棒式涂布机涂膜，加热交联固化，得到聚合物基复合材料。
本发明通过构建合理的纳米结构，将颗粒状纳米微粒通过静电吸附或化学键作用负载于纳米纤维表面，在解决了颗粒状和纤维状纳米材料团聚和缠绕问题的同时，赋予纤维状杂化纳米材料多重功能，以更加方便有效的方式制备性能可控、多功能的聚合物基复合材料。
附图说明
图1为纳米导体纤维表面负载绝缘氧化物或半导体氧化物纳米颗粒的纤维杂化颗粒的结构示意图。
图2为绝缘氧化物纳米纤维或半导体氧化物纳米纤维表面负载导电微粒的纤维杂化颗粒的结构示意图。
图3为CNT-ZnO纤维杂化颗粒的SEM图像，ZnO颗粒负载在CNT表面。
图4为BaTiO3-Ag纤维杂化颗粒的SEM图像，Ag颗粒负载在BaTiO3纤维表面。
图5为CNT-TiO2纤维杂化颗粒的TEM图像，TiO2颗粒负载在CNT纤维表面。
图6为CNT-ZnO/epoxy复合材料的电导率曲线。
图7为CNT-ZnO/epoxy复合材料的I-V特性曲线。
图8为BaTiO3-Ag/epxoy复合材料的介电常数变化曲线。
图9为BaTiO3-Ag/epxoy复合材料的介电损耗变化曲线。
图10为BaTiO3-Ag/epxoy复合材料的电阻率随频率变化曲线。
主要组件符号说明：
11纳米导体纤维 12绝缘氧化或半导体氧化物纳米颗粒 21绝缘氧化物纳米纤维或半导体氧化物纳米纤维 22导电微粒
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。
实施例1
本实施例提供了一种CNT表面负载纳米氧化锌的纤维杂化颗粒，其是通过以下步骤制备得到的：
取1g碳纳米管(CNT)放到200mL浓硝酸和浓硫酸(3:1体积比)混合液中，在65℃下搅拌4小时；
待混合液冷却后用去离子水稀释，待碳纳米管沉下去倒掉其上清液，之后再多次稀释成中性后将其烘干即可得到酸化后的CNT；
将酸化后的CNT分散到300mL的ZnO溶胶当中，用球磨法处理12小时，之后将溶液放入到三口烧瓶中缓慢加热至180℃恒温24小时；
冷却至室温后，用无水乙醇和去离子水多次洗涤，在100℃干燥至少12小时后即可得到CNT-ZnO纤维杂化颗粒。
本实施例的CNT-ZnO纤维杂化颗粒，是通过酸化处理后的CNT表面带羧基和水解后成碱性的Zn(OH)2的羟基进行结合制备的纤维杂化颗粒。纳米导体纤维11表面负载绝缘氧化物或半导体氧化物纳米颗粒12的纤维杂化颗粒的结构如图1所示。
本实施例制备的纤维杂化颗粒中的CNT的直径为10nm-20nm，长度大于10μm，ZnO纳米颗粒的直径小于10nm，该CNT-ZnO杂化颗粒的SEM如图3所示。
实施例2
本实施例提供了一种CNT表面负载BaTiO3的纤维杂化颗粒，其是通过以下步骤制备得到的：
将0.25g的CNT分散到100mL的无水乙醇中，与0.3mL的28wt％浓氨水混合，超声分散15min；
将0.75mL的钛酸四丁酯缓慢滴入，约5min，在45℃搅拌24h；
用去离子水和无水乙醇分别清洗3次，100℃干燥12h；
500℃，空气气氛中烧结2h的到CNT-TiO2杂化颗粒；
在钡源的水溶液中加入经500℃烧结2小时后的CNT-TiO2，在反应釜中200℃加热12小时即可得到CNT-BaTiO3纤维杂化颗粒。
本实施例的CNT-BaTiO3纤维杂化颗粒，CNT未经处理，与二氧化钛/钛酸钡之间没有化学键的作用，依靠反应体系中各自位置的电负性差异进行静电吸附，从而形成纤维杂化颗粒。
本实施例制备的杂化颗粒中的CNT直径为10nm-20nm，长度大于10μm，BaTiO3的粒径可控制在5nm-15nm。
本实施例的CNT-BaTiO3纤维杂化颗粒与环氧树脂制备的复合材料，既能保证复合材料的绝缘性，又能获得较高的介电常数和较低的介电损耗。
实施例3
本实施例提供了一种铜纳米线表面负载TiO2纤维杂化颗粒，其是通过以下步骤制备得到的：
取0.1M的Cu(NO3)210ml，15M的NaOH 200ml，1.5mL的乙二胺放入500mL圆底烧瓶中，升温至50℃，700rpm搅拌；
5min后取0.25mL的35wt％的N2H4快速加入到上述溶液当中；
2min后加入150mL含3wt％的聚乙烯吡咯烷酮(MW＝10000)和1wt％的二乙羟基胺的水溶液，反应1小时；
经过离心分离即可得到铜纳米线(CuNW)，最后将CuNW分散到乙醇溶液中，取0.5mL的钛酸四丁酯缓慢滴入，约5min，45℃搅拌24h；
