CN115626781B - Metal-plated glass fiber with metal oxide as medium and preparation method thereof - Google Patents

Metal-plated glass fiber with metal oxide as medium and preparation method thereof Download PDF

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CN115626781B
CN115626781B CN202211415333.1A CN202211415333A CN115626781B CN 115626781 B CN115626781 B CN 115626781B CN 202211415333 A CN202211415333 A CN 202211415333A CN 115626781 B CN115626781 B CN 115626781B
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glass fiber
metal
plating solution
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metal oxide
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CN115626781A (en
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徐征
金伟超
徐利文
叶飞
杨雪敏
郭彬
方林玄
尹官武
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Hangzhou Normal University
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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
    • C03C25/52—Coatings containing inorganic materials only

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  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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  • Materials Engineering (AREA)
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  • Chemically Coating (AREA)

Abstract

The invention relates to the technical field of glass fiber production, and discloses a metal-plated glass fiber taking metal oxide as a medium and a preparation method thereof. The preparation method comprises three processes of cleaning, dielectric and chemical plating, so that the traditional glass fiber chemical plating process is greatly simplified, the organic metal reagent is used for replacing expensive inorganic metal salts such as palladium chloride, high-toxicity tin chloride and the like in the activation and sensitization steps in the traditional chemical plating method, the production cost can be greatly reduced, the production efficiency is improved, and the whole process is environment-friendly. The prepared metal-plated glass fiber has the characteristics of good stability and strong binding force, and has great application prospect in the aspect of conductive polymer composite materials.

Description

Metal-plated glass fiber with metal oxide as medium and preparation method thereof
Technical Field
The invention belongs to the field of new functionalized inorganic materials, and particularly relates to a metal-plated glass fiber taking metal oxide as a medium and a preparation method thereof.
Background
The Glass Fiber (GFs) is an inorganic nonmetallic material with excellent performance, and has the characteristics of high mechanical strength, good insulativity, strong heat, good corrosion resistance and the like. Meanwhile, from the industrial application point of view, the advantages of light weight and low cost exist. The surface of the glass fiber is plated with metals such as nickel, copper, gold, silver and the like, so that the glass fiber has the conductivity of the metals while maintaining the original excellent performance, thereby preparing the lightweight conductive filler, and having wide application prospect in conductive polymer materials.
Compared with the production processes such as a vacuum plating method, a vapor deposition method, a hot dipping method and the like, the chemical plating has the characteristics of low cost, simple process, excellent environmental stability and the like, and is widely used for preparing the metal core-shell structure composite material. For metallized glass fibers, copper-plated and nickel-plated glass fibers are most common.
In the traditional glass fiber electroless copper plating or nickel plating process, five processes of cleaning, roughening, activating, sensitization and electroless plating are usually included, high-concentration hydrofluoric acid is often needed for roughening, and expensive palladium chloride, high-toxicity tin chloride or high-concentration nickel salt and other inorganic metal salts are used for activating and sensitizing, so that the production cost is high, the toxicity is high, and the environment is polluted greatly.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a chemical plating metal method without using noble metal and high-concentration hydrogen fluoride, so as to effectively reduce the production cost of plating metal on the surface of glass fiber and solve the problem of environmental pollution.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a metal-plated glass fiber taking metal oxide as a medium sequentially comprises a metal coating, a metal oxide layer and glass fiber from outside to inside.
Further, the glass fiber is long glass fiber or short glass fiber manufactured by taking various types of glass as raw materials through high-level melting and wire drawing processes.
Further, the metal oxide layer is formed by hydrolysis reaction of a metal organic reagent on the surface of the glass fiber under an acidic condition, and is uniformly attached to the glass fiber. The metal organic reagent includes, but is not limited to, one or more of tetrabutyl zirconate, zirconocene dichloride, aluminum triisopropoxide, aluminum tributoxide, lanthanum triisopropoxide, lanthanum triethoxide, aluminum triethoxide, lanthanum tributoxide, and the like.
