CN114921882B - Elastic electromagnetic shielding fiber and preparation method and application thereof - Google Patents
Elastic electromagnetic shielding fiber and preparation method and application thereof Download PDFInfo
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- CN114921882B CN114921882B CN202210544699.2A CN202210544699A CN114921882B CN 114921882 B CN114921882 B CN 114921882B CN 202210544699 A CN202210544699 A CN 202210544699A CN 114921882 B CN114921882 B CN 114921882B
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/441—Yarns or threads with antistatic, conductive or radiation-shielding properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/18—Formation of filaments, threads, or the like by means of rotating spinnerets
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D7/00—Collecting the newly-spun products
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
- D02G3/04—Blended or other yarns or threads containing components made from different materials
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
- D02G3/12—Threads containing metallic filaments or strips
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/32—Elastic yarns or threads ; Production of plied or cored yarns, one of which is elastic
- D02G3/328—Elastic yarns or threads ; Production of plied or cored yarns, one of which is elastic containing elastane
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/061—Load-responsive characteristics elastic
Abstract
The invention provides an elastic electromagnetic shielding fiber and a preparation method and application thereof. The preparation method of the elastic electromagnetic shielding fiber comprises the following steps: firstly, preparing a core layer, and then adopting a centrifugal spinning self-rolling type collecting method, taking the core layer as a self-rolling type collecting unit, and collecting a skin layer to obtain elastic electromagnetic shielding fibers; the core layer has conductivity and elasticity, and the skin layer has high magnetic conductivity and elasticity; the centrifugal spinning self-rolling collecting method is to spin the spinning solution through a self-rolling collecting centrifugal spinning device, so that the spun fiber is wound on a self-rolling collecting unit capable of rotating. According to the invention, centrifugal spinning and self-rolling collection are combined, so that the spinning fiber is transversely wound on the core layer by layer, the elastic electromagnetic shielding fiber with a certain porous structure in the skin layer is obtained, the obtained elastic electromagnetic shielding fiber is excellent in conductivity, elasticity and strength, and the fabric prepared from the elastic electromagnetic shielding fiber has excellent shielding effect on electromagnetic waves with different frequencies.
Description
Technical Field
The invention relates to the technical field of fiber preparation, in particular to an elastic electromagnetic shielding fiber and a preparation method and application thereof.
Background
With the continuous development of the information age, the number of various electronic products is rapidly increased, and the electronic products used in daily life are easily interfered by external electromagnetic waves, so that the electronic products are inconvenient to use. At the same time, the electronic products themselves emit electromagnetic waves outwards, thereby causing pollution to the electromagnetic waves. In order to prevent such damage, electromagnetic shielding materials are often used for protection.
For preparing the electromagnetic shielding material, the electromagnetic shielding material can be realized by preparing conductive fibers and preparing the conductive fibers into fabrics. However, most of the polymer materials are insulating materials, and fibers made of these polymers are also insulating. Therefore, the insulating fiber needs to be prepared into the conductive fiber by a certain means so as to solve the defect that the electromagnetic shielding performance cannot be realized.
The insulating fiber is usually made into conductive fiber by dispersing conductive material, typically carbon black, graphite, metal powder or metal compound, in the insulating fiber or providing conductive coating on the surface of the insulating fiber. The dispersion of the conductive material in the insulating fiber can be accomplished by a method such as miscibility or composite spinning, but the method has the defect of uneven dispersion of the conductive material in the dispersion liquid, thereby causing uneven distribution of the conductive material in the fiber, affecting the conductive performance and further affecting the electromagnetic shielding performance of the fabric. The setting of the conductive coating on the surface of the insulating fiber can be completed by coating, vapor plating, electroplating and other methods, and the method has the following defects: on one hand, the inertia of the fiber is poor in the binding force between the conductive coating and the fiber, so that the coating is easy to fall off, and the conductivity of the fiber is further affected; on the other hand, the uniformity of the coating can affect the electrical conductivity of the fiber, which in turn affects the electromagnetic shielding properties of the fabric. Therefore, the metal wire can be directly used as the conductive medium, and the fiber is coated on the surface of the metal wire to form the conductive fiber, so that the method has no problem of uneven dispersion of the conductive medium in the dispersion medium.
Patent application number CN201510171061.9 discloses a piezoelectric polymer/metal composite nanometer single fiber and a preparation method thereof, wherein the fiber consists of a conductive metal wire core layer and a piezoelectric polymer skin layer, and the preparation steps are as follows: firstly, dissolving a polymer in a single or compound solvent, then spraying the solution on the surface of a metal wire through electrostatic spinning to coat a polymer nanofiber cortex, and finally standing the obtained fiber at room temperature until the solvent volatilizes, thus obtaining the fiber. The method has the following defects: (1) In the electrostatic spinning process, the nano fibers are mutually repelled due to the same charges, so that the nano fibers are irregularly distributed on the surface of the gold layer wire, and the product performance is poor; (2) The jet drawing speed of electrospinning is unstable, which also makes the arrangement of nanofibers on the surface of the wire irregular.