用去离子水和无水乙醇分别清洗3次，100℃干燥12h，之后500℃，空气气氛中烧结2h的到CuNW-TiO2纤维杂化颗粒。
本实施例中得到的CuNW-TiO2纤维杂化颗粒的Cu纳米线的直径为50nm，长度为10μm-20μm，TiO2的粒径为20nm。
实施例4
本实施例提供了一种BaTiO3纤维表面负载纳米Ag的纤维杂化颗粒，其是通过以下步骤制备得到的：
将2.5541g的乙酸钡粉末加入到4mL冰乙酸中，在室温下搅拌，直到完全溶解；
把4.6mL钛酸四丁酯加入到3.5mL乙醇中磁力搅拌30min；
上述两种溶液在室温下混合，搅拌8h，加入0.2g的PVP，搅拌8h，得到黄色透明前驱体溶胶；
将前驱体溶胶转移到注射装置中进行连续纺丝，得到BaTiO3凝胶纤维，将BaTiO3凝胶纤维在85℃烘箱干燥3h，使得纤维表面溶剂挥发，纤维形状固定，再把纤维置于坩埚中，放入马弗炉中进行热处理，BaTiO3纤维热处理分为预烧和烧结两个步骤，预烧的目的是将纤维中大量有机物充分排除，以免造成过多的孔洞和裂缝，因此在升温速率要控制的比较缓慢；首先以2℃/min的速率加热到180℃，在180℃下保温1h，再以5℃/min加热到400℃并保温60min，最后以5℃/min升到600℃保温2h；预烧后的纤维以5℃/min的速率在800℃烧结1h，获得BaTiO3陶瓷纤维。之后称量1g硝酸银粉末加 入到100mL的乙二醇溶液中搅拌30min，得到浅黄色溶液；
称量1g钛酸钡纤维加入到300mL的三口烧瓶中，加入100mL的乙二醇溶液，磁性搅拌1h，将浅黄色溶液缓慢的加入到三口烧瓶中，并搅拌2h，缓慢升温到140℃并保温30分钟，室温冷却得到浅灰色溶液；
将浅灰色溶液静置，上层清液倒掉，下层沉淀物用酒精洗涤3-5次，在80℃下干燥2h，得到钛酸钡纤维表面负载银纳米颗粒的纤维杂化颗粒。
本实施例的钛酸钡纤维表面负载银纳米颗粒的纤维杂化颗粒，是依靠钛酸钡的(1,1,1)晶面间距与银纳米颗粒的(1,1,1)晶面间距接近的原理，银纳米颗粒可以优先在钛酸钡表面进行成核生长，从而形成纤维杂化颗粒。绝缘氧化物纳米纤维或半导体氧化物纳米纤维21表面负载导电微粒22的纤维杂化颗粒的结构如图2所示。
本实施例得到的钛酸钡纤维表面负载银纳米颗粒的纤维杂化颗粒的钛酸钡纳米纤维的直径为500nm，长度为15μm，负载于其表面的纳米Ag的粒径为70nm-80nm。该BaTiO3-Ag纤维杂化颗粒的SEM如图4所示。
实施例5
本实施例提供了一种ZnO纤维表面负载纳米Cu的纤维杂化颗粒，其是通过以下步骤制备得到的：
将ZnAc2·2H2O(1.1g)、PEG400(7.5mL)、NaOH(4.0g)溶于30mL的无水乙醇中，加入到50mL的聚四氟乙烯反应釜中，,然后密封在不锈钢容器内，在120 ℃恒温12h后，自然冷却至室温，分离出白色沉淀，依次用无水乙醇、去离子水洗涤3次，100℃干燥4h，得到ZnO纳米线(ZnONW)；
将一定量的ZnO纳米线(0.1g)超声分散于5mL蒸馏水中，将2mL的0.05mol/L的CuCl2溶液加入ZnO纳米线悬浮体系中，磁力搅拌1h后，离心并用去离子水洗涤3次后重新分散于5mL蒸馏水中，加入5mL的0.05mol/L的NaBH4溶液，于室温条件下磁力搅拌1h，陈化24h，离心分离后得到ZnONW-Cu纤维杂化颗粒。
本实施例得到的ZnO纤维表面负载纳米Cu的纤维杂化颗粒的ZnO纳米纤维的直径为40nm，长度为10μm，负载于其上的纳米Cu的粒径为20nm。
实施例6
本实施例提供了一种BaTiO3纤维表面负载导电聚苯胺的纤维杂化颗粒，其是通过以下步骤制备得到的：
将2.5541g乙酸钡粉末加入到4mL冰乙酸中，在室温下搅拌，直到完全溶解；
把4.6mL的钛酸四丁酯加入到3.5mL的乙醇中磁力搅拌30min；
上述两种溶液在室温下混合，搅拌8h，加入0.2g的PVP，搅拌8h，得到黄色透明前驱体溶胶；
将前驱体溶胶转移到注射装置中进行连续纺丝，得到BaTiO3凝胶纤维，将BaTiO3凝胶纤维在85℃烘箱干燥3h，使得纤维表面溶剂挥发，纤维形状固定；