Further, the metal coating comprises a copper layer, a nickel layer and a copper-nickel layer, the thickness of the metal coating is less than or equal to 500nm, and metal particles are densely covered on the metal oxide layer of the glass fiber.
Further, a method for preparing metal-plated glass fiber with metal oxide as a medium comprises the following steps:
step (1): surface treatment of glass fiber: immersing glass fiber in ethanol, stirring, filtering, adding into sulfuric acid solution, stirring again, cleaning, filtering, cleaning with deionized water, and drying in a vacuum oven;
step (2): adding an organic metal reagent into the glass fiber subjected to surface treatment in the step (1), stirring at room temperature, adding an acidic solution, hydrolyzing for 0.5-5 h, filtering, and drying in a vacuum oven to obtain the glass fiber with the metal oxide layer attached to the surface.
Step (3): mixing the glass fiber attached with the metal oxide layer obtained in the step (2) with the metal plating solution A, slowly dripping a reducing agent at the temperature of 30-98 ℃ to react for 0.5-5 h, filtering, and drying in a vacuum oven to obtain the glass fiber plated with the metal A;
further, the concentration of the sulfuric acid solution in the step (1) is 1-4wt%;
further, the pH of the acidic solution in step (2) is 0.1-4.0;
further, the mass ratio of the acid solution to the glass fiber in the step (2) is 2-10:1;
further, the acidic solution in step (2) includes, but is not limited to, nitric acid, hydrochloric acid, or sulfuric acid;
further, the mass ratio of the organic metal reagent to the glass fiber in the step (2) is 0.1-0.8:1.
Further, in the step (3), the metal plating solution A adopts a copper plating solution or a nickel plating solution;
the copper plating solution adopts CuSO 4 、NaKC 4 H 4 O 6 After mixing, regulating the pH value to 12-14 by using sodium hydroxide solution; wherein CuSO 4 With NaKC 4 H 4 O 6 The mass ratio of (2) is 15:40;
the nickel plating solution adopts NiSO 4 ·6H 2 O、CH 3 COONa、C 6 H 9 Na 3 O 9 Adding CH 3 In COOH, regulating the pH value to 8-9 by ammonia water solution; wherein NiSO 4 ·6H 2 O、CH 3 COONa、C 6 H 9 Na 3 O 9 The mass ratio of (2) is 30:18:20; CH (CH) 3 The consumption of COOH is 15mLCH added into each liter of nickel plating solution 3 COOH。
Further, in the step (3), if the metal plating solution adopts a copper plating solution, formaldehyde is adopted as the reducing agent; if the metal plating solution adopts nickel plating solution, the reducing agent adopts NaH 2 PO 2 。
Further, after the step (3), the glass fiber with the metal A plated on the surface can be mixed with the metal plating solution B, and a reducing agent is slowly added dropwise at the temperature of 30-98 ℃ for oxidation-reduction reaction for 0.5-1.5 h, so that the glass fiber with the metal A-B plated on the surface can be obtained; the metal plating solution B adopts copper plating solution or nickel plating solution; the metal A, B in the metal plating solution A, B is a different metal.
Compared with the prior art, the invention has the following beneficial effects:
according to the method for generating the high-activity metal oxide medium by the acid-catalyzed reaction of the organic metal reagent on the surface of the glass fiber, the three processes of roughening, activating and sensitizing in the traditional electroless plating method are combined into one medium process, so that the use of expensive palladium salt, high-toxicity tin salt and high-corrosivity hydrofluoric acid is effectively avoided. The method not only greatly simplifies the technological process of chemically plating the glass fiber, but also effectively reduces the production cost and realizes the greenization of the technological process. The metal-plated composite glass fiber prepared by the method has the advantages of high bonding strength and difficult falling off, and can be widely used as conductive filler in conductive polymer composite materials, such as conductive silicon rubber, conductive adhesive tape, gauze conductive cloth, non-pattern conductive cloth and the like.
