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KR20150048935A - Polyimide nanofiber with metal nanoparticle layer and fabrication method thereof - Google Patents

Polyimide nanofiber with metal nanoparticle layer and fabrication method thereof Download PDF

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KR20150048935A
KR20150048935A KR1020130128278A KR20130128278A KR20150048935A KR 20150048935 A KR20150048935 A KR 20150048935A KR 1020130128278 A KR1020130128278 A KR 1020130128278A KR 20130128278 A KR20130128278 A KR 20130128278A KR 20150048935 A KR20150048935 A KR 20150048935A
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polyimide
metal
nanofibers
nanofiber
nanoparticle layer
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KR1020130128278A
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Korean (ko)
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김일두
윤두영
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한국과학기술원
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    • D—TEXTILES; PAPER
    • 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
    • D06M11/83—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 metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • D—TEXTILES; PAPER
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Chemically Coating (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The present invention relates to a polyimide nanofiber with a metal nanoparticle layer bound thereto and a method for producing the polyimide nanofiber. More particularly, the present invention relates to a polyimide nanofiber having a metal nanoparticle layer, Nanofiber and a method of manufacturing the same.
(A) replacing hydrogen of a carboxyl group contained in a polyimide nanofiber with an alkali metal using an alkali solution; (b) contacting the alkali metal-substituted polyimide nanofibers with a solution in which the catalyst salt is dissolved to replace the alkali metal again with the catalyst metal; (c) heat-treating the polyimide nanofibers substituted with the catalyst metal to form polyimide nanofibers bound to the surface of the catalyst particles; And (d) a step of forming a metal nanoparticle layer on the surface of the polyimide nanofiber bound to the surface of the catalyst particle, wherein the metal nanoparticle layer is bound to the surface of the polyimide nanofiber. According to the present invention, the catalyst particles are uniformly bonded to the polyimide nanofibers by a chemical method, and the metal nanoparticles are bonded to the polyimide nanofibers through plating, whereby the metal nanoparticle layer is strongly bound and the metal nanoparticle layer The present invention has the effect of disclosing mid nanofibers and a method of manufacturing the same.

Description

TECHNICAL FIELD The present invention relates to a polyimide nanofiber having a metal nanoparticle layer bound thereto,

The present invention relates to a polyimide nanofiber with a metal nanoparticle layer bound thereto and a method for producing the polyimide nanofiber. More particularly, the present invention relates to a polyimide nanofiber having a metal nanoparticle layer, Nanofiber and a method of manufacturing the same.

Polyimide is a polymer resin synthesized from an imide monomer and has heat resistance, abrasion resistance, chemical resistance, radiation resistance and insulation properties, and is applied to a wide variety of applications such as aircraft parts, automobile parts, semiconductor industry, . There have been various attempts to bond the metal surface to the polyimide surface so as to have conductivity. In particular, plating has attracted a great deal of interest in that the metal material can be strongly adhered to the plated body to secure physical and chemical stability. come.

In the prior art, an electroless plating method has generally been used for plating a polyimide having no conductivity. The electroless plating method is a method in which a catalyst is activated on a substrate and is immersed in an acidic or basic solution to which a metal salt, a reducing agent, a stabilizer and the like are added to perform plating by using an oxidation or reduction reaction between a catalyst and a metal ion. In order to attach the catalyst to the substrate as described above, a method of using Sn 2 + + Pd 2 + -> Pd + Sn 4 + is mainly used. After immersing in a hydrochloric acid aqueous solution of tin chloride (SnCl 2 ), palladium chloride 2 ) The catalyst is immersed in an acidic aqueous solution.

However, since the solution used in the plating process is an aqueous solution, plating can be performed only on a hydrophilic substrate. In order to attach the catalyst to the substrate, a hydroxyl group (-OH) or an amine group (-NH x ) must be present on the surface of the substrate. However, in the case of polyimide, since it includes a group having hydrophobicity, it is difficult to use the electroless plating method as described above.

In order to solve such a problem, a method of adding a hydrophilic functional group through surface modification can be considered. Therefore, in order to modify the polyimide surface, a method of attaching a catalyst after increasing the surface roughness through chemical etching is widely used. Further, in order to solve the problem that the adhesion property is lowered, H 2 / N 2 plasma is used And a method of attaching a functional group to the polyimide surface. However, the above-described technique is suitable when plating on a two-dimensional substrate such as a planar substrate, but is not structurally suitable for polyimide nanofibers having a three-dimensional shape.

