CN112010572A - Conductive glass fiber and preparation method thereof - Google Patents

Conductive glass fiber and preparation method thereof Download PDF

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Publication number
CN112010572A
CN112010572A CN202010825724.5A CN202010825724A CN112010572A CN 112010572 A CN112010572 A CN 112010572A CN 202010825724 A CN202010825724 A CN 202010825724A CN 112010572 A CN112010572 A CN 112010572A
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glass fiber
solution
tannic acid
silver
prepared
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潘春呈
张志良
刘洪刚
侯勇
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Taishan Fiberglass Inc
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/48—Coating with two or more coatings having different compositions
    • C03C25/54—Combinations of one or more coatings containing organic materials only with one or more coatings containing inorganic materials only
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/42—Coatings containing inorganic materials
    • C03C25/46—Metals

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  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Conductive Materials (AREA)

Abstract

The invention provides a conductive glass fiber and a preparation method thereof, and the preparation method comprises the following specific steps of adding tannic acid into a buffer solution, rapidly stirring and dissolving, dispersing the glass fiber into the buffer solution containing tannic acid, and depositing on the surface of the glass fiber to form a poly-tannic acid functional coating through the self-oxidation of the tannic acid; then uses the unique molecular structure of tannic acid to react Ag+Complexing on the surface of the silver, and complexing Ag by utilizing the self-reducing capacity of phenolic hydroxyl in tannin molecules+While reducing the Cu into silver nano-particles in situ, and finally utilizing the autocatalysis of the silver nano-particles to reduce the Cu2+Reducing to form a continuous, compact and firm conductive copper layer on the surface of the glass fiber; the preparation method disclosed by the invention is simple and convenient in process, free of environmental pollution, green and environment-friendly, and can be used for preparing the electric and heat conducting coatingElectromagnetic shielding coating, wave-absorbing material and the like; the conductive glass fiber prepared by the invention has the characteristics of good conductivity, high adhesion, good oxidation resistance and the like.

Description

Conductive glass fiber and preparation method thereof
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of conductive composite materials, in particular to a conductive glass fiber and a preparation method thereof.
[ background of the invention ]
The conductive glass fiber is an important electromagnetic shielding conductive filler prepared by taking glass fiber as a base material and depositing a layer of metal on the surface of the glass fiber, not only retains the excellent physical and chemical properties of the glass fiber, but also endows the glass fiber with excellent conductivity and chemical stability, and has the excellent characteristics of small elongation, large specific surface area, good corrosion resistance, high tensile strength and the like, so the conductive glass fiber becomes a research hotspot in the field of material science and engineering technology in recent years.
The chemical plating process has low requirement on equipment and simple and convenient operation, and can deposit a metal conducting layer on a non-conductor substrate, so that the chemical plating process obtains the common attention of the majority of scientific researchers and is the most common method for preparing a metal plating layer on the surface of a substrate such as glass fiber and the like at present. Huang et al, washing glass fiber with acetone and ethanol, etching with hydrofluoric acid, surface functionalizing with tetraethyl orthosilicate solution, and finally adding silver ammonia solution to deposit silver layer, thus preparing silver-coated glass fiber, wherein the lowest volume resistance is 1.56 × 10 by testing with four-probe method3Ω/cm2(Applied Surface Science,2012,258(7), 2246-. Zhang coarsens the glass fiber by potassium permanganate and concentrated sulfuric acid, performs stannous chloride sensitization and palladium chloride activation pretreatment, and performs treatment by mixed bath solution of copper sulfate, hydrazine hydrate and sodium citrate to obtain the glass fiber with the resistivity of 8.62 multiplied by 10-4Omega cm metallic copper loaded glass fiber (Micro)&Nano Letters,2014,9(2): 83-86). However, these methods are too complicated to be prepared by complicated pretreatment and preparation processes; more serious, the interfacial adhesion between the metal coating and the glass substrate is not stable enough, which greatly affects the application of the conductive glass fiber in the electromagnetic shielding material. In order to solve the problems, the surface of a glass fiber substrate is modified by dopamine such as flos farinae and the like, stronger adhesive property and adsorption capacity to metal ions can be formed between polydopamine and the substrate, and a silver layer is chemically reduced in situ on the surface of the polydopamine functionalized modified substrate by chemical plating to prepare the conductive glass fiber (Journal) with strong interface adhesionof The Electrochemical Society,2012,159,217). However, this method has a significant disadvantage in that dopamine and silver sources necessary for the preparation process are expensive, resulting in very high preparation costs, making it difficult to apply such methods to electromagnetic shielding materials.