Drawings
FIG. 1 is a scanning electron micrograph of example 2.
FIG. 2 is a spectrum analysis chart of example 2.
FIG. 3 is a scanning electron micrograph of example 7.
FIG. 4 is a spectrum analysis chart of example 7.
FIG. 5 is a photograph of a copper layer scanning electron microscope of example 8.
FIG. 6 is a photograph of a nickel-copper layer scanning electron microscope of example 8.
FIG. 7 is a chart of the copper layer spectrum analysis of example 8.
FIG. 8 is a chart of the energy spectrum of the nickel-copper layer of example 8.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. The specific embodiments described herein are to be considered in an illustrative sense only and are not intended to limit the invention.
Meanwhile, technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other. The invention is described in further detail below with reference to the examples, in which the starting materials are either commercially available or are prepared by conventional methods.
Example 1:
adding a proper amount of ethanol into 2g of glass fiber, stirring and cleaning, vacuum filtering, taking out, adding a 1wt% sulfuric acid solution, stirring and cleaning, vacuum filtering, and then placing in a vacuum oven for drying at 60-70 ℃; adding 0.8g tetrabutyl zirconate solution into the treated glass fiber, fully stirring for 0.5h, adding 4ml nitric acid solution with pH of 1.5 for hydrolysis for 0.5h, vacuum-pumping, filtering, and drying in a vacuum oven to obtain ZrO 2 @ GFs, a copper plating solution (CuSO) 4 15g/L,NaKC 4 H 4 O 6 40g/L, pH=12-14) 20ml with sodium hydroxide solution, add ZrO 2 Stirring at a constant temperature of 60 ℃ and dropwise adding formaldehyde solution, reacting for 0.5h, taking out, vacuum filtering and drying. The obtained Cu@ZrO 2 The yield of @ GFs is 85.3%, and the copper layer is distributed more loosely.
Example 2
Adding a proper amount of ethanol into 2g of glass fiber, stirring and cleaning, vacuum filtering, taking out, adding a 4wt% sulfuric acid solution, stirring and cleaning, vacuum filtering, and then placing in a vacuum oven for drying at 60-70 ℃; adding 1.0g of triisopropoxyl aluminum solution into the treated glass fiber, fully stirring for 5.0h, adding 10ml of hydrochloric acid solution with pH of 0.1 for hydrolysis for 3.2h, vacuum-filtering, and drying in a vacuum oven to obtain Al 2 O 3 @ GFs, a copper plating solution (CuSO) 4 15g/L,NaKC 4 H 4 O 6 40g/L, pH=12-14) 20ml with sodium hydroxide solution, adding Al 2 O 3 Stirring at a constant temperature of 60 ℃ and dropwise adding formaldehyde solution, reacting for 1.0h, taking out, vacuum filtering and drying. The Cu@Al obtained 2 O 3 The yield of @ GFs is 92.1%, a complete copper layer is attached to the surface of the glass fiber, the copper content is 9.14% of the total weight as measured by EDS, and the copper layer is about 150nm thick. The scanning electron microscope photograph is shown in fig. 1, and the energy spectrum analysis chart is shown in fig. 2.
Example 3
Adding a proper amount of ethanol into 2g of glass fiber, stirring and cleaning, vacuum filtering, taking out, adding 3wt% sulfuric acid solution, stirring and cleaning, vacuum filtering, and drying in a vacuum oven at 60-70 ℃; adding 1.0g of triethoxy lanthanum solution into the treated glass fiber, fully stirring for 1.5h, adding 16ml of sulfuric acid solution with pH of 4 for hydrolysis for 5h, vacuum-filtering, and drying in a vacuum oven to obtain La 2 O 3 @ GFs, a copper plating solution (CuSO) 4 15g/L,NaKC 4 H 4 O 6 40g/L, pH=12-14) 20ml with sodium hydroxide solution, adding La 2 O 3 Stirring at a constant temperature of 60 ℃ and dropwise adding formaldehyde solution, reacting for 1.5h, taking out, vacuum filtering and drying. Obtained Cu@La 2 O 3 The yield of @ GFs is 90.5%, the copper layers are densely distributed and are densely hemispherical and attached to the surface of the glass fiber.