In addition, since polyimide is chemically stable, it is difficult to dissolve in a solvent and generally has a glass transition temperature exceeding 280 캜, which causes many limitations in molding. Accordingly, polyamic acid (PAA), which is a step before the polyimide is formed, is dissolved in an organic solvent such as dimethylformamide and dimethylacetamide. In the process of synthesizing polyimide, PAA is formed by chain polymerization of diamine and anhydride, followed by heat treatment to induce dehydration reaction of amine group (-NHx) and carboxyl group (-COOH) to form polyimide .

Although various methods can be used to form polymeric materials into nanofibers, electrospinning is one of the ways to easily produce nanofibers using polymer solutions together with simple equipment. The electrospinning device is composed of a dc power supply, a syringe pump, a needle, and a current collector. The polymer solution having a constant viscosity is injected into a syringe at a constant speed And the voltage is applied, the polymer solution takes the shape of a Taylor cone at the tip of the needle, and the polymer solution is stretched and the solvent is evaporated at the same time to form a nanofiber of 100 nm to 2 μm in thickness So that it is collected in the current collector.

However, in the case of producing polyimide nanofibers in which the catalyst is activated on the surface in order to form nanofibers by forming polyimide by electrospinning and binding metal particles to the fibers, the tin / palladium reaction described above is used There are many limitations in activating the catalyst:

First, when the polyimide nanofiber network is formed, it is difficult to attach the catalyst to the micropores having a diameter of several tens of nanometers, and the catalyst can be activated at the junction of the fibers other than the polyimide fibers due to the large pores having a diameter of several tens of micrometers .

Second, because of the hydrophobic nature of the polyimide, it is not suitable for the plating process in aqueous solution, and it is also difficult to attach the tin / palladium catalyst on its surface.

Third, when a plasma treatment is performed to attach an amine group (-NHx) or a hydroxyl group (-OH) to a polyimide surface, it is also possible to uniformly distribute the polyimide surface to a three- The problem is quite difficult.

Accordingly, there is a demand for polyimide nanofibers in which metal nanoparticles capable of solving the above-mentioned problems are uniformly bound to the surface through plating, and a manufacturing method thereof, but an appropriate solution for this problem has not been proposed yet.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in an effort to solve the above problems of the prior art, and an object of the present invention is to provide a polyimide nanofiber in which catalyst particles are uniformly adhered on the surface and metal nanoparticles are uniformly bound, .

According to an aspect of the present invention, there is provided a method for preparing a polyimide nanofiber having a metal nanoparticle layer bound thereto, comprising the steps of: (a) using an alkali solution to convert hydrogen of a carboxyl group contained in the polyimide nanofiber into an alkali metal Substituting; (b) contacting the alkali metal-substituted polyimide nanofibers with a solution in which the catalyst salt is dissolved to replace the alkali metal again with the catalyst metal; (c) heat-treating the polyimide nanofibers substituted with the catalyst metal to form polyimide nanofibers bound to the surface of the catalyst particles; And (d) forming a metal nanoparticle layer on the surface of the polyimide nanofibers bound to the surface of the catalyst particles.

In the step (b), the catalyst metal may be at least one selected from the group consisting of Ag, Au, Cu, Fe, Ni, Ru, Pd, Pt) or iridium (Ir) may be used.

In the step (d), one or more of copper (Cu), silver (Ag), gold (Au), nickel (Ni), and aluminum .

The step (d) may be a step of forming the metal nanoparticle layer using an electroless plating method or an electrolytic plating method.

The step (d) may be performed by physical vapor deposition (PVD) or metal organic chemical vapor deposition (MOCVD) including sputtering, pulsed laser deposition (PLD), and vacuum evaporation (Vacuum Evaporation) , Chemical vapor deposition (CVD) including plasma enhanced chemical vapor deposition (PECVD), and atmospheric layer deposition (ALD), to form the metal nanoparticle layer.

Prior to the step (a), (p1) synthesizing PAA (polyamic acid); (p2) electrospinning a solution containing the synthesized PAA (polyamic acid) to form a PAA polymer nanofiber; (p3) heat-treating the PAA polymer nanofiber to form a polyimide nanofiber.

In step (p1), an anhydride used in the synthesis of PAA (polyamic acid) may be selected from phthalic anhydride (PA), pyromellitic dianhydride (PMDA), biphenyl tetra 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4'-4-oxydiphthalic anhydride (ODPA), benzophenotetracarboxylic dianhydride (BTDA, 3,3'4,4'-benxophenonetetracar boxylic dianhydride, trimellitic ethylene glygol, 4'4-isopropyl biphenoxybitalic anhydride (BPADA, 4,4 ' One or both of - (4'4-isopropylbiphenoxy) biphthalic anhydride, perfluoroisopropylidene-containing acid dianhydride (6FDA) or trimellitic anhydride (TMA) Or more can be used.