In view of the foregoing, there is a need for an improved elastic electromagnetic shielding fiber, and a method for preparing the same and applications thereof, so as to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to provide an elastic electromagnetic shielding fiber and a preparation method and application thereof, wherein centrifugal spinning and self-rolling collection are combined, so that skin fibers are uniformly and compactly transversely wound on a core layer to obtain the elastic electromagnetic shielding fiber with a special structure, wherein the pores are uniformly distributed and the thickness is uniform; the core layer and the skin layer of the fiber can be conductive, and the conductive particles of the copper wires and the skin layer of the core layer are uniformly distributed in the core layer and the skin layer of the fiber, so that the conductivity of the obtained fiber is better, and the special surface structure with uniform pore distribution and uniform thickness is combined, so that the prepared fabric forms a compact and uniform conductive layer, and the uniform pores have a certain reflection effect on electromagnetic waves, so that the electromagnetic shielding performance of the fabric is better.
In order to achieve the above-mentioned purpose, the present invention provides a method for preparing elastic electromagnetic shielding fiber, which comprises the steps of firstly preparing a core layer, then adopting a centrifugal spinning self-rolling collecting method, taking the core layer as a self-rolling collecting unit, and collecting a skin layer to obtain the elastic electromagnetic shielding fiber; the core layer and the skin layer both have electromagnetic shielding performance and elasticity;
the centrifugal spinning self-rolling collecting method comprises the following steps:
s1, preparing spinning solution;
s2, centrifugally spinning the spinning solution prepared in the step S1 through a self-rolling type collecting centrifugal spinning device, so that the spun fibers are wound on the self-rolling type collecting unit capable of rotating.
As a further improvement of the present invention, the core layer includes elastic fibers and high-conductivity wires spirally wound around the surfaces of the elastic fibers.
As a further improvement of the present invention, the skin layer includes an elastic material, polyacrylonitrile, and high magnetic permeability particles; the spinning solution comprises the following components in percentage by mass: the elastic material is 10% -25%, the polyacrylonitrile is 0.1% -15%, the high magnetic permeability particles are 0.1% -5%, and the balance is organic solvent.
As a further improvement of the invention, the method comprises the following steps:
s11, spirally winding metal wires on the surfaces of the elastic fibers to obtain a core layer; the diameter of the elastic fiber is 0.1-2mm, and the distance between adjacent metal wires in the spiral structure is 0.1-2mm;
s21, mixing an elastic material, polyacrylonitrile and high-permeability particles according to a certain proportion, uniformly dispersing the mixture in an organic solvent, and carrying out defoaming treatment to obtain a cortex spinning solution;
s31, carrying out centrifugal spinning on the cortex spinning solution prepared in the step S2 through the self-rolling type collecting centrifugal spinning device, so that the cortex fibers are wound on the core layer which can rotate and is prepared in the step S11 until the core layer is completely wrapped by the cortex, and the elastic electromagnetic shielding fibers are obtained.
As a further improvement of the invention, in the step S31, the rotational speed of the centrifugal spinning is 1000-8000r/min, the temperature is 30-60 ℃ and the environmental humidity is 30% -50%; the rotating speed of the core layer collecting line is 30-300r/min.
As a further improvement of the invention, in the step S31, the spinning hole diameter of the centrifugal spinning is 0.1-1mm, and the collecting distance is 7-20cm; in the step S21, the concentration of the cortex spinning solution is 20-30wt%.
As a further improvement of the present invention, in step S11, the elastic fiber includes one of polyurethane fiber, polyester composite elastic fiber, polyolefin elastic fiber and spandex; the metal wire comprises one of a copper wire, a nickel wire, a platinum wire and an aluminum wire; in step S21, the elastic material includes one or more of polyurethane, polyether block amide, styrenic thermoplastic rubber, and thermoplastic vulcanized rubber; the high magnetic permeability particles comprise one or more of ferroferric oxide nano particles, ferric oxide nano particles and cobalt oxide nano particles; the organic solvent is good solvent of polyacrylonitrile and elastic material, preferably one or more of N, N-dimethylformamide and N, N-dimethylacetamide.
The invention also provides an elastic electromagnetic shielding fiber, which is prepared by adopting the preparation method of the elastic electromagnetic shielding fiber.
As a further improvement of the present invention, the elongation of the elastic electromagnetic shielding fiber is 10% -35%, the electromagnetic shielding effectiveness of the fabric prepared from the elastic electromagnetic shielding fiber is 30-40dB, and the electromagnetic shielding efficiency is 90% -99%.