The tannin as a plant polyphenol compound has the outstanding advantages of low price, wide source, good biocompatibility and the like; meanwhile, in view of the super-strong interfacial adhesion of catechol groups in tannin molecules, the tannin functional layer can be formed on the surfaces of various substrates through oxidation and self-polymerization, and can form super-strong bonding force with the surfaces of various materials, so that the tannin functional layer can show super-strong adhesion and long-term stability in most environments; and the catechol group in the tannin molecule can also adsorb and complex various metal ions, so that the metal ions are reduced to a metal simple substance in situ, and the surface metallized composite conductive material with ultrahigh interface adhesion can be prepared through the bridging action of the poly tannin molecule.
[ summary of the invention ]
Aiming at the defects in the prior art, the invention aims to provide the conductive glass fiber and the preparation method thereof, wherein the method is used for preparing a uniform and compact metal copper layer with strong interface bonding force on the surface of the glass fiber by utilizing the bridging effect of poly-tannic acid molecules between the metal copper layer and a substrate.
The invention adopts the following technical scheme: a preparation method of conductive glass fiber comprises the following steps:
(1) dissolving tannic acid in a buffer solution to prepare a buffer solution containing tannic acid;
(2) placing Glass Fiber (GF) in the tannin-containing buffer solution prepared in the step (1) for polymerization reaction to prepare first glass fiber (GF @ TA) coated with a poly-tannin functional coating on the surface;
(3) dispersing the first glass fiber prepared in the step (2) in a solution containing silver ions for a complex reaction to prepare a second glass fiber (GF @ TA @ AgNPs) with silver nanoparticles growing on the surface;
(4) and (4) dispersing the second glass fiber prepared in the step (3) in a solution containing copper ions for reaction to prepare the conductive glass fiber (GF @ TA @ Cu) with copper plated on the surface.
Preferably, the buffer solution in step (1) is selected from one of Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCl), Tris (hydroxymethyl) aminomethane, Bis (2-hydroxyethylamino) Tris (hydroxymethyl) methane or Bis (2-hydroxyethylamino) Tris (hydroxymethyl) methane hydrochloride (Bis-Tris-HCl), and the pH is 6.0-10.0.
Preferably, the concentration of the tannic acid in the tannin containing buffer solution in the step (1) is 1.0g/L to 5.0g/L, and in the range, more copper ions can be complexed to form a more complete copper layer on the surface of the glass fiber, and the conductivity is better.
Preferably, the Glass Fiber (GF) in the step (2) is selected from one of alkali-free glass fiber, high-alkali glass fiber or special glass fiber, and the fiber diameter is between 3 and 30 mu m.
Preferably, the specific preparation process of the first glass fiber in the step (2) is as follows: placing glass fiber in a buffer solution containing tannic acid, stirring, controlling the rotating speed at 100-1200rpm, reacting for 1-24 h, and then separating and filtering; the process utilizes the autoxidation of tannic acid to polymerize on the surface of glass fiber to form a poly-tannic acid functional coating.
Preferably, the specific preparation process of the second glass fiber in the step (3) is as follows: dispersing the first glass fiber prepared in the step (2) in a solution containing silver ions, stirring, controlling the rotating speed at 1200rpm, reacting for 0.5-12h, separating and filtering, and then washing with deionized water for 2-3 times to obtain a second glass fiber (GF @ TA @ AgNPs) with silver nanoparticles (AgNPs) growing on the surface; the process is to mix Ag+Complexing on the surface of tannin molecules, and complexing Ag by utilizing the self-reducing capability of phenolic hydroxyl in the tannin molecules+While reducing the silver nanoparticles in situ.