The diamine used in the synthesis of PAA (polyamicacid) in the step (p1) may include p-phenyl diamine (p-PDA), 4,4'-oxydianiline (4,4 ' -oxydianiline, 4,4 '-ODA); 2,2-bis (4- (4-aminophenoxy) -phenyl) propane, BAPP, p-methylenedianiline (p-MDA); Propyltetramethyl disiloxane (GAPD), jeffamine (polyaromatic amine), 4,4'-diaminodiphenylsulfone (DDS), 2,2'-bistripple Diaminobiphenyl (TFDB) or 3,5-diamino-1,2,4-triazole (2,2'-bis (trifluoromethyl) -4,4'- , Triazole) may be used.

According to another aspect of the present invention, a polyimide nanofiber to which a metal nanoparticle layer is bound is a polyimide nanofiber; A plurality of catalyst particles bound to the surface of the polyimide nanofibers; And a metal nanoparticle layer formed on the surface of the polyimide nanofiber using the catalyst particle as a seed.

The catalyst particles may be made of one or more of Ag, Ir, Pl, Pd, and Ru.

The diameter of the catalyst particles may be in the range of 0.1 nm to 30 nm.

The metal nanoparticles may be made of one or more of copper (Cu), silver (Ag), nickel (Ni), and aluminum (Al).

The thickness of the metal nanoparticle layer may range from 5 nm to 500 nm.

According to the present invention, the catalyst particles are uniformly bonded to the polyimide nanofibers by a chemical method, and the metal nanoparticles are bound to the polyimide nanofibers through plating, whereby the metal nanoparticle layer is firmly bonded and the metal nanoparticle layer having excellent conductivity binds And a method for producing the polyimide nanofiber. In the case of the above-mentioned fibers, not only has excellent conductivity but also strong physical, chemical and thermal stability by forming a strong bond between the plated layer and the fibrous layer, and thus can be applied as an electrode requiring a harsh environment and a high surface area.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
1 is a flow chart of a method of manufacturing a polyimide nanofiber in which a metal nanoparticle layer is plated according to an embodiment of the present invention.
FIG. 2 is an exemplary view illustrating a step of manufacturing a polyimide nanofiber plated with a metal nanoparticle layer according to an embodiment of the present invention. Referring to FIG.
FIG. 3 is a view illustrating the structure of a polyimide nanofiber plated with a metal nanoparticle layer according to an embodiment of the present invention. Referring to FIG.
4 is an electron micrograph of the polyimide nanofiber after heat treatment according to an embodiment of the present invention.
FIG. 5 is a photograph of silver, iridium, platinum, palladium, and ruthenium substituted polyimide nanofibers produced according to an embodiment of the present invention.
FIG. 6 is a photograph of a polyimide nanofiber in which a silver catalyst prepared according to an embodiment of the present invention is deposited on a surface.
FIG. 7 is an electron micrograph of a polyimide nanofiber having a silver catalyst deposited on its surface according to an embodiment of the present invention. FIG.
8 is an electron micrograph of a polyimide nanofiber in which an iridium catalyst is deposited on a surface according to an embodiment of the present invention.
9 is an electron micrograph of a polyimide nanofiber plated with a copper nanoparticle layer according to an embodiment of the present invention.
10 is a photograph of a polyimide nanofiber plated with a copper nanoparticle layer according to an embodiment of the present invention.
11 is a photograph of a copper-plated polyimide nanofiber as a comparative example according to the prior art.
12 is an electron micrograph of copper-plated polyimide nanofiber as a comparative example according to the prior art.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and specific embodiments will be described in detail below with reference to the accompanying drawings.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The terms first, second, etc. may be used to describe various components, but the components are not limited by the terms, and the terms are used only for the purpose of distinguishing one component from another Is used.

In the present invention, in the case where electroless plating is used for plating a polyimide having no conductivity in the prior art, it is necessary to attach the catalyst through chemical etching in order to modify the hydrophobicity of the polyimide, However, such a method is not suitable for polyimide nanofibers in a three-dimensional shape. Moreover, due to the composite structure of micropores or macropores due to the formation of the polyimide nanofiber web, It is difficult to appropriately activate it.

Accordingly, in view of the above problems, the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a method of manufacturing a polyimide nanofiber by activating a catalyst uniformly over a polyimide nanofiber by using a chemical wet process, And the metal nanoparticles are firmly bonded to the surface of the polyimide nanofiber to bind to the metal nanoparticle layer having flexibility and conductivity and having chemical and thermal stability, and a process for producing the polyimide nanofiber.

