CN114921882A - 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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- CN114921882A CN114921882A CN202210544699.2A CN202210544699A CN114921882A CN 114921882 A CN114921882 A CN 114921882A CN 202210544699 A CN202210544699 A CN 202210544699A CN 114921882 A CN114921882 A CN 114921882A
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- D—TEXTILES; PAPER
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- 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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- 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
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- 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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- 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
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
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- Manufacturing & Machinery (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
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, then adopting a centrifugal spinning self-rolling type collection method, taking the core layer as a self-rolling type collection unit, and collecting a skin layer to obtain the elastic electromagnetic shielding fiber; the core layer has conductivity and elasticity, and the skin layer has high magnetic conductivity and elasticity; the centrifugal spinning self-rolling type collecting method is that spinning solution is centrifugally spun by a centrifugal spinning device for self-rolling type collection, and fibers after spinning are wound on a self-rolling type collecting unit capable of rotating. The invention combines centrifugal spinning and self-rolling type collection, so that the spinning fiber is transversely wound on the core layer by layer to obtain the elastic electromagnetic shielding fiber with a certain porous structure on the skin layer, the obtained elastic electromagnetic shielding fiber has better conductivity, elasticity and strength, and the fabric prepared by 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. Meanwhile, these electronic products also emit electromagnetic waves to the outside, thereby causing electromagnetic wave pollution. In order to prevent such damage, electromagnetic shielding materials are often used for protection.
In order to prepare the electromagnetic shielding material, it can be realized by preparing the conductive fiber and then making the conductive fiber into a fabric. However, most polymeric materials are insulating materials, and fibers made from these polymers are also insulating. Therefore, it is necessary to prepare the insulating fiber into the conductive fiber by a certain means to solve the disadvantage that the electromagnetic shielding performance cannot be realized.
The method of making the insulating fibers into the conductive fibers is generally to disperse a conductive substance, such as carbon black, graphite, metal powder or metal compound, in the insulating fibers or to provide a conductive coating on the surface of the insulating fibers. Dispersing the conductive substance in the insulating fiber can be completed by methods such as mixing and dissolving or composite spinning, but the method has the defect of uneven dispersion of the conductive substance in the dispersion liquid, so that the conductive substance in the fiber is unevenly distributed, the conductive performance is influenced, and the electromagnetic shielding performance of the fabric is further influenced. The conductive coating can be arranged on the surface of the insulating fiber by coating, evaporation, electroplating and other methods, and the method has the following defects: on one hand, due to the inertia of the fiber, the bonding force between the conductive coating and the fiber is weak, so that the coating is easy to fall off, and the conductive performance of the fiber is influenced; on the other hand, the uniformity of the coating can affect the conductivity of the fiber, and further affect the electromagnetic shielding performance of the fabric. Therefore, the metal wire can be directly used as a conductive medium, and the fiber is coated on the surface of the metal wire to form the conductive fiber.
The patent with the application number of CN201510171061.9 discloses a piezoelectric polymer/metal composite nano 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 skin layer, and finally standing the obtained fiber at room temperature until the solvent is volatilized to obtain the nano-fiber composite material. The method has the following defects: (1) in the electrostatic spinning process, as the nano fibers carry the same charges to repel each other, the nano fibers are randomly arranged on the surface of the gold threads, so that the performance of a product is poor; (2) the jet drawing speed of electrospinning is not stable, which also makes the arrangement of the nanofibers on the surface of the metal filament irregular.
In view of the above, there is a need for an improved elastic electromagnetic shielding fiber, a method for preparing the same, and applications thereof.
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 type collection are combined, so that skin layer fibers are uniformly, compactly and transversely wound on a core layer, and the elastic electromagnetic shielding fiber with a special structure and uniform pore distribution and thickness is obtained; the core layer and the skin layer of the fiber can be conductive, 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 conductive performance of the obtained fiber is excellent, the special surface structure with uniform pore distribution and uniform thickness is combined, the prepared fabric forms a compact and uniform conductive layer, uniform pores have a certain reflection effect on electromagnetic waves, and the electromagnetic shielding performance of the fabric is excellent.