Preferably, the silver ion-containing solution in step (3) is selected from one of silver nitrate aqueous solution, silver ammonia solution or a complexing solution of silver ions and EDTA; and the concentration of the silver ion-containing solution is 1-10 g/L, preferably 4-6 g/L.
The silver ion-containing solution selected in the step (3) has an autocatalysis effect after silver nanoparticles are formed by in-situ reduction of silver ions, and can accelerate Cu2+The copper layer is formed on the surface of the glass fiber, and other metal ions can not be reduced into the nano structure in situ.
The diameter of the silver nanoparticles (AgNPs) formed on the surface of the first glass fiber (GF @ TA) in the step (3) is between 5 and 60nm, and the formed silver nanoparticles (AgNPs) are used as active catalytic points for quickly forming a conductive copper layer on the surface of the first glass fiber (GF @ TA).
Preferably, the specific preparation process of the surface copper-plated conductive glass fiber (GF @ TA @ Cu) in the step (4) is as follows: dispersing the second glass fiber (GF @ TA @ AgNPs) prepared in the step (3) in a solution containing copper ions, reacting for 0.5-16h, taking out the material, washing with deionized water for 1-3 times, washing with absolute ethyl alcohol for 1-3 times, and then drying in a vacuum oven at 60 ℃ for 2-3 h to obtain the conductive glass fiber (GF @ TA @ Cu) with copper plated on the surface; the process utilizes the autocatalysis of silver nanoparticles to convert Cu into Cu2+Reducing to form a conductive copper layer on the surface of the glass fiber.
Preferably, the solution containing copper ions in the step (4) is one of copper nitrate, copper chloride, copper sulfate aqueous solution or a complexing solution of copper ions and EDTA; and the concentration of the copper ion-containing solution is 1-20 g/L, preferably 10-20 g/L, and more preferably 15-20 g/L.
It is another object of the present invention to provide an electrically conductive glass fiber prepared according to the above method.
The invention has the beneficial effects that:
the invention uses the unique molecular structure of tannic acid, firstly forms a poly-tannic acid functional coating on the surface of glass fiber through auto-oxidation polymerization, and then Ag is added+Complexing on the surface of the silver, and complexing Ag by utilizing the self-reducing capacity of phenolic hydroxyl in tannin molecules+While reducing the Cu into silver nano-particles in situ, and finally utilizing the autocatalysis of the silver nano-particles to reduce the Cu2+Reducing to form a conductive copper layer on the surface of the glass fiber;the preparation process is simple to operate, mild in condition, low in manufacturing cost and controllable in reaction process, and can be used for preparing the copper-plated glass fiber in batches;
the conductive glass fiber prepared by the method can form a uniform and compact metal copper layer on the surface of the glass fiber, has good conductivity, and has strong interface adhesion force due to the bridging effect of the poly-tannic acid between the conductive copper layer and the glass fiber matrix.
[ description of the drawings ]
FIG. 1 is a schematic view of a process for preparing the conductive glass fiber of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of example 1; wherein, FIG. 2a is a Scanning Electron Microscope (SEM) image of the glass fiber; FIG. 2b is a Scanning Electron Microscope (SEM) image of the first glass fiber; FIG. 2c is a Scanning Electron Microscope (SEM) image of the conductive glass fiber;
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) chart of example 1; wherein, FIG. 3a is an XPS spectrum of a glass fiber; FIG. 3b is an XPS spectrum of a first glass fiber; FIG. 3c is an XPS spectrum of a conductive glass fiber; FIG. 3d is a high resolution XPS spectrum of copper.