FIG. 1 shows a flowchart of a method for manufacturing a polyimide nanofiber 300 on which a metal nanoparticle layer is plated according to an embodiment of the present invention. As shown in FIG. 1, the method for manufacturing the polyimide nanofibers 300 coated with the metal nanoparticle layer according to an embodiment of the present invention includes synthesizing PAA (S110), electrospinning the PAA solution, Forming a polyimide nanofiber 310 by heat treating the PAA polymer nanofibers 310 in step S130; forming a polyimide nanofiber 310 on the surface of the polyimide nanofiber 310 by hydrolyzing the hydrogen of the carboxyl group contained in the polyimide nanofiber 310; The step of replacing the alkaline metal of the polyimide nanofiber 310 with the catalyst metal is performed in step S150 and the polyimide nanofiber 310 is heat treated to remove the catalyst particles 320 from the surface (S160); and forming a metal nanoparticle layer (330) on the surface of the polyimide nanofiber (310) by plating (S170).

FIG. 2 illustrates a step of manufacturing a polyimide nanofiber 300 on which a metal nanoparticle layer is plated according to an embodiment of the present invention. As shown in FIG. 2, (a) first, the PAA polymer nanofiber is formed, (b) the polyimide nanofiber 310 is formed through heat treatment, and (c) the polyimide nanofiber 310 After the catalyst particles 320 are bound (d), the metal nanoparticles are uniformly bonded to the surface of the catalyst particles 320 by plating using the catalyst particles 320 as a seed to form a polyimide nanofiber 310 .

In the following, we divide into the production steps described above and study them in detail. First, a step of synthesizing PAA (S110) and a step S120 of forming a PAA polymer nanofiber by electrospunning the PAA solution will be described. The polyimide is chemically stable and difficult to be dissolved in a solvent, and usually has a glass transition temperature exceeding 280 ° C, which is difficult to form. Accordingly, polyamic acid (PAA), which is a pre-stage material for forming polyimide, is dissolved in an organic solvent such as dimethylformamide and dimethylacetamide. Accordingly, there is a step of preparing a PAA solution in the production of the polyimide nanofiber, wherein various types of PAA fibers can be synthesized by appropriately selecting the kinds of diamine and anhydride.

The anhydrides used in the PAA synthesis include phthalic anhydride (PA); Pyromellitic dianhydride (PMDA); Biphenyl tetracarboxylic dianhydride (BPDA, 3,3'4,4'-biphenyltertracarboxylic dianhydride); 4'-4-oxydiphthalic anhydride (ODPA); Benzophenotetracycloxyric acid dihydride (BTDA, 3,3'4,4'-benxophenonetetracar boxylic dianhydride); Trimellitic ethylene glygol (TMEG); 4'4-isopropyl biphenoxybiphthaloxy anhydride (BPADA, 4,4'- (4'4-isopropylbiphenoxy) biphthalic anhydride); Perfluoroisopropylidene-containing acid dianhydride (6FDA); One or more of trimellitic anhydride (TMA) may be used.

Examples of diamines used in the synthesis of PAA include para-phenyl diamine (p-PDA); 4,4'-oxydianiline (4,4'-ODA, 4,4'-oxydianiline); 2,2-bis 4-4 aminophenoxyphenyl propane (BAPP, 2,2-bis (4- (4-aminophenoxy) -phenyl) propane); Para-methylenedianiline (p-MDA, p-methylenedianiline); Propyltetramethyl disiloxane (GAPD), jeffamine (polyaromatic amine); 4,4'-diaminodiphenylsulfone (DDS, 4,4'-diaminodiphenylsulfone); 2,2'bistrifluoromethyl-4,4'-diaminobiphenyl (TFDB, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl); Triazole (3,5-diamino-1,2,4-triazole) may be used.

Next, a step S130 of forming the polyimide nanofibers 310 by heat-treating the PAA polymer nanofibers will be described. In order to convert the synthesized PAA polymer nanofiber into the polyimide nanofiber 310, a dehydration reaction of an amine group (-NH x ) and a carboxyl (-COOH) is performed through heat treatment to imidize the polymer do. When this process is performed, the structure becomes chemically and thermally stable polyimide, and it becomes colorless or yellow depending on the type of diamine and anhydride.

(S140) replacing the hydrogen of the carboxyl group contained in the polyimide nanofiber 310 with an alkali metal, replacing the alkali metal of the polyimide nanofiber 310 with the catalyst metal (S150) And a step S160 of heat-treating the polyimide nanofibers 310 to precipitate the catalyst particles 320 on the surface thereof.

The present invention solves the above problems by solving the problems of the prior art by activating the catalyst uniformly over the entire surface of the polyimide nanofiber 310 using a chemical wet process. When the polyimide is exposed to the alkali solution, the alkali metal ion is substituted with the hydrogen of the carboxyl group (-COOH). For example, when the potassium ion is substituted, it has the form of -COOK. When the polyimide thus formed is exposed again to a solution containing a metal ion, the metal ion replaces the potassium, so that the carboxyl group is converted into the form of -COOM (M = metal element). The metal can be reduced by thermal energy or chemical energy to precipitate on the polyimide surface. At this time, the metal (M) generated on the surface is present in a size of several nm to several hundred nm by the process time and temperature control. In addition, the polyimide and the metal have a strong bonding force through chemical bonding, resulting in a physically and chemically stable structure.