In order to achieve the purpose, the invention provides a preparation method of elastic electromagnetic shielding fiber, which comprises the steps of firstly preparing a core layer, then adopting a centrifugal spinning self-rolling type collection method, taking the core layer as a self-rolling type collection unit, and then 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 type collection method comprises the following steps:
s1, preparing a spinning solution;
s2, carrying out centrifugal spinning on the spinning solution prepared in the step S1 through a centrifugal spinning device for self-winding collection, and winding the spun fibers on a self-winding collection unit capable of rotating automatically.
As a further improvement of the invention, the core layer comprises elastic fibers and high-conductivity metal wires spirally wound on the surfaces of the elastic fibers.
As a further improvement of the present invention, the skin layer comprises an elastic material, polyacrylonitrile and high magnetic permeability particles; 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.
As a further improvement of the invention, the method comprises the following steps:
s11, spirally winding a metal wire on the surface of the elastic fiber 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 0.1-2 mm;
s21, mixing the elastic material, polyacrylonitrile and high-permeability particles according to a certain proportion, uniformly dispersing the mixture in an organic solvent, and performing defoaming treatment to obtain a cortex spinning solution;
s31, carrying out centrifugal spinning on the skin layer spinning solution prepared in the step S2 through the self-winding type collected centrifugal spinning device, and winding skin layer fibers on the core layer which is prepared in the step S11 and can rotate until the core layer is completely wrapped by the skin layer, so that the elastic electromagnetic shielding fibers are obtained.
As a further improvement of the invention, in step S31, the rotation 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 30-300 r/min.
As a further improvement of the invention, in step S31, the spinning aperture of the centrifugal spinning is 0.1-1mm, and the collection distance is 7-20 cm; in step S21, the concentration of the sheath spinning dope is 20 wt% to 30 wt%.
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 vulcanizate; the high magnetic permeability particles comprise one or more of ferroferric oxide nanoparticles, ferric oxide nanoparticles and cobalt oxide nanoparticles; the organic solvent is a good solvent of polyacrylonitrile and elastic materials, and is preferably one or more of N, N-dimethylformamide and N, N-dimethylacetamide.
The invention also provides the elastic electromagnetic shielding fiber which is prepared by the preparation method of the elastic electromagnetic shielding fiber.
As a further improvement of the 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 an application of the elastic electromagnetic shielding fiber, and the elastic electromagnetic shielding fiber is applied to the preparation of electromagnetic shielding materials.
The beneficial effects of the invention are:
(1) the elastic electromagnetic shielding fiber prepared by the invention is prepared by spirally winding a metal wire on the surface of the elastic fiber to form a core layer, and then combining centrifugal spinning with self-winding type collection to enable a skin layer to be wound on the surface of the core layer rotating at high speed through centrifugal spinning, so that the elastic electromagnetic shielding fiber is obtained. In the centrifugation in-process of spinning, when cortex spinning dope throws away, carry out certain drawing to the spinning trickle, when the spinning trickle meets the high-speed rotatory sandwich layer (be the sandwich layer collection line), take place the drawing once more, obtain fine single fiber, and convolute it on the sandwich layer of rotation, make the crisscross winding of cortex fiber layer upon layer on the sandwich layer, take place the intertwine of not equidimension between the single fiber, there is certain hole between the cortex fiber, simultaneously because the centrifugation rotational speed is high, the fibre of centrifugal spinning is comparatively even in certain regional area, if the sandwich layer collection line is continuous and when can following the rotation of fibre direction operation, there is the prospect that realizes large tracts of land industrialization production. The collecting method is simple and novel, high in efficiency, good in controllability and convenient for large-scale production.
(2) The core layer and the skin layer of the elastic electromagnetic shielding fiber prepared by the invention can conduct electricity, and the metal wires of the core layer and the high magnetic permeability 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, and the skin layer has high magnetic permeability, conductivity and elasticity), namely, conductive substances distributed at all parts of the fiber are uniform, so that the conductivity of the obtained fiber is better, and the prepared fabric forms a compact and uniform conductive layer by combining a special surface structure with relatively uniform pore distribution and uniform thickness, and the pores between the fiber have a certain reflection effect on electromagnetic waves, so that the fabric has an excellent electromagnetic shielding effect on the electromagnetic waves with different frequencies. The high magnetic conductivity particles in the skin layer have excellent electromagnetic shielding effectiveness, and the electromagnetic shielding effectiveness of the fabric is improved by the cooperation of the conductivity and the high magnetic conductivity particles. Meanwhile, the surface of the core layer is densely wrapped by the skin layer, and the core layer is of a metal wire and elastic fiber composite structure, so that the elastic performance of the fiber is improved, the strength of the fiber is improved, and the elastic performance and the strength of the fabric are further improved. In addition, the metal wires are relatively soft, and the prepared fabric has certain flexibility.