The invention also provides application of the elastic electromagnetic shielding fiber, and the elastic electromagnetic shielding fiber is applied to preparation of electromagnetic shielding materials.
The beneficial effects of the invention are as follows:
(1) The elastic electromagnetic shielding fiber prepared by the invention is characterized in that metal wires are spirally wound on the surface of the elastic fiber to form a core layer, and centrifugal spinning and self-rolling collection are combined, so that a skin layer is wound on the surface of the core layer in a high-speed autorotation manner through centrifugal spinning, and the elastic electromagnetic shielding fiber is obtained. In the centrifugal spinning process, when the spinning trickle is thrown out, the spinning trickle is stretched to a certain extent, when the spinning trickle encounters a core layer rotating at a high speed (namely a core layer collecting line), stretching occurs again to obtain fine single fibers, the fine single fibers are wound on the core layer rotating, so that the skin fibers are alternately wound on the core layer by layer, the single fibers are interlaced to different degrees, certain pores are formed among the skin fibers, meanwhile, due to high centrifugal spinning speed, the centrifugally spun fibers are relatively uniform in a certain area, and the prospect of realizing large-area industrialized production is realized if the core layer collecting line is continuous and can rotate along the fiber direction. The collecting method is simple and novel, high in efficiency, good in controllability and convenient for large-scale production.
(2) The elastic electromagnetic shielding fiber prepared by the invention has the advantages that both the core layer and the skin layer can conduct electricity, the metal wires of the core layer and the high-magnetic-conductivity particles of the skin layer are uniformly distributed in the core layer and the skin layer of the fiber (the core layer has conductivity and elasticity, the skin layer has high magnetic conductivity and elasticity), namely, the conductive substances distributed at all parts of the fiber are uniform, so that the conductivity of the obtained fiber is better, and the special surface structure with relatively uniform pore distribution and uniform thickness is combined, so that the prepared fabric forms a compact and uniform conductive layer, and the pores between the fiber and the fiber have a certain reflection effect on electromagnetic waves, so that the fabric has excellent electromagnetic shielding effect on electromagnetic waves with different frequencies. The high magnetic permeability particles in the skin layer have excellent electromagnetic shielding effectiveness, and the conductivity and the high magnetic permeability particles cooperate to improve the electromagnetic shielding effectiveness of the fabric. Meanwhile, the skin layer is densely wrapped on the surface of the core layer, and the core layer adopts a metal wire and elastic fiber composite structure, so that not only is the elastic performance of the fiber increased, but also the strength of the fiber is increased, and further the elastic performance and strength of the fabric are increased. In addition, the metal wires are softer, and the prepared fabric has certain flexibility.
(3) According to the collecting device adopted in the fiber collecting process, the clamps used for clamping the two ends of the core layer collecting wire are arranged at the two ends of the core layer collecting wire, and in the process of autorotation of the core layer collecting wire, the rotation states of the two ends of the core layer collecting wire are kept consistent due to the existence of the clamps, so that single fibers are distributed at the positions of the core layer collecting wire, fiber bundles with good uniformity are obtained, and the preparation of elastic electromagnetic shielding fibers is guaranteed.
Drawings
FIG. 1 is a schematic illustration of the process for preparing the elastic electromagnetic shielding fiber of the present invention.
Fig. 2 is a schematic structural view of the elastic electromagnetic shielding fiber prepared in the present invention.
FIG. 3 is a drawing of a fiber collecting apparatus of a self-winding collecting centrifugal spinning apparatus of the present invention.
Reference numerals
10-mounting plates; 11-connecting rods; 20-an electric drive; 21-a speed regulator; 30-connecting shafts; 31-a first gear; 40-mounting a shaft; 41-a second gear; 42-clamping; 50-driving belt.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of elastic electromagnetic shielding fiber, which comprises the steps of firstly preparing a core layer, adopting a centrifugal spinning self-rolling collecting method, taking the core layer as a self-rolling collecting unit, and collecting a skin layer to obtain the elastic electromagnetic shielding fiber; both the core layer and the skin layer have electromagnetic shielding performance and elasticity;
the centrifugal spinning self-rolling collecting method comprises the following steps:
s1, preparing spinning solution;
s2, centrifugally spinning the spinning solution prepared in the step S1 through a self-rolling type collecting centrifugal spinning device, so that the spun fibers are uniformly and compactly wound on a self-rolling type collecting unit capable of rotating.
Preferably, the self-rolling collecting unit is a core collecting wire, the fiber is wound on the core collecting wire, and in this embodiment, the core of the elastic electromagnetic shielding fiber is the core collecting wire.
The core layer comprises elastic fibers and high-conductivity metal wires spirally wound on the surfaces of the elastic fibers; the elastic fiber comprises one of polyurethane fiber, polyester composite elastic fiber, polyolefin elastic fiber and spandex; the metal wire comprises one of a copper wire, a nickel wire, a platinum wire and an aluminum wire.