纤维置于坩埚中，放入马弗炉中进行热处理，BaTiO3纤维热处理分为预烧和烧结两个步骤，预烧的目的是将纤维中大量有机物充分排除，以免造成过多的孔洞和裂缝，因此在升温速率要控制的比较缓慢；首先以2℃/min的速率加热到180℃，在180℃下保温1h，再以5℃/min加热到400℃并保温60min，最后以5℃/min升到600℃保温2h；预烧后的纤维以5℃/min的速率在800℃烧结1h，获得BaTiO3陶瓷纤维，取BaTiO3陶瓷纤维1g，20mL的KH550的1wt％醇水溶液，放入100mL三口瓶当中，机械搅拌30min。将2mL(0.02mol)的苯胺单体配成2M的盐酸溶液70mL，并将其倒入三口烧瓶中，继续机械搅拌1h；称量4.564gAPS(0.02mol)溶解于20mL的去离子水中；将引发剂APS的水溶液滴加入三口烧瓶中，随着APS的滴加，烧瓶内的液体逐渐由无色变成淡蓝色，最后变成墨绿色，继续搅拌反应3h；
反应结束后，对烧瓶中的液体进行抽滤，用无水乙醇和去离子水洗涤至滤液呈无色，将抽滤得到的粉末80℃真空干燥24h后得到钛酸钡纤维表面负载导电聚苯胺的杂化颗粒。
实施例7
本实施例提供了一种CNT表面负载纳米二氧化钛的纤维杂化颗粒，其是通过以下步骤制备得到的：
将CNT 0.25g分散到100mL无水乙醇当中，与0.3mL的8wt％的浓氨水混合，超声分散15min；
将0.75mL的钛酸四丁酯缓慢滴入，约5min，45℃搅拌24h，用去离子水和无水乙醇分别清洗3次，100℃干燥12h，500℃，空气气氛中烧结2h，去除有机物和提高结晶性，得到CNT-TiO2纤维杂化颗粒，CNT-TiO2纤维杂化颗粒的TEM如图5所示。
实施例8
本实施例提供了一种含有实施例1的纤维杂化颗粒的聚合物基复合材料，其是通过以下步骤制备得到的：
取10g实施例1制得的CNT-ZnO纤维杂化颗粒分散于20mL的丁酮溶液中，搅拌 和超声分散1小时，加入溶解于20mL丁酮中的10g环氧树脂Epon828；
经过搅拌和超声分散2小时，加入溶解于5mL的N,N-二甲基甲酰胺的0.8g双氰胺和0.1g的2-甲基-4-乙基咪唑混合液，超声搅拌0.5小时后，得到含有杂化颗粒的环氧树脂浆料；
经过棒式涂布机涂膜，180℃热固化2小时，得到CNT-ZnO/epoxy复合材料。其中，该复合材料中纤维杂化颗粒的质量含量48％。
图6为CNT-ZnO/epoxy复合材料的电导率曲线，图7为CNT-ZnO/epoxy复合材料的I-V特性曲线。由图6和图7可知，该复合材料后既能保证复合材料的绝缘性，又能是复合材料具有抗静电的功能。
实施例9
本实施例提供了一种含有实施例4的纤维杂化颗粒的聚合物基复合材料，其是通过以下步骤制备得到的：
取10g实施例4得到的BaTiO3-Ag纤维杂化颗粒分散于20mL丁酮溶液中，搅拌和超声分散1小时，加入溶解于20mL的丁酮中的10g环氧树脂Epon828；
经过搅拌和超声分散2小时，加入溶解于5mL的N,N-二甲基甲酰胺的0.8g的双氰胺和0.1g的2-甲基-4-乙基咪唑混合液，超声搅拌0.5小时，得到含有杂化颗粒的环氧树脂浆料；
经过棒式涂布机涂膜，180℃热固化2小时，得到BaTiO3-Ag/epxoy复合材料。其中，该复合材料中纤维杂化颗粒的质量含量为48％。
图8为BaTiO3-Ag/epxoy复合材料的介电常数变化曲线，图9为BaTiO3-Ag/epxoy复合材料的介电损耗变化曲线，图10为BaTiO3-Ag/epxoy复合材料的电阻率随频率变化曲线。由图8、图9和图10可知，该复合材料既能得到较高的介电常数和较低的介电损耗，同时还能保证其绝缘性和频率稳定性，另外，其在催化领域中应用既能保证其化学稳定性，又能提高其催化性能。
以上实施例说明，本发明的纤维杂化颗粒及聚合物基复合材料，解决了颗粒状和纤维状纳米材料团聚和缠绕问题的同时，赋予了纤维状杂化纳米材料多重功能，可以更加方便有效的方式制备含有该纤维杂化颗粒的聚合物基复合材料，该复合物基复合材料的性能可控。

Claims (15)

  1. 一种纤维杂化颗粒，其特征在于，该纤维杂化颗粒由纳米纤维和负载在纳米纤维表面的纳米颗粒组成；
    其中，所述纳米颗粒在所述纳米纤维的表面覆盖率为5％-100％；
    所述纳米纤维的直径为50nm-300nm，长度为1μm-100μm；
    所述纳米颗粒的粒径等于或小于所述纳米纤维的直径；
    所述纳米纤维与所述纳米颗粒的界面连接作用为物理吸附或/和化学键结合。