(3) According to the collecting device adopted in the fiber collecting process, the clamps for clamping the two ends of the core layer collecting line are arranged at the two ends of the core layer collecting line, and in the autorotation process of the core layer collecting line, due to the existence of the clamps, the rotation states of the two ends of the core layer collecting line are kept consistent, so that single fibers are distributed at the positions of the core layer collecting line, fiber bundles with good uniformity are obtained, and the preparation of the elastic electromagnetic shielding fibers is guaranteed.
Drawings
Fig. 1 is a schematic view of a 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 by the present invention.
Fig. 3 is a view of a fiber collecting apparatus of the self-wound collecting centrifugal spinning apparatus of the present invention.
Reference numerals
10-mounting a plate; 11-a connecting rod; 20-an electric drive; 21-a rotational speed regulator; 30-a connecting shaft; 31-a first gear; 40-mounting the shaft; 41-a second gear; 42-a clamp; 50-transmission 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 with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be 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, then adopting a centrifugal spinning self-rolling type collection method, taking the core layer as a self-rolling type collection unit, and then 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 type collecting method comprises the following steps:
s1, preparing a spinning solution;
s2, carrying out centrifugal spinning on the spinning solution prepared in the step S1 through a centrifugal spinning device for self-winding collection, so that the spun fibers are uniformly and densely wound on a self-winding collection unit capable of rotating automatically.
Preferably, the self-rolling type collecting unit is a core layer collecting wire, and the fiber is wound on the core layer collecting wire, in this embodiment, the core layer of the elastic electromagnetic shielding fiber is the core layer 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 copper wire, nickel wire, platinum wire and aluminum wire.
The cortex comprises elastic materials, polyacrylonitrile and high magnetic conductivity particles, and the spinning solution comprises the following components in percentage by mass: 10 to 25 percent of elastic material, 0.1 to 15 percent of polyacrylonitrile, 0.1 to 5 percent of high magnetic permeability particles and the balance of organic solvent. Wherein the elastic material comprises one or more of polyurethane, polyether block amide, styrenic thermoplastic rubber and thermoplastic vulcanizate; the high magnetic permeability particles comprise one or more of ferroferric oxide nanoparticles, ferric oxide nanoparticles and cobalt oxide nanoparticles. The organic solvent is a good solvent of polyacrylonitrile and elastic materials, and comprises one or more of N, N-dimethylformamide and N, N-dimethylacetamide.
In some embodiments, the skin layer further comprises a flame retardant to produce the elastic electromagnetic shielding fiber having flame retardant properties.
Specifically, as shown in fig. 1, the method for preparing 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 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 0.1-2 mm.
Adopt the sandwich layer structure of metal silk and elastic fiber complex, at flexible in-process, elastic fiber and spiral helicine metal silk stretch out and draw back simultaneously, the elasticity performance of sandwich layer has not only been increased, and the intensity of sandwich layer has been increased, and the metal silk evenly adheres to the elastic fiber surface simultaneously, makes the electric conductive property of sandwich layer superior, these are elastic electromagnetic shielding fiber's performance and provide the assurance, make the elastic electromagnetic shielding fiber elasticity, electric conductivity and the intensity of preparation all superior, and then make the electromagnetic shielding performance of the fabric made by this elastic electromagnetic shielding fiber superior.
S21, preparing a skin layer spinning solution:
mixing the elastic material, polyacrylonitrile and high-permeability particles according to a certain proportion, uniformly dispersing the mixture in an organic solvent, and defoaming the mixture to obtain the cortex spinning solution.