The cortex comprises elastic material, polyacrylonitrile and high magnetic permeability particles, and the spinning solution comprises the following components in percentage by mass: 10% -25% of elastic material, 0.1% -15% of polyacrylonitrile, 0.1% -5% of high magnetic permeability particles and the balance of organic solvent. Wherein the elastic material comprises one or more of polyurethane, polyether block amide, styrene thermoplastic rubber and thermoplastic vulcanized rubber; the high magnetic permeability particles comprise one or more of ferroferric oxide nanoparticles, ferric oxide nanoparticles, and cobalt oxide nanoparticles. The organic solvent is good solvent of polyacrylonitrile and elastic material, and comprises one or more of N, N-dimethylformamide and N, N-dimethylacetamide.
In some embodiments, the skin layer further includes a flame retardant to produce an elastic electromagnetic shielding fiber having flame retardant properties.
Specifically, as shown in fig. 1, the preparation method of the elastic electromagnetic shielding fiber comprises the following steps:
s11, preparing a core layer:
and spirally winding the metal wire on the surface of the elastic fiber to obtain the core layer. The diameter of the elastic fiber is 0.1-2mm, and the distance between adjacent wires in the spiral structure is 0.1-2mm.
The elastic fiber and the spiral metal wire are simultaneously stretched in the stretching process, so that the elastic performance of the core layer is increased, the strength of the core layer is increased, the metal wire is uniformly attached to the surface of the elastic fiber, the conductivity of the core layer is superior, the performances of the elastic electromagnetic shielding fiber are ensured, the elasticity, the conductivity and the strength of the prepared elastic electromagnetic shielding fiber are superior, and the electromagnetic shielding performance of the fabric made of the elastic electromagnetic shielding fiber is further superior.
S21, preparing a cortex spinning solution:
the elastic material, the polyacrylonitrile and the high magnetic permeability particles are mixed according to a certain proportion and uniformly dispersed in an organic solvent, and the skin spinning solution is obtained after defoaming treatment.
Specifically, the high magnetic permeability particles are placed in an organic solvent for ultrasonic oscillation for 1-2 hours, polyacrylonitrile and an elastic material are added into a water bath with the temperature of 40-60 ℃ and stirred for 1-3 hours to form a mixed solution, and then the mixed solution is subjected to defoaming treatment for 3-5 hours to obtain the cortex spinning stock solution with the concentration of 20-30 wt%. Preferably, the spinning dope comprises the following components in percentage by mass: 10% -25% of elastic material, 0.1% -15% of polyacrylonitrile, 0.1% -5% of high magnetic permeability particles and the balance of organic solvent. The vacuum degree of the defoaming treatment is (-0.08) - (-0.1) MPa, and the temperature is 30-50 ℃.
S31, preparing elastic electromagnetic shielding fibers:
and (2) carrying out centrifugal spinning on the cortex spinning solution prepared in the step (S21) through a centrifugal spinning device for self-rolling collection, so that the cortex fibers are wound on the autorotatable core layer prepared in the step (S1) until the core layer is completely wrapped by the cortex, and the elastic electromagnetic shielding fibers are obtained, wherein the structure of the elastic electromagnetic shielding fibers is shown in figure 2.
Wherein, the rotation speed of centrifugal spinning is 1000-8000r/min, the temperature is 30-60 ℃, the environmental humidity is 30-50%, the spinning aperture of centrifugal spinning is 0.1-1mm, and the collecting distance is 7-20cm; the rotating speed of the core layer collecting line is 30-300r/min.
The centrifugal spinning device for collecting the fibers from the rolls comprises a spinning tank and a fiber collecting device arranged below the spinning tank;
specifically, the fiber collecting device comprises a collecting assembly, a rotating assembly used for driving the collecting assembly to rotate and a driving device used for driving the rotating assembly to rotate; the rotating assembly is connected with the driving device, and the rotating assembly is connected with the collecting assembly through a conveying belt; the collecting assembly comprises a core collecting wire and two clamps 42 for clamping two ends of the core collecting wire; the drive assembly drives the rotating assembly to rotate, thereby driving the conveyor belt to rotate, which in turn drives the clamp 42 and the core collection wire to rotate, collecting the fibers on the core collection wire.
As shown in fig. 3, a preferred structure of the fiber collecting apparatus includes a connection shaft 30, first gears 31 separately provided at both ends of the connection shaft 30, a driving device for driving one of the first gears 31 to rotate, and two sets of installation shafts 40 provided at one side of the connection shaft 30; the two sets of mounting shafts 40 are coaxially arranged and provided thereon with second gears 41 respectively corresponding to the two sets of first gears 31 connected by means of a belt 50, and the opposite ends of the two sets of mounting shafts 40 are each provided with a clamp 42 for clamping the fibers.