[ detailed description ] embodiments
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described with the following embodiments, but is by no means limited thereto. The following is a description of the preferred embodiments of the present invention, and should not be taken as limiting the invention, but rather as embodying the invention in its broadest form and as indicating any variations, equivalents and modifications within the spirit and scope of the present invention.
As shown in fig. 1, the preparation method of the conductive glass fiber of the present invention comprises forming a poly-tannic acid functional coating on the surface of the glass fiber, then forming silver nanoparticles on the surface of the poly-tannic acid functional coating, and finally generating a uniform and dense conductive copper layer on the surface of the poly-tannic acid functional coating by utilizing the autocatalysis of the silver nanoparticles. The specific process refers to the following examples:
example 1
(1) Dissolving tannic acid in Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCl) solution with pH of 8.5 under stirring to obtain tannin-containing buffer solution with concentration of 1.0 g/L;
(2) putting the alkali-free glass fiber with the fiber diameter of 3 mu m into the tannin-containing buffer solution prepared in the step (1), uniformly mixing by ultrasonic waves, stirring at room temperature, controlling the rotating speed to be 200rpm, reacting for 12h, separating and filtering to obtain a first glass fiber (GF @ TA) with the surface coated with the poly-tannin functional coating;
(3) dispersing the first glass fiber prepared in the step (2) in a silver nitrate solution with the concentration of 3.0g/L, stirring at room temperature, controlling the rotating speed to be 500rpm, reacting for 6 hours, separating and filtering, and washing with deionized water for 2 times to obtain a second glass fiber (GF @ TA @ AgNPs) with silver nanoparticles (AgNPs) growing on the surface;
(4) and (3) dispersing the second glass fiber prepared in the step (3) in a copper nitrate solution with the concentration of 10.0g/L, reacting for 12h at room temperature, taking out the material, washing with deionized water for 1 time, then washing with absolute ethyl alcohol for 3 times, and then drying in a vacuum oven at 60 ℃ for 2h to obtain the conductive glass fiber (GF @ TA @ Cu) with copper plated on the surface.
Example 2
(1) Dissolving tannic acid in Tris (hydroxymethyl) aminomethane solution with pH of 8.5 under stirring to obtain tannic acid-containing buffer solution with concentration of 3.0 g/L;
(2) placing a special glass fiber with the fiber diameter of 23 mu m into the tannin-containing buffer solution prepared in the step (1), ultrasonically mixing uniformly, stirring at room temperature, controlling the rotating speed to be 300rpm, reacting for 12h, separating and filtering to obtain a first glass fiber (GF @ TA) with the surface coated with the poly-tannin functional coating;
(3) dispersing the first glass fiber prepared in the step (2) in a silver nitrate solution with the concentration of 6g/l, stirring at room temperature, reacting for 6h at the rotating speed of 800rpm, separating and filtering, and washing with deionized water for 3 times to obtain a second glass fiber (GF @ TA @ AgNPs) with silver nanoparticles (AgNPs) growing on the surface;
(4) and (3) dispersing the GF @ TA @ AgNPs prepared in the step (3) in 18g/l copper chloride solution, reacting for 12h at room temperature, taking out the material, washing the material for 3 times by using deionized water, then washing the material for 3 times by using absolute ethyl alcohol, and drying the material for 3h in a vacuum oven at the temperature of 60 ℃ to obtain the conductive glass fiber (GF @ TA @ Cu) with copper plated on the surface.