  2. 根据权利要求1所述的纤维杂化颗粒，其特征在于，所述纳米颗粒的粒径为1nm-50nm。
  3. 根据权利要求1所述的纤维杂化颗粒，其特征在于，所述纳米纤维为纳米导体纤维，所述纳米颗粒为绝缘氧化物纳米颗粒或半导体氧化物纳米颗粒。
  4. 根据权利要求3所述的纤维杂化颗粒，其特征在于，所述纳米导体纤维包括无机纳米导体纤维和/或有机纳米导体纤维。
  5. 根据权利要求4所述的纤维杂化颗粒，其特征在于，所述无机纳米导体纤维包括碳纳米管、纳米金、纳米银、纳米铜、纳米镍、纳米钛、纳米钴、纳米铝、纳米铁、纳米铟、纳米锡和纳米锌中的一种或几种组合的合金。
  6. 根据权利要求4所述的纤维杂化颗粒，其特征在于，所述有机纳米导体纤维包括由聚乙炔、聚噻吩、聚吡咯、聚苯胺、对位聚苯、聚苯撑乙烯和聚双炔中的至少一种组成的纳米导体纤维。
  7. 根据权利要求3所述的纤维杂化颗粒，其特征在于，所述绝缘氧化物纳米颗粒包括钛酸钡纳米颗粒、钛酸锶钡纳米颗粒、钛酸铅纳米颗粒、钛酸铜钙纳米颗粒、氮化硼纳米颗粒、氮化铝纳米颗粒、氧化铝纳米颗粒、二氧化硅纳米颗粒、二氧化钛纳米颗粒、钛酸钙纳米颗粒和硫酸钙纳米颗粒中的至少一种。
  8. 根据权利要求3所述的纤维杂化颗粒，其特征在于，所述半导体氧化物纳米颗粒包括氧化银纳米颗粒、氧化锌纳米颗粒、氧化亚铜纳米颗粒、氧化铜纳米颗粒、氧化锰纳米颗粒、氧化铁纳米颗粒和氧化钛纳米颗粒中的至少一种。
  9. 根据权利要求1所述的纤维杂化颗粒，其特征在于，所述纳米纤维为绝缘氧化物纳米纤维或半导体氧化物纳米纤维，所述纳米颗粒为导电微粒。
  10. 根据权利要求9所述的纤维杂化颗粒，其特征在于，所述绝缘氧化物纳米纤维或半导体氧化物纳米纤维包括由钛酸钡、钛酸锶钡、钛酸铅、钛酸铜钙、氮化硼、氮化 铝、氧化铝、二氧化硅、二氧化钛、钛酸钙、硫酸钙、氧化银、氧化锌、氧化亚铜、氧化铜、氧化锰和氧化铁中的至少一种构成的绝缘氧化物纳米纤维或半导体氧化物纳米纤维。
  11. 根据权利要求9所述的纤维杂化颗粒，其特征在于，所述导电微粒包括金微粒、银微粒、铜微粒、镍微粒、钛微粒、钴微粒、铝微粒、铁微粒和锰微粒中的至少一种；或
    所述导电微粒为导电碳微粒；或
    所述导电微粒为导电聚合物微粒。
  12. 根据权利要求11所述的纤维杂化颗粒，其特征在于，所述导电碳微粒包括石墨、氧化石墨、石墨烯、纳米炭管和炭黑中的至少一种。
  13. 根据权利要求11所述的纤维杂化颗粒，其特征在于，所述导电聚合物微粒包括由聚乙炔、聚噻吩、聚吡咯、聚苯胺、对位聚苯、聚苯撑乙烯和聚双炔中的至少一种组成的导电聚合物微粒。
  14. 一种聚合物基复合材料，其特征在于，该聚合物基复合材料包括聚合物和填充于所述聚合物中的纤维杂化颗粒；
    所述纤维杂化颗粒是权利要求1-13任一项所述的纤维杂化颗粒；
    所述纤维杂化颗粒占该聚合物基复合材料总质量的10％-80％。
  15. 根据权利要求14所述的聚合物基复合材料，其特征在于，所述聚合物包括环氧树脂、聚酰亚胺树脂、聚酯树脂、酚醛树脂和双马来酰亚胺三嗪树脂中的至少一种。
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110655846A (zh) * 2019-10-14 2020-01-07 李道勤 一种增强防腐性能的增韧环氧树脂涂料
GB2578668B (en) * 2018-08-31 2021-08-11 Airbus Defence & Space Gmbh Process for the nanostructuring of carbon fiber surfaces in fiber-composite plastics based on sulfur and on aromatic hydrocarbons
CN115028932A (zh) * 2022-06-24 2022-09-09 郑荣妹 一种有机高分子复合陶瓷材料的制备方法
CN117383855A (zh) * 2023-09-25 2024-01-12 武汉理工大学 基于负载导电相纤维的导电水泥基复合材料及制备方法
CN117813265A (zh) * 2023-11-19 2024-04-02 广东邦普循环科技有限公司 一种重金属捕捉剂及其制备方法与应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107488277A (zh) * 2017-09-06 2017-12-19 深圳市峰泳科技有限公司 一种负载异质颗粒的无机填料及其制备方法