According to the above-described principle, in order to attach the catalyst particles 320 to the polyimide nanofibers 310 synthesized in the previous step S130, a solution of potassium hydroxide at a concentration of 0.01M to 8.0M is added to the polyimide nanofiber 310 at a temperature range of room temperature to 300 ° C If it is immersed for an appropriate time, the polyimide undergoes a hydrolytic reaction and is converted into the PAA form, and the -H of the carboxyl group contained in the PAA is substituted with potassium.

When the PAA polymer containing a carboxyl-substituted carboxyl group is precipitated in a metal salt solvent containing gold, copper, iron, nickel, ruthenium, palladium, platinum or iridium, potassium is converted into an ionic form, Potassium.

Subsequently, when the PAA fibers are heat-treated at a temperature of 250 ° C to 350 ° C, the substituted metal is deposited on the surface of the polyimide nanofibers 310 in the form of catalyst particles 320.

Finally, a step (S170) of forming the metal nanoparticle layer 330 on the surface of the polyimide nanofiber 310 by plating is described. The metal nanoparticle layer 330 bonded to the outside of the polyimide nanofiber 310 is strongly bonded to the polyimide nanofiber 310 through plating. Therefore, the polyimide nanofiber 310 can be chemically, thermally, and mechanically stable So that it can operate stably even in harsh environments such as electrodes.

However, as a method for binding the metal nanoparticle layer 330 to the outside of the polyimide nanofibers 310, it is not always necessary to use a plating process, and even a plating process is not necessarily limited to a non-electrolytic plating process. For example, electroplating, electroless-plating, or the like can be used by wet coating using a solution or ink containing a metal precursor. Sputtering, PLD Physical vapor deposition (PVD) including techniques such as pulsed laser deposition and vacuum evaporation; Chemical Vapor Deposition (CVD) including MOCVD (Metal Organic Chemical Vapor Deposition), PECVD (Plasma Enhanced Chemical Vapor Deposition), ALD (Atomic Layer Deposition), and the like; Can also be used. However, considering the characteristics of the polyimide nanofiber 310 as described above, it may be more preferable to form the polyimide nanofiber 300 on which the metal nanoparticle layer is plated using electroless plating.

FIG. 3 shows the structure of a polyimide nanofiber 300 on which a metal nanoparticle layer is plated according to an embodiment of the present invention. 3, the polyimide nanofibers 300 coated with the metal nanoparticle layer according to an embodiment of the present invention include polyimide nanofibers 310, catalyst particles chemically bonded to the polyimide nanofibers 310, And a metal nanoparticle layer 330 formed on the surface of the polyimide nanofibers through a plating process using the catalyst particles 320 as seeds.

Here, the polyimide nanofiber 310 functions as a substrate on which the catalyst particles 320 and the metal nanoparticle layer 330 bind to each other as polymer nanofibers having flexibility and high stability. Since the polyimide nanofiber 310 can be formed of a polymer nanofiber having various molecular formulas through various combinations of anhydrides and diamines as described above, the polyimide nanofiber 310 can be suitably selected in consideration of the characteristics of the polyimide nanofiber 310 required for the user .

In addition, the polyimide nanofiber 310 can be prepared by electrospinning, and a polymer nanofiber network in which a plurality of polymer nanofibers are dispersed, having heterogeneous macropores and micropore distribution, can be synthesized on a large scale . In this case, when nanofibers are formed through electrospinning, they are dispersed in a random form, but they may have a lattice-like arrangement shape by applying an additional voltage during the electrospinning process.

The polyimide nanofiber 310 may be selected from a range of 10 nm to 1 μm in diameter, and may be composed of a polymer nanofiber having a length of 300 μm or more. Further, considering the practicality, the length of the polyimide nanofiber 310 may be in the range of 300 μm to 30 cm . ≪ / RTI > The polyimide nanofibers 310 have a porous structure in which a plurality of polyimide nanofibers 310 are dispersed to form an empty space between the polyimide nanofibers 310. In this case, The flexibility and the penetration rate of reactive elements or ions can be improved.

The catalyst particles 320 are chemically bonded to the polyimide nanofibers 310 to have a strong adhesive force and function as a seed for forming the metal nanoparticle layer 330. The catalyst particles 320 may be made of one or more of silver (Ag), iridium (Ir), platinum (Pt), palladium (Pd), or ruthenium (Ru) Is preferably in the range of 0.1 nm to 30 nm.