Example 3
(1) Placing tannic acid in a bis (2-hydroxyethylamino) tris (hydroxymethyl) methane solution with pH of 8.5, stirring and dissolving to prepare a tannic acid-containing buffer solution with a concentration of 5.0 g/L;
(2) placing the high-alkali glass fiber with the fiber diameter of 30 mu m into the tannin-containing buffer solution prepared in the step (1), ultrasonically mixing uniformly, stirring at room temperature, controlling the rotating speed to be 1000rpm, reacting for 12h, separating and filtering to obtain a first glass fiber (GF @ TA) with the surface coated with the poly-tannin functional coating;
(3) dispersing the first glass fiber prepared in the step (2) in a silver ammonia solution with the concentration of 8g/l, stirring at room temperature, controlling the rotating speed to be 1000rpm, reacting for 6h, separating and filtering, washing with deionized water for 3 times, and obtaining a second glass fiber (GF @ TA @ AgNPs) with silver nano particles (AgNPs) growing on the surface;
(4) and (3) dispersing the second glass fiber prepared in the step (3) in 15g/l copper sulfate solution, reacting for 12h at room temperature, taking out the material, washing with deionized water for 1 time, then washing with absolute ethyl alcohol for 3 times, and drying in a vacuum oven at 60 ℃ for 3h to obtain the conductive glass fiber (GF @ TA @ Cu) with copper plated on the surface.
Example 4
(1) Placing tannic acid in a solution of bis (2-hydroxyethylamino) tris (hydroxymethyl) methane hydrochloride with pH of 10, stirring and dissolving to prepare a tannin-containing buffer solution with a concentration of 5.0 g/L;
(2) putting the alkali-free glass fiber with the fiber diameter of 15 mu m into the tannin-containing buffer solution prepared in the step (1), uniformly mixing by ultrasonic waves, stirring at room temperature at the rotating speed of 100rpm, reacting for 12h, separating and filtering to obtain a first glass fiber (GF @ TA) with the surface coated with the poly-tannin functional coating;
(3) dispersing the first glass fiber prepared in the step (2) in a 2g/l complexing solution of silver ions and EDTA, stirring at room temperature, reacting for 6 hours at the rotation speed of 1000rpm, separating and filtering, and washing with deionized water for 3 times to obtain a second glass fiber (GF @ TA @ AgNPs) with silver nanoparticles (AgNPs) growing on the surface;
(4) and (3) dispersing the second glass fiber prepared in the step (3) in a copper ion solution with the concentration of 5.0g/L, reacting for 12h at room temperature, taking out the material, washing for 1 time by using deionized water, then washing for 3 times by using absolute ethyl alcohol, and then drying for 3h in a vacuum oven at 60 ℃ to obtain the conductive glass fiber (GF @ TA @ Cu) with copper plated on the surface.
Example 5
(1) Placing tannic acid in a solution of bis (2-hydroxyethylamino) tris (hydroxymethyl) methane hydrochloride with pH of 10.0, stirring to dissolve, and preparing a buffer solution containing tannic acid with concentration of 5.0 g/L;
(2) putting the alkali-free glass fiber with the fiber diameter of 15 mu m into the tannin-containing buffer solution prepared in the step (1), uniformly mixing by ultrasonic waves, stirring at room temperature at the rotating speed of 100rpm, reacting for 12h, separating and filtering to obtain a first glass fiber (GF @ TA) with the surface coated with the poly-tannin functional coating;
(3) dispersing the first glass fiber prepared in the step (2) in a silver ion solution with the concentration of 5g/L, stirring at room temperature, reacting for 6h at the rotation speed of 1000rpm, separating and filtering, and washing with deionized water for 3 times to obtain a second glass fiber (GF @ TA @ AgNPs) with silver nanoparticles (AgNPs) growing on the surface;
(4) and (3) dispersing the second glass fiber prepared in the step (3) in a complexing solution of copper ions and EDTA (ethylene diamine tetraacetic acid) with the concentration of 20.0g/L, reacting for 12h at room temperature, taking out the material, washing with deionized water for 1 time, washing with ethanol for 3 times, and drying in a vacuum oven at 60 ℃ for 3h to obtain the conductive glass fiber (GF @ TA @ Cu) with copper plated on the surface.
The glass fiber, the first glass fiber and the conductive glass fiber are respectively placed under an electron microscope for observation, the scanning electron microscope images of the glass fiber, the first glass fiber and the conductive glass fiber are shown in fig. 2, and in fig. 2, fig. 2a to 2c show that the surface appearance changes from the glass fiber (2a) to the first glass fiber (2b) and then to the conductive glass fiber (2c), and meanwhile, the conductive copper layer on the surface of the obtained conductive glass fiber (2c) is dense and continuous and has good conductive performance.