CN113754925B (zh) * 2021-09-28 2023-04-07 浙江荣泰科技企业有限公司 一种绝缘基材-碳纳米管杂化材料及其制备方法和用途
CN117654166A (zh) * 2023-12-05 2024-03-08 松山湖材料实验室 一种负载纤维及其制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2505653A1 (en) * 2004-04-28 2005-10-28 National Research Council Of Canada Composite catalyst layer, electrode and passive mixing flow field for compressionless fuel cells
CN101508418A (zh) * 2009-03-17 2009-08-19 中国科学院长春应用化学研究所 一种制备铂/碳纳米管杂化材料的方法
CN101604753A (zh) * 2009-07-24 2009-12-16 成都中科来方能源科技有限公司 碳硅复合材料及其制备方法和用途
CN101662029A (zh) * 2009-09-25 2010-03-03 北京化工大学 一种金属氧化物/碳纤维复合材料及其制备方法和应用
US20130108702A1 (en) * 2011-11-01 2013-05-02 Swadeshmukul Santra Copper/silica nanoparticles, methods of making, and methods of use
CN104221101A (zh) * 2012-02-10 2014-12-17 赛陆泰科公司 用磁性纳米粒子修饰的纤维素纳米纤丝
CN105118682A (zh) * 2015-09-14 2015-12-02 清华大学 活性炭与石墨烯杂化物构成的复合颗粒、制备方法及应用

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101413210B (zh) * 2008-11-12 2011-08-31 东华大学 等离子体处理涂覆纳米二氧化硅的碳纤维表面改性的方法
CN102059113B (zh) * 2010-11-30 2014-03-19 北京化工大学 一种碳纳米纤维生长用层状双金属氢氧化物的应用
CN102277648B (zh) * 2011-05-30 2013-08-28 中国科学院青岛生物能源与过程研究所 无机/有机复合聚酰亚胺基纳米纤维膜及制法和应用
KR101324279B1 (ko) * 2012-03-05 2013-11-01 인하대학교 산학협력단 니켈산화물/활성흑연나노섬유 복합체 및 상기 복합체를 포함하는 슈퍼커패시터용 전극
CN103849008B (zh) * 2012-11-29 2018-04-13 深圳先进技术研究院 杂化颗粒、聚合物基复合材料及其制备方法与应用
CN103611531A (zh) * 2013-12-16 2014-03-05 长春工业大学 氧化银/二氧化钛复合纳米纤维光催化剂的制备方法及其应用
CN103643350B (zh) * 2013-12-19 2015-12-09 齐鲁工业大学 一种Co3O4/In2O3异质结构纳米管及其制备方法与应用
CN103721705B (zh) * 2014-01-14 2015-12-02 武汉理工大学 一种多孔TiO2纤维负载贵金属甲醛室温氧化催化剂及其制备方法
CN105126836A (zh) * 2015-08-31 2015-12-09 河海大学 银修饰的螺旋形二氧化钛纳米纤维光催化剂的制备和应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2505653A1 (en) * 2004-04-28 2005-10-28 National Research Council Of Canada Composite catalyst layer, electrode and passive mixing flow field for compressionless fuel cells