Specifically, the high-permeability particles are placed in an organic solvent for ultrasonic oscillation for 1-2 hours, polyacrylonitrile and an elastic material are added in a water bath at the temperature of 40-60 ℃, the mixture is stirred for 1-3 hours to form a mixed solution, and the cortex spinning solution with the concentration of 20-30 wt% is obtained after defoaming treatment for 3-5 hours. Preferably, the spinning solution comprises the following components in percentage by mass: 10 to 25 percent of elastic material, 0.1 to 15 percent of polyacrylonitrile, 0.1 to 5 percent 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 (4) carrying out centrifugal spinning on the cortex spinning solution prepared in the step (S21) by a centrifugal spinning device collected in a self-winding manner, so that the cortex fiber is wound on the core layer which is prepared in the step (S1) and can rotate until the core layer is completely wrapped by the cortex, thus obtaining the elastic electromagnetic shielding fiber, wherein the structure of the obtained elastic electromagnetic shielding fiber is shown in figure 2.
Wherein the rotating speed of the centrifugal spinning is 1000-; the rotating speed of the core layer collecting line is 30-300 r/min.
The spinning device comprises a spinning tank and a fiber collecting device arranged below the spinning tank;
the fiber collecting device comprises a collecting component, a rotating component and a driving device, wherein the rotating component is used for driving the collecting component 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 line and two clamps 42 for clamping both ends of the core collecting line; the drive arrangement drives the rotation assembly to rotate, thereby driving the conveyor belt to rotate, further driving the clamp 42 and the core layer collecting line to rotate, and collecting the fibers on the core layer collecting line.
As shown in fig. 3, a preferred structure of the fiber collecting device includes a connecting shaft 30, first gears 31 respectively disposed at two ends of the connecting shaft 30, a driving device for driving one of the first gears 31 to rotate, and two sets of mounting shafts 40 disposed at one side of the connecting 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 a transmission belt 50, and opposite ends of the two sets of mounting shafts 40 are each provided with a jig 42 for holding fibers.
The driving device is an electric driving device 20, and the electric driving device 20 is connected with a rotating speed regulator 21 through a wire. The device is further provided with a mounting plate 10 and a connecting rod 11 for support.
The specific operation is as follows: the two ends of the core layer collecting line are clamped by a clamp 42, and the core layer collecting line is ensured to be coaxial with the mounting shaft 40 (the core layer collecting line of the invention is a core layer formed by spirally winding metal wires on the surface of elastic fibers, and the spiral winding structure can increase the strength of the core layer and prevent the core layer from being broken 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 located at the near side to rotate, and the first gear 31 further drives the other first gear 31 to rotate synchronously through the connecting shaft 30. Meanwhile, the two sets of first gears 31 drive the second gears 41 to rotate through the transmission belts 50. The second gear 41 drives the clamp 42 to rotate through the mounting shaft 40, and the clamp 42 clamps the core layer collecting line to drive the core layer collecting line to rotate synchronously with the core layer collecting line, so that the rotation of the core layer collecting line is realized, and the polyacrylonitrile fibers are collected on the core layer collecting line.
The whole process is completed through the matching of the spinning tank and the fiber collecting device, for example, the relative position of the spray head on the spinning tank and the fiber collecting device can be adjusted to improve the uniformity and compactness of fiber collecting and winding, specifically, the spray head on the spinning tank can be set to freely move, so that the spray head can move left and right in a reciprocating manner relative to the core layer collecting line, and therefore, the skin layer fibers can be 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 relative to the spray head in a reciprocating manner, and the skin layer fibers are uniformly wound on the whole core layer collecting line to form the elastic electromagnetic shielding fibers (as shown in figure 1, the fiber collecting device is horizontally arranged).
According to the characteristics of centrifugal spinning, the cortical fibers can be uniformly distributed in a centrifugal area, so that the cortical fibers can be uniformly wound on the core layer collecting wire; meanwhile, the spinning trickle ejected from a spinning tank nozzle of centrifugal spinning has incomplete volatilization of a solvent in the stretching process, so that the centrifugally spun skin layer 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 the elastic electromagnetic shielding fiber which is prepared by the preparation method of the elastic electromagnetic shielding fiber. 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%.
The invention also provides an application of the elastic electromagnetic shielding fiber, and the elastic electromagnetic shielding fiber is applied to the preparation of electromagnetic shielding materials.