As can be seen from FIG. 3, the absorption peaks of Ca2p, Si2p and Al2p are significantly reduced and the absorption peak of C1s is significantly enhanced in FIG. 3b compared to FIG. 3a, indicating that a poly-tannic acid functional coating is formed on the surface of the glass fiber; the copper and silver peaks absent from fig. 3a and 3b appear in fig. 3c, illustrating the deposition of copper and silver particles on the surface of the glass fiber, and fig. 3d is a high resolution XPS spectrum of copper, which is the same absorption peak for Cu1s in GF @ TA @ Cu as the Cu peak in fig. 3 c.
Comparative example 1
(1) Placing tannic acid in a solution of bis (2-hydroxyethylamino) tris (hydroxymethyl) methane hydrochloride with pH of 10.0, stirring to dissolve, and preparing a buffer solution containing tannic acid with concentration of 5.0 g/L;
(2) putting the alkali-free glass fiber with the fiber diameter of 15 mu m into the tannin-containing buffer solution prepared in the step (1), uniformly mixing by ultrasonic waves, stirring at room temperature at the rotating speed of 100rpm, reacting for 6 hours, separating and filtering to obtain a first glass fiber (GF @ TA) with the surface coated with the poly-tannin functional coating;
(3) and (3) dispersing the first glass fiber prepared in the step (2) in 15.0g/L copper ion solution, reacting for 12h at room temperature, taking out the material, washing with deionized water for 1 time, then washing with ethanol for 3 times, and drying in a vacuum oven at 60 ℃ for 3h to obtain the conductive glass fiber (GF @ TA @ Cu) with copper plated on the surface.
Comparative example 2
(1) Placing tannic acid in a solution of bis (2-hydroxyethylamino) tris (hydroxymethyl) methane hydrochloride with pH of 10.0, stirring to dissolve, and preparing a buffer solution containing tannic acid with concentration of 5.0 g/L;
(2) putting the alkali-free glass fiber with the fiber diameter of 15 mu m into the tannin-containing buffer solution prepared in the step (1), uniformly mixing by ultrasonic waves, stirring at room temperature at the rotating speed of 100rpm, reacting for 12h, separating and filtering to obtain a first glass fiber (GF @ TA) with the surface coated with the poly-tannin functional coating;
(3) dispersing the first glass fiber prepared in the step (2) in a silver ion solution with the concentration of 0.5g/L, stirring at room temperature, reacting for 6 hours at the rotation speed of 1000rpm, separating and filtering, and washing with deionized water for 3 times to obtain a second glass fiber (GF @ TA @ AgNPs) with silver nanoparticles (AgNPs) growing on the surface;
(4) and (3) dispersing the second glass fiber prepared in the step (3) in a complexing solution of copper ions and EDTA (ethylene diamine tetraacetic acid) with the concentration of 0.8g/L, reacting for 12h at room temperature, taking out the material, washing with deionized water for 1 time, washing with ethanol for 3 times, and drying in a vacuum oven at 60 ℃ for 3h to obtain the conductive glass fiber (GF @ TA @ Cu) with copper plated on the surface.
The electrical resistivity and adhesion properties of the glass fibers prepared in the above examples and comparative examples were measured, wherein the adhesion properties were measured by a tape method, a 3M Scotch tape was adhered to the glass fibers according to ASTM D3359, pressed, and peeled off after being left for 24 hours.
The results are shown in the following table:
TABLE 1
Figure BDA0002636090060000071
Figure BDA0002636090060000081
As can be seen from the data in table 1, the conductive glass fibers prepared in examples 1 to 5 of the present invention have good conductivity (the lower the resistivity, the better the conductivity), and the resistivity of the glass fibers prepared in examples 1 to 5 and the comparative example is detected after being left for 30 days, and the change of the resistivity of the conductive glass fibers prepared in examples 1 to 5 is not large, which indicates that the conductive glass fibers prepared in the present invention have good oxidation resistance; after the test of the tape method, the glass fibers prepared in examples 1-5 and comparative examples 1-2 have no obvious copper layer peeling on the surface, the adhesion performance between the plating layer and the fiber interface is good, and the conductivity is not changed greatly after the glass fibers are adhered by the tape.