Example 4
Adding a proper amount of ethanol into 2g of glass fiber, stirring and cleaning, vacuum filtering, taking out, adding 3wt% sulfuric acid solution, stirring and cleaning, vacuum filtering, and drying in a vacuum oven at 60-70 ℃; adding 1.2g of tetraethyl zirconate solution into the treated glass fiber, fully stirring for 1.0h, adding 10ml of nitric acid solution with pH of 0.45 for hydrolysis for 1.0h, vacuum-filtering, and drying in a vacuum oven to obtain ZrO 2 @ GFs, a copper plating solution (CuSO) 4 15g/L,NaKC 4 H 4 O 6 40g/L, pH=12-14) 20ml with sodium hydroxide solution, add ZrO 2 Stirring at a constant temperature of 60 ℃ and dropwise adding formaldehyde solution,after 1.0h the reaction was taken out, filtered in vacuo and dried. The obtained Cu@ZrO 2 The yield of @ GFs is 91.8%, and a complete copper layer is attached to the surface of the glass fiber.
Example 5
Adding a proper amount of ethanol into 3.0g of glass fiber, stirring and cleaning, vacuum filtering, taking out, adding a sulfuric acid solution with the weight percent of 4%, stirring and cleaning, vacuum filtering, and then placing in a vacuum oven for drying at the temperature of 60-70 ℃; adding 1.0g of tributoxy aluminum solution into the treated glass fiber, fully stirring for 2.0h, adding 10ml of nitric acid solution with pH of 2.3 for hydrolysis for 1.0h, vacuum-filtering, and drying in a vacuum oven to obtain Al 2 O 3 @ GFs, a copper plating solution (CuSO) 4 15g/L,NaKC 4 H 4 O 6 40g/L, pH=12-14) 20ml with sodium hydroxide solution, adding Al 2 O 3 Stirring at a constant temperature of 60 ℃ and dropwise adding formaldehyde solution, reacting for 1.0h, taking out, vacuum filtering and drying. The Cu@Al obtained 2 O 3 The yield of @ GFs is 91.3%, the copper layers are densely distributed and are densely hemispherical and attached to the surface of the glass fiber.
Example 6
Adding a proper amount of ethanol into 3.0g of glass fiber, stirring and cleaning, vacuum filtering, taking out, adding a sulfuric acid solution with the weight percent of 4%, stirring and cleaning, vacuum filtering, and then placing in a vacuum oven for drying at the temperature of 60-70 ℃; adding 0.8g of zirconocene dichloride solution into the treated glass fiber, fully stirring for 1.0h, adding 10ml of nitric acid solution with pH of 0.45 for hydrolysis for 0.5h, vacuum-filtering, and drying in a vacuum oven to obtain ZrO 2 @ GFs, a nickel plating solution (NiSO) 4 ·6H 2 O30g/L,CH 3 COONa 18g/L,C 6 H 9 Na 3 O 9 20g/L,CH 3 COOH 15ml/L, adjusting pH to 8-9) 15ml with ammonia solution, adding ZrO 2 Stirring at constant temperature of 85 ℃ and dropwise adding 200g/LNaH 2 PO 2 The solution was taken out after the reaction was continued for 1.0h until the blue-green liquid was completely reacted to a grey-black system, vacuum filtered and dried. The obtained Ni@ZrO 2 The yield of @ GFs was 92.1% and the nickel layer was spherically distributed on the surface of the glass fiber.