The driving device is an electric driving device 20, and the electric driving device 20 is connected with a rotating speed regulator 21 in a line. The device is further provided with a mounting plate 10 for support and a connecting rod 11.
The specific operation is as follows: the two ends of the core layer collecting wire are clamped by the clamp 42, and the core layer collecting wire is coaxial with the installation shaft 40 (the core layer collecting wire is formed by spirally winding metal wires on the surface of the elastic fiber, and the spiral winding structure can increase the strength of the core layer and prevent the core layer from breaking in the spinning process). Subsequently, the electric drive device 20 is turned on, and the output power of the electric drive device 20 is adjusted by the speed knob. The electric driving device 20 drives the first gear 31 on the adjacent side to rotate, and the first gear 31 drives the other first gear 31 to synchronously rotate through the connecting shaft 30. At the same time, the two sets of first gears 31 drive the second gears 41 to rotate through the transmission belts 50, respectively. The second gear 41 further drives the clamp 42 to rotate through the mounting shaft 40, and the clamp 42 clamps the core collecting wire to drive the core collecting wire to synchronously rotate with the core collecting wire, so that the rotation of the core collecting wire is realized, and the polyacrylonitrile fiber is collected on the core collecting wire.
The whole process is completed through the cooperation of the spinning tank and the fiber collecting device, for example, the uniformity and compactness of fiber collecting winding can be improved by adjusting the relative positions of the spray heads on the spinning tank and the fiber collecting device, specifically, the spray heads on the spinning tank can be arranged to freely move, so that the spray heads reciprocate left and right relative to the core layer collecting line, and the cortex fibers are uniformly wound on the whole core layer collecting line in a certain area; or the core layer collecting line can be set to freely move, so that the core layer collecting line can move left and right in a reciprocating manner relative to the spray head, and the skin layer fibers are uniformly wound on the whole core layer collecting line, so that elastic electromagnetic shielding fibers are formed (as shown in fig. 1, the fiber collecting device is horizontally arranged).
According to the characteristics of centrifugal spinning, the sheath fibers can be uniformly distributed in a centrifugal area, so that the sheath fibers are uniformly wound on a core layer collecting line; meanwhile, the solvent is not completely volatilized in the stretching process of the spinning trickle sprayed from the spinning tank nozzle of the centrifugal spinning, so that the centrifugally spun skin fiber has certain adhesive force to the core layer collecting line, and the skin layer can be wound on the core layer collecting line with certain adhesive force.
The invention also provides an elastic electromagnetic shielding fiber, which is prepared by adopting the preparation method of the elastic electromagnetic shielding fiber. The elongation of the obtained elastic electromagnetic shielding fiber is 10% -35%, the electromagnetic shielding efficiency of the fabric prepared from the elastic electromagnetic shielding fiber is 30-40dB, and the electromagnetic shielding efficiency is 90% -99%.
The invention also provides application of the elastic electromagnetic shielding fiber, and the elastic electromagnetic shielding fiber is applied to preparation of electromagnetic shielding materials.
The invention is described in detail below by means of several examples:
example 1
A preparation method of elastic electromagnetic shielding fiber comprises the following steps:
s11, preparing a core layer:
and uniformly and spirally winding the copper wire on the surface of the elastic polyurethane fine wire to obtain the core layer. The diameter of the elastic fiber is 1mm. The distance between adjacent copper wires in the spiral structure is 1mm.
S21, preparing a cortex spinning solution:
placing ferroferric oxide nano particles in N, N-dimethylformamide, carrying out ultrasonic oscillation for 1h, adding polyacrylonitrile and polyurethane into a water bath with the temperature of 50 ℃, and stirring for 2h to form a mixed solution. According to mass fraction, polyurethane is 15%, polyacrylonitrile is 5%, ferroferric oxide nano particles are 2.5%, and the balance is N, N-dimethylformamide, then the polyurethane is placed into a deaerator, and deaeration treatment is carried out for 4 hours under the vacuum degree of-0.09 MPa and the temperature of 40 ℃ to obtain the cortex spinning stock solution.
S31, preparing elastic electromagnetic shielding fibers:
and (3) carrying out centrifugal spinning on the cortex spinning solution prepared in the step (S21) through a centrifugal spinning device for self-rolling collection, so that the cortex fibers are wound on the autorotation core layer prepared in the step (S11) until the core layer is completely wrapped by the cortex, and the elastic electromagnetic shielding fibers are obtained.
Wherein, the rotational speed of centrifugal spinning is 4000r/min, the temperature is 30 ℃, the environmental humidity is 40%, and the collecting distance is 15cm; the rotational speed of the core layer collecting line is 150r/min.
Examples 2 to 3
The difference between the preparation method of the elastic electromagnetic shielding fiber and the embodiment 1 is that in the step S11, the diameter of the elastic fiber is different, and the other steps are substantially the same as those in the embodiment 1, and are not described herein.