Claims (10)

1. The preparation method of the conductive glass fiber is characterized by comprising the following steps of:
(1) dissolving tannic acid in a buffer solution to prepare a buffer solution containing tannic acid;
(2) placing the glass fiber in the tannin-containing buffer solution prepared in the step (1) for polymerization reaction to prepare a first glass fiber coated with a poly-tannin functional coating;
(3) dispersing the first glass fiber prepared in the step (2) in a solution containing silver ions for a complexing reaction to prepare a second glass fiber with silver nanoparticles growing on the surface;
(4) and (4) dispersing the second glass fiber prepared in the step (3) in a solution containing copper ions for reaction to prepare the conductive glass fiber with the copper plated on the surface.
2. The method for preparing a conductive glass fiber according to claim 1, wherein the buffer solution in step (1) is selected from one of tris (hydroxymethyl) aminomethane hydrochloride, tris (hydroxymethyl) aminomethane, bis (2-hydroxyethylamino) tris (hydroxymethyl) methane, or bis (2-hydroxyethylamino) tris (hydroxymethyl) methane hydrochloride, and the pH of the buffer solution is 6.0 to 10.0.
3. The method of claim 1, wherein the concentration of tannic acid in the buffered solution containing tannic acid produced in step (1) is from about 1.0g/L to about 5.0 g/L.
4. The method for preparing the conductive glass fiber according to claim 1, wherein the glass fiber in the step (2) is selected from one of alkali-free glass fiber, high alkali glass fiber or special glass fiber, and the fiber diameter is between 3 and 30 μm.
5. The method for preparing the conductive glass fiber according to claim 1, wherein the first glass fiber is prepared by the following specific steps in step (2): and (2) placing the glass fiber in a buffer solution containing tannic acid, stirring, controlling the rotating speed at 100-1200rpm, reacting for 1-24 h, and then separating and filtering to obtain the first glass fiber coated with the poly-tannic acid functional coating.
6. The method for preparing the conductive glass fiber according to claim 1, wherein the second glass fiber is prepared by the following specific steps in step (3): and (3) dispersing the first glass fiber prepared in the step (2) in a solution containing silver ions for stirring, controlling the rotating speed at 1200rpm, reacting for 0.5-12h, separating and filtering, and then washing for 2-3 times by using deionized water to obtain a second glass fiber with silver nano particles (AgNPs) growing on the surface.
7. The method for preparing conductive glass fiber according to claim 6, wherein the silver ion-containing solution in step (3) is one selected from silver nitrate aqueous solution, silver ammonia solution or a complexing solution of silver ions and EDTA, and the concentration of the silver ion-containing solution is 1-10 g/L.
8. The method for preparing the conductive glass fiber according to claim 1, wherein the specific preparation process of the conductive glass fiber in the step (4) is as follows: and (3) dispersing the second glass fiber prepared in the step (3) in a solution containing copper ions, reacting for 0.5-16h, taking out the material, washing with deionized water for 1-3 times, washing with absolute ethyl alcohol for 1-3 times, and then drying in a vacuum oven at 60 ℃ for 2-3 h to obtain the conductive glass fiber with the copper-plated surface.
9. The method for preparing conductive glass fiber according to claim 8, wherein the copper ion-containing solution in step (4) is selected from one of copper nitrate solution, copper chloride solution, copper sulfate solution or a complexing solution of copper ions and EDTA, and the concentration is 1-20 g/L.
10. The conductive glass fiber prepared by the preparation method of any one of claims 1 to 9.
CN202010825724.5A 2020-08-17 2020-08-17 Conductive glass fiber and preparation method thereof Pending CN112010572A (en)

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