Example 7
Adding a proper amount of ethanol into 2.0g of glass fiber, stirring and cleaning, vacuum filtering, taking out, adding a sulfuric acid solution with the weight percent of 4%, stirring and cleaning, vacuum filtering, and then placing in a vacuum oven for drying at the temperature of 60-70 ℃; adding 1.0g of triisopropoxyl aluminum into the treated glass fiber, fully stirring for 1.0h, adding 10ml of nitric acid solution with pH of 0.45 for hydrolysis for 1.0h, vacuum-filtering, and drying in a vacuum oven to obtain Al 2 O 3 @ GFs, a nickel plating solution (NiSO) 4 ·6H 2 O30g/L,CH 3 COONa 18g/L,C 6 H 9 Na 3 O 9 20g/L,CH 3 COOH 15ml/L, adjusting pH to 8-9) 15ml with ammonia solution, adding Al 2 O 3 Stirring at constant temperature of 85 ℃ and dropwise adding 200g/LNaH 2 PO 2 The solution was reacted until the blue-green liquid was completely reacted to a grey-black system, the reaction was continued for 0.5h, vacuum filtered and dried. The obtained Ni@Al 2 O 3 The yield of @ GFs is 91.3%, the nickel layer is densely distributed on the surface of the glass fiber, the nickel content accounts for 9.46% of the total weight through EDS detection, and the thickness of the nickel layer reaches 200nm. The scanning electron microscope photograph is shown in fig. 3, and the energy spectrum analysis chart is shown in fig. 4.
Example 8
Adding a proper amount of ethanol into 3.0g of glass fiber, stirring and cleaning, vacuum filtering, taking out, adding a sulfuric acid solution with the weight percent of 4%, stirring and cleaning, vacuum filtering, and then placing in a vacuum oven for drying at the temperature of 60-70 ℃; adding 2.5g of triisopropoxyl aluminum into the treated glass fiber, fully stirring for 1.0h, adding 10ml of nitric acid solution with pH of 0.45 for hydrolysis for 1.0h, vacuum-filtering, and drying in a vacuum oven to obtain Al 2 O 3 @ GFs, a copper plating solution (CuSO) 4 15g/L,NaKC 4 H 4 O 6 40g/L, pH=12-14) 20ml with sodium hydroxide solution, adding Al 2 O 3 Stirring at constant temperature of 80 ℃ and dropwise adding formaldehyde solution, reacting for 1h, taking out, vacuum filtering and drying. The Cu@Al obtained 2 O 3 @ GFs. Preparing nickel plating solution (NiSO) 4 ·6H 2 O 30g/L,CH 3 COONa 18g/L,C 6 H 9 Na 3 O 9 20g/L,CH 3 COOH 15ml/L, pH 8-9) 10ml with aqueous ammonia solution, 1.5g C was addedu@Al 2 O 3 Stirring at constant temperature of GFs and 85 ℃ and dropwise adding 200g/L NaH 2 PO 2 The solution was reacted until the blue-green liquid was completely reacted to a grey-black system, the reaction was continued for 0.5h, vacuum filtered and dried. Obtaining Ni-Cu@Al 2 O 3 The yield is 90.8%, and the thickness of the Cu-Ni layer reaches 300nm. The scanning electron microscope photograph of the copper layer is shown in fig. 5, and the energy spectrum analysis chart is shown in fig. 7; the scanning electron microscope photograph of the nickel-copper layer is shown in fig. 6, and the spectrum analysis chart is shown in fig. 8.

Claims (8)

1. A metal-plated glass fiber taking metal oxide as a medium, which is characterized by sequentially comprising a metal coating, a metal oxide layer and glass fiber from outside to inside; the metal oxide layer is an organic metal reagent M under acidic condition x O y R z Uniformly attaching a thin metal oxide layer M on the surface of glass fiber m O n The method comprises the steps of carrying out a first treatment on the surface of the The organic metal reagent comprises one or more of tetrabutyl zirconate, zirconocene dichloride, aluminum triisopropoxide, aluminum tributoxide, lanthanum triisopropoxide, lanthanum triethoxide, aluminum triethoxide and lanthanum tributoxide; the metal coating is a copper layer, a nickel layer or a copper-nickel composite layer, and is densely covered on the metal oxide layer on the surface of the glass fiber, and the thickness is within 500 and nm.