Examples 4 to 5
The difference in the step S11 compared with the embodiment 1 is that the winding density of the copper wires is different, the distance between the adjacent copper wires in the spiral structure is different, and the other steps are substantially the same as the embodiment 1, and will not be described here.
As shown in table 1, for the elongation (i.e., elastic elongation) of the elastic electromagnetic shielding fibers prepared in examples 1 to 5 and the electromagnetic shielding related data (electromagnetic shielding effectiveness and electromagnetic shielding efficiency) of the fabrics prepared from the elastic electromagnetic shielding fibers, the frequency of electromagnetic waves was 20MHz to 2GHz. (the fabric is directly produced by a braiding machine)
TABLE 1 data relating to elastic electromagnetic shielding fibers prepared in examples 1-5
As can be seen from table 1, as the diameter of the elastic fiber increases (examples 1, 2, and 3), the elastic elongation of the prepared fiber gradually decreases, and the electromagnetic shielding effectiveness and electromagnetic shielding efficiency of the fabric gradually increase. This is mainly because, as the diameter of the elastic fiber increases, the degree of difficulty in elastic deformation, i.e., the degree of difficulty in elastic deformation of the core layer increases, thereby reducing the elongation of the fiber produced; in the centrifugal spinning self-rolling collecting process, the skin layers are uniformly and compactly wound on the core layers along with the increase of the diameters of the fibers, the obtained fibers have large porosity, and the existence of the pores has a certain reflection effect on electromagnetic waves, so that the electromagnetic shielding effectiveness and the electromagnetic shielding efficiency of the fabric are gradually increased. However, when the diameter of the elastic fiber is too large, various properties of the fiber and the fabric are degraded.
As the distance between adjacent copper wires decreases (examples 1, 4, 5), the elastic elongation of the prepared fibers, the electromagnetic shielding effectiveness of the fabric, and the electromagnetic shielding efficiency all tended to increase. This is mainly because, as the distance between adjacent copper wires decreases, the copper wires on the core layer are denser and the conductivity of the core layer is better; meanwhile, the core layer collecting line is more compact and uniform, and the skin layer material is more easily and uniformly wound on the core layer in the centrifugal spinning self-rolling collecting process, so that the electromagnetic shielding fiber with uniform pores and better structure is obtained, and the electromagnetic shielding efficiency of the fabric are gradually increased.
Examples 6 to 11
The difference between the preparation method of the elastic electromagnetic shielding fiber and the embodiment 1 is that in the step S21, the ratio of the polyurethane, the polyacrylonitrile and the ferroferric oxide nanoparticles is different, and the other steps are substantially the same as the embodiment 1, and are not repeated here.
As shown in Table 2, for the elongation of the elastic electromagnetic shielding fibers prepared in examples 6 to 11 and the electromagnetic shielding related data (electromagnetic shielding effectiveness and electromagnetic shielding efficiency) of the fabrics prepared from the elastic electromagnetic shielding fibers, the frequency of electromagnetic waves was 20MHz to 2GHz. (the fabric is directly produced by a braiding machine)
TABLE 2 data relating to elastic electromagnetic shielding fibers prepared in examples 6-11
As can be seen from table 2, as the polyacrylonitrile content increases (examples 1, 6, and 7), the elastic elongation of the prepared fibers, the electromagnetic shielding effectiveness of the fabrics, and the electromagnetic shielding efficiency gradually decrease. This shows that the addition of polyacrylonitrile, while advantageous for spinning the fibers, can enhance the strength of the fibers, its content has an effect on the properties of the fibers and their fabrics.
As the content of ferroferric oxide nanoparticles was increased (examples 6, 8, 9), the elastic elongation of the prepared fibers was decreased, and the electromagnetic shielding effectiveness and electromagnetic shielding efficiency of the fabrics were gradually increased. This is mainly because as the content of the ferroferric oxide nanoparticles increases, the elastic deformation of the sheath material decreases, and thus the elastic elongation of the fiber decreases, but the conductivity and magnetic permeability of the sheath increase, and thus the electromagnetic shielding effectiveness and electromagnetic shielding efficiency of the fabric gradually increase.
As the polyurethane content was increased (examples 1, 10, 11), the elastic elongation of the prepared fiber was increased, and the electromagnetic shielding effectiveness and electromagnetic shielding efficiency of the fabric were gradually decreased.
Examples 12 to 16
The difference of the preparation method of the elastic electromagnetic shielding fiber compared with the embodiment 1 is that in the step S31, the rotational speed of the centrifugal spinning, the rotational speed of the core layer collecting line and the collecting distance in the centrifugal spinning process are different, and the other steps are substantially the same as the embodiment 1, and are not described herein.