Finally, the metal nanoparticle layer 330 is searched. The metal nanoparticle layer 330 formed through the above-described series of steps may have a thickness of usually 2 nm to 1 μm, and more preferably, a thickness of 10 nm to 500 nm from a practical point of view. When the thickness of the metal nanoparticle layer 330 is as thin as 2 nm or less, the electrical conductivity of the metal nanoparticle layer 330 is low. When the thickness of the metal nanoparticle layer 330 is too thick as 1 μm or more, (Peel off) may occur between the first electrode 310 and the second electrode 310, which is undesirable.

Hereinafter, the present invention will be described in more detail by way of examples. It should be understood, however, that the present invention is not limited thereto.

[Example 1] Production of polyimide nanofiber 310 by electrospinning

In this embodiment, the polyimide nanofiber 310 is synthesized by using electrospinning as one example. First, 2 g of pyromellitic dianhydride (PMDA) and 1.84 g of 4,4'-oxydianiline (ODA) were added to 16 g of dimethylformamide (DMF) And the mixture was stirred for 12 hours while rotating to prepare a PAA solution.

Subsequently, the PAA solution was placed in a syringe, and a voltage of 15 kV was applied at a rate of 0.2 ml / h, followed by electrospinning for about 2 hours to form a PAA (poly (amic acid)) nanofiber network having a thickness of about 50 μm. The needle size used was 21G, and the distance between the needle and the collector was 15cm. The PAA nanofiber network was heat treated at 300 ° C, 200 ° C, and 300 ° C for 1 hour, respectively, to fabricate a polyimide nanofiber 310 network.

4 shows an electron micrograph of the polyimide nanofiber 310 after the heat treatment according to an embodiment of the present invention. As can be seen from the photograph, the polyimide nanofibers 310 have a straight and smooth surface structure. The fibers produced according to the embodiments have a thickness ranging from 700 nm to 900 nm and have a randomly scattered mesh-like structure.

[Example 2] Preparation of polyimide nanofiber 310 in which silver catalyst particles 320 were uniformly bound

The polyimide nanofibers 310 were recovered and immersed in 0.5 M potassium hydroxide solution at 50 DEG C for 30 minutes and then washed with secondary distilled water. Thereafter, the resultant was immersed in 0.1 M silver nitrate solution at room temperature for 30 minutes and then washed with secondary distilled water to prepare silver-substituted polyimide nanofiber 310. FIG. 5 shows a polyimide nanofiber 310 substituted with silver, iridium, platinum, palladium, and ruthenium substituted according to an embodiment of the present invention. It can be confirmed that even if the polyimide nanofiber 310 is replaced with a metal containing silver, the color change does not appear much. On the other hand, when ruthenium was substituted, it showed a dark brown color.

Then, the silver-substituted polyimide nanofibers 310 were heated at a rate of 5 deg. C / minute and heat-treated at 250 deg. C for 1 hour. FIG. 6 shows the polyimide nanofibers 310 in which a silver catalyst is deposited on the surface through heat treatment. Even if the nanofibers are substituted with silver, the change in color is not remarkable. However, it can be seen that as the silver catalyst particles 320 are deposited through the heat treatment, they become dark brown. No change in volume was observed after heat treatment and no damage to the appearance of nanofibers was observed. The nanofibers after the heat treatment have a deep brown color, so that it is indirectly confirmed that the silver catalyst particles 320 have been deposited on the surface.

FIG. 7 is an electron micrograph of a polyimide nanofiber 310 having silver catalyst particles 320 deposited on its surface according to an embodiment of the present invention. The polyimide nanofiber 310 of FIG. 4 has a smooth surface while the surface of the polyimide nanofiber 310 on which silver catalyst particles 320 have been deposited has silver catalyst particles of a size of several nanometers to several tens of nanometers 320) are uniformly distributed. The even distribution of the catalyst particles 320 provides an environment in which even plating can occur throughout the plating process.

[Example 3] Production of polyimide nanofiber 310 in which iridium catalyst particles 320 were uniformly deposited

Except that the polyimide nanofibers 310 in which the iridium catalyst particles 320 were precipitated were prepared using a solution of chloroimidic acid (H 2 IrCl 6 ) dissolved at a concentration of 0.1 M in place of the silver nitrate solution, .

8 is an electron micrograph of a polyimide nanofiber 310 having iridium catalyst particles 320 deposited on its surface according to an embodiment of the present invention. The size and shape of the iridium catalyst particles 320 can not be accurately measured, but it can be confirmed that the iridium catalyst particles 320 are uniformly distributed as in the case of the silver catalyst particles 320.