The invention is described in detail below by means of a number of examples:
example 1
A preparation method of elastic electromagnetic shielding fiber comprises the following steps:
s11, preparing a core layer:
and winding copper wires on the surface of the elastic polyurethane fine wire uniformly and spirally to obtain the core layer. The elastic fiber had a diameter of 1 mm. The distance between adjacent copper wires in the helical structure is 1 mm.
S21, preparing a skin layer spinning solution:
and (2) placing the ferroferric oxide nano particles in N, N-dimethylformamide for ultrasonic oscillation for 1h, adding polyacrylonitrile and polyurethane in a water bath at the temperature of 50 ℃, and stirring for 2h to form a mixed solution. According to the mass fraction, 15% of polyurethane, 5% of polyacrylonitrile, 2.5% of ferroferric oxide nano particles and the balance of N, N-dimethylformamide are placed into a defoaming machine, and defoaming treatment is carried out for 4 hours at the vacuum degree of-0.09 MPa and the temperature of 40 ℃ to obtain the cortex spinning solution.
S31, preparing elastic electromagnetic shielding fibers:
and (4) carrying out centrifugal spinning on the skin layer spinning solution prepared in the step (S21) through a centrifugal spinning device collected in a self-winding mode, and winding skin layer fibers on the core layer which is prepared in the step (S11) and can rotate until the core layer is completely wrapped by the skin layer to obtain the elastic electromagnetic shielding fibers.
Wherein the rotation speed of centrifugal spinning is 4000r/min, the temperature is 30 ℃, the environmental humidity is 40%, and the collection distance is 15 cm; the rotation speed of the core layer collection line is 150 r/min.
Examples 2 to 3
Compared with the embodiment 1, the difference of the preparation method of the elastic electromagnetic shielding fiber is that in the step S11, the diameter of the elastic fiber is different, and the rest is substantially the same as that of the embodiment 1, and the description is omitted.
Examples 4 to 5
Compared with embodiment 1, the difference of the preparation method of the elastic electromagnetic shielding fiber is that in step S11, the winding density of the copper wires is different, the distance between adjacent copper wires in the spiral structure is different, and the others are substantially the same as those in embodiment 1, and are not repeated herein.
As shown in table 1, 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 were obtained, and the frequency of the electromagnetic waves was 20MHz to 2 GHz. (the fabric is made directly by the knitting machine)
Table 1 data on elastic electromagnetic shielding fibers prepared in examples 1 to 5
As can be seen from table 1, as the diameter of the elastic fiber increases (examples 1, 2, 3), the elastic elongation of the prepared fiber gradually decreases, and the electromagnetic shielding effectiveness and 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 increases, i.e., the degree of difficulty in elastic deformation of the core layer increases, thereby decreasing the elongation of the fiber produced; and along with the increase of fiber diameter, the centrifugal spinning is from rolling up the formula collection in-process, along with the cortex evenly densely winds on the sandwich layer, the porosity of the fibre that obtains is great, and the existence in hole has certain reflection effect to the electromagnetic wave to make the electromagnetic shielding efficiency and the electromagnetic shielding efficiency of fabric increase gradually. 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 decreased (examples 1, 4, 5), the elastic elongation of the prepared fiber, the electromagnetic shielding effectiveness of the fabric, and the electromagnetic shielding efficiency all showed a tendency to increase. This is mainly because, with the reduction of the distance of the adjacent copper wires, the copper wires on the core layer are more compact, and the electrical conductivity of the core layer is better; meanwhile, the core layer collecting line is more compact and uniform, and in the process of centrifugal spinning self-rolling type collection, the skin layer material is more easily and uniformly wound on the core layer to obtain the electromagnetic shielding fiber with uniform pores and a better structure, so that the electromagnetic shielding efficiency and the electromagnetic shielding efficiency of the fabric are gradually increased.
Examples 6 to 11
Compared with the embodiment 1, the difference of the preparation method of the elastic electromagnetic shielding fiber is that in step S21, the proportions of polyurethane, polyacrylonitrile and ferroferric oxide nanoparticles are different, and the others are substantially the same as those in the embodiment 1, and are not repeated herein.