2. The metal-plated glass fiber with metal oxide as a medium according to claim 1, wherein the glass fiber can be long glass fiber or short glass fiber manufactured by high-level melting and wire drawing processes by taking various types of glass as raw materials.
3. A method for preparing a metal oxide-mediated metallized glass fiber according to any one of claims 1-2, comprising the steps of:
step (1): glass fiber surface pretreatment
Immersing glass fiber in ethanol, stirring, filtering, adding into sulfuric acid solution, stirring again, cleaning, filtering, cleaning with deionized water, and drying in a vacuum oven;
step (2): adding an organic metal reagent into the glass fiber subjected to surface treatment in the step (1), stirring at room temperature, adding an acidic solution, hydrolyzing for 0.5-5 h, filtering, and drying in a vacuum oven to obtain the glass fiber with metal oxide as a medium;
step (3): mixing glass fiber with metal oxide as medium obtained in the step (2) with metal plating solution A, and carrying out treatment on the mixture at 30-98 o Dropwise adding a reducing agent under the condition C to perform oxidation-reduction reaction for 0.5-5 h to obtain metal-plated A glass fiber taking metal oxide as a medium;
step (4): after the reaction is finished, vacuum filtration is carried out after the temperature is reduced to room temperature, and a vacuum oven is dried, so that the metal-plated glass fiber with the metal oxide as a medium is obtained.
4. A method according to claim 3, wherein the sulfuric acid solution in step (1) has a concentration of 0.1 to 4 wt%.
5. The method according to claim 3, wherein the pH of the acidic solution in step (2) is 0.1 to 4.0; the mass ratio of the acidic solution to the glass fiber is 2-10: 1, a step of; the acid solution is one of nitric acid, hydrochloric acid or sulfuric acid; the mass ratio of the organic metal reagent to the glass fiber is 0.1-0.8: 1.
6. a method according to claim 3, wherein in step (3) the metal plating solution a is a copper plating solution or a nickel plating solution;
the copper plating solution adopts copper sulfate CuSO 4 Sodium potassium tartrate NaKC 4 H 4 O 6 After mixing, regulating the pH to 12-14 by using a sodium hydroxide solution; wherein CuSO 4 With NaKC 4 H 4 O 6 The mass ratio of (2) is 15:40, a step of performing a;
the nickel plating solution adopts hexahydrate nickel sulfate NiSO 4 ·6H 2 O, sodium acetate CH 3 COONa, sodium citrate dihydrate C 6 H 9 Na 3 O 9 Adding CH 3 In COOH, regulating the pH value to 8-9 by using an ammonia water solution; wherein NiSO 4 ·6H 2 O、CH 3 COONa、C 6 H 9 Na 3 O 9 The mass ratio of (2) is 30:18:20, a step of; CH (CH) 3 The consumption of COOH is 15mLCH added into each liter of nickel plating solution 3 COOH。
7. The method of claim 6, wherein in step (3) if the metal plating solution is copper plating solution, formaldehyde is used as the reducing agent; if the metal plating solution adopts nickel plating solution, the reducing agent adopts sodium hypophosphite NaH 2 PO 2 。
8. The method of claim 7, wherein the metal-plated glass fiber A and the metal plating solution B are mixed before the step (4) in a range of 30 to 98 o Slowly dripping a reducing agent under the condition C to perform oxidation-reduction reaction for 0.5-1.5 h to obtain metal-plated A-B glass fiber; the metal plating solution B adopts copper plating solution or nickel plating solution; the metal A, B in the metal plating solution A, B is a different metal.
CN202211415333.1A 2022-11-11 2022-11-11 Metal-plated glass fiber with metal oxide as medium and preparation method thereof Active CN115626781B (en)

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