[Example 4] Production of polyimide nanofiber 310 in which silver catalyst particles 320 were deposited on the surface and copper nanoparticles were plated

The silver catalyst particles 320 prepared in Example 2 were precipitated in a copper plating solution at room temperature for 30 minutes in order to perform copper plating on the polyimide nanofibers 310 on which the silver catalyst particles 320 were precipitated. The solution used for plating includes copper sulfate (CuSO 4 L, 10 g / L of formaldehyde (HCHO), 10 mg / L of cyanogen sodium (NaCN), 10 g / L of Tryptone X (5 g H 2 O), 16 g / L of Rochelle salt (KNaC 4 H 4 O 6 4 H 2 O) X) 300 mg / L was contained and adjusted to pH 12 ~ 13 using potassium hydroxide. The plating was carried out at room temperature.

9 is an electron microscope photograph of a polyimide nanofiber 300 on which a copper nanoparticle layer is plated according to an embodiment of the present invention. It can be confirmed that copper is plated at regular intervals according to the position where the catalyst particles 320 are bonded to the surface. The size of the particles is formed to several hundred nm.

10, there is shown a photograph of a polyimide nanofiber 300 on which a copper nanoparticle layer is plated according to an embodiment of the present invention. The polyimide nanofibers 310 have a yellow color, but when copper is plated, the surface of the polyimide nanofibers 310 becomes copper-colored and conductive. 10, it was confirmed that the surface color of the polyimide nanofiber 310 changed from yellow to copper color.

Also, the polyimide nanofibers 310 which were plated were confirmed by using a multimeter that electricity flowed, and there was no significant change in the electric conductivity even after one week after the plating. Further, it was confirmed that the copper of the plated polyimide nanofiber 310 did not fall off for a considerable period of time, and that it had high adhesion and stability.

[Comparative Example 1] Preparation of copper-plated polyimide nanofiber 310 without using catalyst particles

Tin chloride and a palladium chloride solution were prepared at 3 mM concentration in the acidic solution to attach the palladium catalyst to the polyimide nanofibers 310 synthesized in Example 1. The fibers are immersed in a tin chloride solution for 3 minutes and then immersed in a palladium chloride solution for 3 minutes. The catalyst-treated fiber was immersed in the plating solution prepared in Example 3 and plated at room temperature for 1 hour.

FIG. 11 shows a photograph of a copper-plated polyimide nanofiber 310 as a comparative example according to the prior art. Here, plating was performed using a tin-palladium reaction according to the prior art. Copper appears to be plated on the surface of the polyimide nanofiber 310, but the color is dark brown rather than copper light.

FIG. 12 shows an electron micrograph of a copper-plated polyimide nanofiber 310 as a comparative example according to the prior art. It can be confirmed that the copper particles are unevenly distributed, and partly, it can be confirmed that the polyimide fiber 310 is not plated.

Also, it has been confirmed that the copper-plated polyimide nanofiber 310 according to the related art exhibits a very low electrical conductivity of several MOhm when the electrical conductivity is measured using a multimeter.

The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments described in the present invention are not intended to limit the technical spirit of the present invention but to illustrate the present invention. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents thereof should be construed as being included in the scope of the present invention.

300: polyimide nanofibers plated with metal nanoparticle layers
310: polyimide nanofibers
320: catalyst particle
330: metal nanoparticle layer

Claims (13)