As shown in Table 2, 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 were measured, and the frequency of the electromagnetic waves was 20MHz to 2 GHz. (the fabric is made directly by the knitting machine)
Table 2 data on elastic electromagnetic shielding fibers prepared in examples 6 to 11
As can be seen from table 2, as the polyacrylonitrile content increases (examples 1, 6, 7), the elastic elongation of the prepared fiber, the electromagnetic shielding effectiveness of the fabric, and the electromagnetic shielding efficiency all gradually decrease. This shows that the addition of polyacrylonitrile, although beneficial to spinning the fiber, can enhance the strength of the fiber, but its content has an influence on the properties of the fiber and its fabric.
With the increase of the content of the ferroferric oxide nanoparticles (examples 6, 8 and 9), the elastic elongation of the prepared fiber is reduced, and the electromagnetic shielding effectiveness and the electromagnetic shielding efficiency of the fabric are gradually increased. The reason is mainly that the elastic deformation of the skin layer material is reduced along with the increase of the content of the ferroferric oxide nano particles, so that the elastic elongation of the fiber is reduced, but the conductivity and the magnetic conductivity of the skin layer are increased, so that the electromagnetic shielding efficiency and the electromagnetic shielding efficiency of the fabric are gradually increased.
As the content of the polyurethane increases (examples 1, 10, 11), the elastic elongation of the prepared fiber increases, and the electromagnetic shielding effectiveness and the electromagnetic shielding efficiency of the fabric gradually decrease.
Examples 12 to 16
Compared with embodiment 1, the difference between the preparation method of the elastic electromagnetic shielding fiber and the embodiment 1 is that in step S31, the rotational speed of the centrifugal spinning, the rotational speed of the core layer collecting line and the collecting distance are different in the centrifugal spinning process, and the others are substantially the same as those in embodiment 1, and are not repeated herein.
As shown in Table 3, for the elongation of the elastic electromagnetic shielding fibers prepared in examples 12 to 16 and the data (electromagnetic shielding effectiveness and electromagnetic shielding efficiency) regarding the electromagnetic shielding of the fabrics prepared from the elastic electromagnetic shielding fibers, the frequency of the electromagnetic wave was 20MHz to 2 GHz. (the fabric is made directly by the knitting machine)
Table 3 data on elastic electromagnetic shielding fibers prepared in examples 12 to 16
As can be seen from table 3, as the rotational speed of the centrifugal spinning and the rotational speed of the core layer collecting line are increased simultaneously (examples 1 and 14), the elastic elongation of the prepared fiber, the electromagnetic shielding effectiveness of the fabric, and the electromagnetic shielding efficiency do not change much, which indicates that when the rotational speed of the centrifugal spinning and the rotational speed of the core layer collecting line are matched, and the core layer and the skin layer are both at appropriate rotational speeds, the obtained fiber has good uniformity of pores and components, so that the structure of the fiber is good, and further the performance of the fabric is good. When the spin speed is lower and the core collector speed is higher (example 15), the properties of the fibers and fabrics produced are affected. When the rotation speed of the centrifugal spinning and the rotation speed of the core layer collecting wire are reduced simultaneously (example 16), the elastic elongation of the prepared fiber is better, and the electromagnetic shielding effectiveness and the electromagnetic shielding efficiency of the fabric are reduced, which is mainly because the obtained skin-core structure is different along with the reduction of the rotation speed of the centrifugal spinning and the rotation speed of the core layer collecting wire, thereby affecting the performance of the fabric.
As the collection distance increases (examples 1, 12, 13), the elastic elongation of the prepared fiber increases, and the electromagnetic shielding effectiveness and efficiency of the fabric decrease.
Comparative example 1
Compared with the embodiment 1, the preparation method of the elastic electromagnetic shielding fiber is characterized in that the core layer only comprises polyurethane fibers, the outer layer is not coated with copper wires, and the polyurethane fibers are directly used as the core layer collecting wires to obtain the elastic electromagnetic shielding fiber. The elongation of the elastic electromagnetic shielding fiber is 24.7 percent, and the elongation is increased; the electromagnetic shielding effectiveness of the fabric is 22dB, the electromagnetic shielding efficiency is 81.9%, and the electromagnetic shielding effectiveness and the electromagnetic shielding efficiency of the fabric are obviously reduced, which shows that only the skin layer conductive fiber and the single fiber have poor conductive performance, so that 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 characterized in that the core layer material only contains copper wires and does not contain polyurethane, and the thin and straight copper wires are directly used as the core layer collecting wires to obtain the elastic electromagnetic shielding fiber. The elongation of the elastic electromagnetic shielding fiber is 18.9%, the electromagnetic shielding efficiency of the fabric is 33dB, the electromagnetic shielding efficiency 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 wire, a conductive layer formed by a conductive substance is more compact, so that the electromagnetic shielding performance of the manufactured fabric is better. The elongation is significantly reduced, which indicates that the linear copper wire limits the elastic properties of the fiber.