CN101508418A (zh) * 2009-03-17 2009-08-19 中国科学院长春应用化学研究所 一种制备铂/碳纳米管杂化材料的方法
CN101604753A (zh) * 2009-07-24 2009-12-16 成都中科来方能源科技有限公司 碳硅复合材料及其制备方法和用途
CN101662029A (zh) * 2009-09-25 2010-03-03 北京化工大学 一种金属氧化物/碳纤维复合材料及其制备方法和应用
US20130108702A1 (en) * 2011-11-01 2013-05-02 Swadeshmukul Santra Copper/silica nanoparticles, methods of making, and methods of use
CN104221101A (zh) * 2012-02-10 2014-12-17 赛陆泰科公司 用磁性纳米粒子修饰的纤维素纳米纤丝
CN105118682A (zh) * 2015-09-14 2015-12-02 清华大学 活性炭与石墨烯杂化物构成的复合颗粒、制备方法及应用

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2578668B (en) * 2018-08-31 2021-08-11 Airbus Defence & Space Gmbh Process for the nanostructuring of carbon fiber surfaces in fiber-composite plastics based on sulfur and on aromatic hydrocarbons
GB2593842A (en) * 2018-08-31 2021-10-06 Airbus Defence & Space Gmbh Process for the nanostructuring of carbon fiber surfaces in fiber-composite plastics based on sulfur and on aromatic hydrocarbons
US11318690B2 (en) 2018-08-31 2022-05-03 Airbus Defence and Space GmbH Process for nanostructuring carbon fibers embedded in FRPS based on the use of sulphur in combination with aromatic hydrocarbon groups and on the use of laser radiation
GB2593842B (en) * 2018-08-31 2023-04-19 Airbus Defence & Space Gmbh Process for the nanostructuring of carbon fiber surfaces in fiber-composite plastics based on sulfur and on aromatic hydrocarbons
CN110655846A (zh) * 2019-10-14 2020-01-07 李道勤 一种增强防腐性能的增韧环氧树脂涂料
CN115028932A (zh) * 2022-06-24 2022-09-09 郑荣妹 一种有机高分子复合陶瓷材料的制备方法
CN115028932B (zh) * 2022-06-24 2024-03-22 郑荣妹 一种有机高分子复合陶瓷材料的制备方法
CN117383855A (zh) * 2023-09-25 2024-01-12 武汉理工大学 基于负载导电相纤维的导电水泥基复合材料及制备方法
CN117813265A (zh) * 2023-11-19 2024-04-02 广东邦普循环科技有限公司 一种重金属捕捉剂及其制备方法与应用

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