As shown in Table 3, for the elongation of the elastic electromagnetic shielding fibers prepared in examples 12 to 16 and the electromagnetic shielding related data (electromagnetic shielding effectiveness and electromagnetic shielding efficiency) of the fabrics prepared from the elastic electromagnetic shielding fibers, the frequency of electromagnetic waves was 20MHz to 2GHz. (the fabric is directly produced by a braiding machine)
TABLE 3 data relating to elastic electromagnetic shielding fibers prepared in examples 12-16
As can be seen from table 3, with the increase of the rotational speed of the centrifugal spinning and the rotational speed of the core collecting line (examples 1 and 14), the elastic elongation of the prepared fiber, the electromagnetic shielding effectiveness and the electromagnetic shielding efficiency of the fabric were not greatly changed, which means that when the rotational speed of the centrifugal spinning and the rotational speed of the core collecting line are matched, the pores and the component uniformity of the obtained fiber were better when the core and the skin were at the proper rotational speeds, so that the structure of the fiber was better, and the performance of the fabric was better. And when the rotational speed of the centrifugal spinning is small and the rotational speed of the core collecting wire is large (example 15), the properties of the produced fibers and fabrics are affected. When the rotational speed of the centrifugal spinning and the rotational speed of the core collecting wire are simultaneously reduced (example 16), the elastic elongation of the prepared fiber is superior, and the electromagnetic shielding effectiveness and the electromagnetic shielding efficiency of the fabric are reduced, mainly because the obtained sheath-core structure is different with the reduction of the rotational speed of the centrifugal spinning and the rotational speed of the core collecting wire, thereby affecting the performance of the fabric.
As the collection distance increases (examples 1, 12, 13), the elastic elongation of the prepared fibers increases and the electromagnetic shielding effectiveness and electromagnetic shielding efficiency of the fabric decrease.
Comparative example 1
Compared with the embodiment 1, the preparation method of the elastic electromagnetic shielding fiber is different in that the core layer material is only polyurethane fiber, the outer layer is not coated with copper wires, and the polyurethane fiber is directly used as a core layer collecting wire to obtain the elastic electromagnetic shielding fiber. The elongation of the elastic electromagnetic shielding fiber is 24.7%, and the elongation is increased; the electromagnetic shielding effectiveness of the fabric is 22dB, the electromagnetic shielding effectiveness is 81.9%, and the electromagnetic shielding effectiveness of the fabric are obviously reduced, which means that only the conductive fiber of the skin layer is poor in conductivity of single fiber, and the electromagnetic shielding performance (effectiveness and efficiency) of the prepared fabric is poor.
Comparative example 2
Compared with the embodiment 1, the preparation method of the elastic electromagnetic shielding fiber is different in that the core layer material only has copper wires and polyurethane, and the elastic electromagnetic shielding fiber is obtained by directly taking the thin straight copper wires as core layer collecting wires. The elongation of the elastic electromagnetic shielding fiber is 18.9%, the electromagnetic shielding efficiency of the fabric is 33dB, the electromagnetic shielding efficiency of the fabric is 94.18%, and the electromagnetic shielding performance (efficiency and efficiency) of the fabric is reduced, which indicates that in the fabric made of the spiral copper wires, the conductive layer formed by the conductive substance is more compact, and the electromagnetic shielding performance of the fabric is better. The elongation is significantly reduced, which means that the linear copper wire limits the elastic properties of the fiber.
Comparative example 3
The preparation method of the elastic electromagnetic shielding fiber is different from that in the embodiment 1 in that the skin layer does not contain polyacrylonitrile, only polyurethane and ferroferric oxide nano-particles are contained, and the ferroferric oxide nano-particles still keep the original mass ratio, so that the elastic electromagnetic shielding fiber is obtained. The elongation of the elastic electromagnetic shielding fiber is 39.9%, the electromagnetic shielding efficiency of the fabric is 37dB, the electromagnetic shielding efficiency is 96.98%, although various performances of the fiber and the fabric are improved, the existence of polyacrylonitrile is avoided, the spinning process is not well controlled, and the strength of the fiber is obviously poor.
Comparative example 4
The preparation method of the elastic electromagnetic shielding fiber is different from example 1 in that ferroferric oxide nano particles in the cortex are changed into graphene to obtain the elastic electromagnetic shielding fiber. The elongation of the elastic electromagnetic shielding fiber is 20.3%, the electromagnetic shielding efficiency of the fabric is 30dB, the electromagnetic shielding efficiency of the fabric is 91.09%, and the electromagnetic shielding performance of the fabric is reduced, so that the magnetic permeability particles (both conductive and magnetic permeability) have positive effects on the electromagnetic shielding performance of the fabric, and further the electric conductivity and high magnetic permeability particles cooperatively improve the electromagnetic shielding efficiency of the fabric.