(a) replacing the hydrogen of a carboxyl group contained in the polyimide nanofiber with an alkali metal by using an alkali solution;
(b) contacting the alkali metal-substituted polyimide nanofibers with a solution in which the catalyst salt is dissolved to replace the alkali metal again with the catalyst metal;
(c) heat-treating the polyimide nanofibers substituted with the catalyst metal to form polyimide nanofibers bound to the surface of the catalyst particles; And
(d) forming a metal nanoparticle layer on the surface of the polyimide nanofibers having the catalyst particles bound to the surface thereof, wherein the metal nanoparticle layer is bound to the surface of the polyimide nanofiber. The method according to claim 1,
In the step (b)
As the catalytic metal, at least one of Ag, Au, Cu, Fe, Ni, Ru, Pd, Pt, Or two or more of the metal nanoparticle layers are bonded to each other. The method according to claim 1,
In the step (d)
Wherein at least one of copper (Cu), silver (Ag), gold (Au), nickel (Ni), and aluminum (Al) is used as the metal forming the metal thin film, Method for manufacturing mid nanofibers. The method according to claim 1,
The step (d)
Wherein the metal nanoparticle layer is formed using an electroless plating method or an electrolytic plating method. The method according to claim 1,
The step (d)
Physical vapor deposition (PVD), metal organic chemical vapor deposition (MOCVD), or plasma enhanced chemical vapor deposition (PECVD), including sputtering, pulsed laser deposition (PLD) Wherein the metal nanoparticle layer is formed using a chemical vapor deposition (CVD) method including ALD (Atomic Layer Deposition). The method of manufacturing a polyimide nanofiber according to claim 1, The method according to claim 1,
Prior to step (a)
(p1) synthesizing PAA (Polyamicacid);
(p2) electrospinning a solution containing the synthesized PAA (polyamic acid) to form a PAA polymer nanofiber;
(p3) heat-treating the PAA polymer nanofibers to form polyimide nanofibers. The method of claim 1, wherein the polyimide nanofibers are bound to the polyimide nanofibers. The method according to claim 6,
In the step (p1)
As an anhydride used in the synthesis of PAA (Polyamicacid)
Phthalic anhydride (PA), pyromellitic dianhydride (PMDA), biphenyl tetracarboxylic dianhydride (BPDA, 3,3'4,4'-biphenyltertracarboxylic dianhydride), oxy 4-oxydiphthalic anhydride (ODPA), 3,3'4,4'-benxophenonetetracar boxylic dianhydride (BTDA), trimellitic ethylene glycol (TMEG, trimellitic ethylene glygol), 4'4-isopropyl biphenoxybiphthaloxy anhydride (BPADA, 4,4'- (4'4-isopropylbiphenoxy) biphthalic anhydride), perfluoro isopropylidene- Characterized in that one or both of perfluoroisopropylidene-containing acid dianhydride (6FDA) or trimellitic anhydride (TMA) is used as the polyimide Method of producing a fiber furnace. The method according to claim 6,
In the step (p1)
As diamines used in the synthesis of PAA (Polyamicacid)
Para-phenyldiamine (p-PDA), 4,4'-oxydianiline, 4,4'-ODA; 2,2-bis (4- (4-aminophenoxy) -phenyl) propane, BAPP, p-methylenedianiline (p-MDA); Propyltetramethyl disiloxane (GAPD), jeffamine (polyaromatic amine), 4,4'-diaminodiphenylsulfone (DDS), 2,2'-bistripple Diaminobiphenyl (TFDB) or 3,5-diamino-1,2,4-triazole (2,2'-bis (trifluoromethyl) -4,4'- , And Triazole) is used as the metal nanoparticle layer. Polyimide nanofibers;
A plurality of catalyst particles bound to the surface of the polyimide nanofibers; And
And a metal nanoparticle layer formed on the surface of the polyimide nanofiber using the catalyst particle as a seed. 10. The method of claim 9,
Wherein the catalyst particles are composed of one or more of silver (Ag), iridium (Ir), platinum (Pt), palladium (Pd) or ruthenium (Ru). 10. The method of claim 9,
Wherein the diameter of the catalyst particles is in the range of 0.1 nm to 30 nm. 10. The method of claim 9,
Wherein the metal nanoparticles are composed of one or more of copper (Cu), silver (Ag), nickel (Ni), and aluminum (Al). 10. The method of claim 9,
Wherein the thickness of the metal nanoparticle layer is in the range of 5 nm to 500 nm.
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CN106238726A (en) * 2016-08-04 2016-12-21 北京化工大学常州先进材料研究院 A kind of flexible compound nano-silver thread and preparation method thereof
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CN106637472A (en) * 2016-11-29 2017-05-10 江西师范大学 Method for preparing polyimide micron fiber by electricity spinning method
KR20180071136A (en) * 2016-12-19 2018-06-27 경희대학교 산학협력단 Method of producing a nerve electrode
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106238726A (en) * 2016-08-04 2016-12-21 北京化工大学常州先进材料研究院 A kind of flexible compound nano-silver thread and preparation method thereof
CN106283615A (en) * 2016-08-19 2017-01-04 北京化工大学常州先进材料研究院 A kind of compliant conductive polyimide/silver composite nano tube and preparation method thereof
CN106283615B (en) * 2016-08-19 2018-12-11 北京化工大学常州先进材料研究院 A kind of compliant conductive polyimide/silver composite nano tube and preparation method thereof
CN106637472A (en) * 2016-11-29 2017-05-10 江西师范大学 Method for preparing polyimide micron fiber by electricity spinning method
KR20180071136A (en) * 2016-12-19 2018-06-27 경희대학교 산학협력단 Method of producing a nerve electrode
WO2018117338A1 (en) * 2016-12-19 2018-06-28 경희대학교 산학협력단 Method for manufacturing neural electrode
WO2019223798A1 (en) * 2018-05-25 2019-11-28 东莞超盈纺织有限公司 Method for preparing conductive yarn by using vacuum thermal vapor deposition technique
CN113638239A (en) * 2021-09-08 2021-11-12 北京化工大学常州先进材料研究院 Polyimide/silver composite film with electromagnetic shielding function and preparation method thereof

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