In summary, the elastic electromagnetic shielding fiber and the preparation method and application thereof provided by the invention combine centrifugal spinning and self-rolling collection, so that the skin fiber is uniformly and compactly transversely wound on the core layer, the single fibers are interlaced to different degrees, the skin fibers wound on different parts of the core layer are uniformly distributed, and the elastic electromagnetic shielding fiber with a special structure with uniform pore distribution and uniform thickness is obtained; the core layer and the skin layer of the fiber can be conductive, and the conductive particles of the copper wires and the skin layer of the core layer are uniformly distributed in the core layer and the skin layer of the fiber, so that the conductivity of the obtained fiber is better, and the special surface structure with uniform pore distribution and uniform thickness is combined, so that the prepared fabric forms a compact and uniform conductive layer, and the uniform pores have a certain reflection effect on electromagnetic waves, so that the electromagnetic shielding performance of the fabric is better.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of elastic electromagnetic shielding fiber is characterized in that: firstly preparing a core layer, adopting a centrifugal spinning self-rolling collecting method, taking the core layer as a core layer collecting line through a centrifugal spinning device for self-rolling collection, and collecting a skin layer to obtain elastic electromagnetic shielding fibers; the core layer and the skin layer both have electromagnetic shielding performance and elasticity;
the centrifugal spinning device for collecting the fibers in the self-rolling manner comprises a spinning tank and a fiber collecting device arranged below the spinning tank;
the fiber collecting device comprises a collecting assembly, a rotating assembly used for driving the collecting assembly to rotate and a driving device used for driving the rotating assembly to rotate; the rotating assembly is connected with the driving device, and the rotating assembly is connected with the collecting assembly through a conveying belt; the collecting assembly comprises a core layer collecting line and two clamps used for clamping two ends of the core layer collecting line; the driving device drives the rotating assembly to rotate so as to drive the conveyor belt to rotate, and further drive the clamp and the core layer collecting line to rotate, so that the cortex fibers are collected on the core layer collecting line;
the centrifugal spinning self-rolling collecting method comprises the following steps:
s1, preparing spinning solution; placing ferroferric oxide nano particles in an organic solvent, carrying out ultrasonic oscillation for 1-2h, adding polyacrylonitrile and an elastic material into a water bath at the temperature of 40-60 ℃, stirring for 1-3h to form a mixed solution, and carrying out defoaming treatment for 3-5h to obtain a cortex spinning stock solution with the concentration of 20-30 wt%; the spinning solution comprises the following components in percentage by mass: 10% -25% of elastic material, 0.1% -5% of polyacrylonitrile, 0.1% -5% of ferroferric oxide nano particles and the balance of organic solvent;
s2, carrying out centrifugal spinning on the spinning solution prepared in the step S1 through the self-rolling type collecting centrifugal spinning device, so that the spun fibers are wound on a core layer collecting line capable of rotating; the core layer collecting wire is obtained by spirally winding metal wires on the surface of elastic fiber; the diameter of the elastic fiber is 0.1-2mm, and the distance between adjacent metal wires in the spiral structure is 0.1-2mm;
the rotational speed of the centrifugal spinning is 4000-8000r/min, and the rotational speed of the core layer collecting line is 30-300r/min.
2. The method for producing an elastic electromagnetic shielding fiber according to claim 1, wherein: the temperature of the centrifugal spinning is 30-60 ℃ and the environmental humidity is 30-50%.
3. The method for producing an elastic electromagnetic shielding fiber according to claim 1, wherein: the spinning aperture of the centrifugal spinning is 0.1-1mm, and the collecting distance is 7-20cm.
4. The method for producing an elastic electromagnetic shielding fiber according to claim 1, wherein: in step S2, the elastic fiber includes one of polyurethane fiber, polyester composite elastic fiber, polyolefin elastic fiber and spandex; the metal wire comprises one of a copper wire, a nickel wire, a platinum wire and an aluminum wire; in step S1, the elastic material includes one or more of polyurethane, polyether block amide, styrenic thermoplastic rubber, and thermoplastic vulcanizate; the organic solvent is one or more of N, N-dimethylformamide and N, N-dimethylacetamide.
5. An elastic electromagnetic shielding fiber, characterized in that: is prepared by the preparation method of the elastic electromagnetic shielding fiber of any one of claims 1-4.
6. The elastic electromagnetic shielding fiber according to claim 5, wherein: the elongation of the elastic electromagnetic shielding fiber is 10% -35%, the electromagnetic shielding efficiency of the fabric prepared from the elastic electromagnetic shielding fiber is 30-40dB, and the electromagnetic shielding efficiency is 90% -99%.
7. Use of the elastic electromagnetic shielding fiber prepared by the preparation method of the elastic electromagnetic shielding fiber according to any one of claims 1 to 4 or the elastic electromagnetic shielding fiber according to any one of claims 5 to 6, characterized in that: the elastic electromagnetic shielding fiber is applied to the preparation of electromagnetic shielding materials.
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