Comparative example 3
Compared with the embodiment 1, the preparation method of the elastic electromagnetic shielding fiber is characterized in that polyacrylonitrile is not contained in a skin layer, only polyurethane and ferroferric oxide nano particles are contained, and the ferroferric oxide nano particles still keep the original mass ratio to obtain the elastic electromagnetic shielding fiber. The elastic electromagnetic shielding fiber has the elongation of 39.9 percent, the electromagnetic shielding efficiency of 37dB and the electromagnetic shielding efficiency of 96.98 percent, although various performances of the fiber and the fabric are improved, polyacrylonitrile does not exist, the spinning process is not easy to control, and the strength of the fiber is obviously poor.
Comparative example 4
Compared with the embodiment 1, the preparation method of the elastic electromagnetic shielding fiber is characterized in that the ferroferric oxide nanoparticles in the skin layer are replaced by graphene to obtain the elastic electromagnetic shielding fiber. The elongation of the elastic electromagnetic shielding fiber is 20.3%, the electromagnetic shielding effectiveness of the fabric is 30dB, the electromagnetic shielding efficiency is 91.09%, and the electromagnetic shielding performance of the fabric is reduced, which shows that magnetic conductivity particles (both conducting and magnetic conductivity) have positive effects on the electromagnetic shielding performance of the fabric, and further shows that the conductivity and high magnetic conductivity particles synergistically improve the electromagnetic shielding effectiveness 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 type collection, so that the cortical layer fiber is uniformly and densely and transversely wound on the core layer, the single fiber is interlaced to different degrees, and the cortical layer fiber wound at different parts of the core layer is uniformly distributed, thereby obtaining the elastic electromagnetic shielding fiber with a special structure with uniform pore distribution and uniform thickness; the fibrous core layer and the skin layer can be conductive, the copper wires of the core layer and the conductive particles of the skin layer are uniformly distributed in the fibrous core layer and the skin layer, so that the conductive performance of the obtained fiber is excellent, and the prepared fabric forms a compact and uniform conductive layer by combining a special surface structure with uniform pore distribution and uniform thickness, and the uniform pores have a certain reflection effect on electromagnetic waves, so that the electromagnetic shielding performance of the fabric is excellent.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A preparation method of elastic electromagnetic shielding fiber is characterized by comprising the following steps: firstly, preparing a core layer, then adopting a centrifugal spinning self-rolling type collection method to take the core layer as a self-rolling type collection unit, and then 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 type collection method comprises the following steps:
s1, preparing a spinning solution;
s2, carrying out centrifugal spinning on the spinning solution prepared in the step S1 through a centrifugal spinning device for self-winding collection, and winding the spun fibers on a self-winding collection unit capable of rotating automatically.
2. The method for preparing an elastic electromagnetic shielding fiber according to claim 1, wherein: the core layer comprises elastic fibers and high-conductivity metal wires spirally wound on the surfaces of the elastic fibers.
3. The method for preparing an elastic electromagnetic shielding fiber according to claim 1, wherein: the skin layer comprises an elastic material, polyacrylonitrile and high-permeability particles; 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.
4. The method for preparing an elastic electromagnetic shielding fiber according to claim 1, wherein: the method comprises the following steps:
s11, spirally winding a metal wire on the surface of the elastic fiber 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 0.1-2 mm;
s21, mixing the elastic material, polyacrylonitrile and high-permeability particles according to a certain proportion, uniformly dispersing the mixture in an organic solvent, and performing 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-winding type collected centrifugal spinning device, and winding the cortex fibers on the core layer which is prepared in the step S11 and can rotate until the core layer is completely wrapped by the cortex, so that the elastic electromagnetic shielding fibers are obtained.
5. The method of preparing an elastic electromagnetic shielding fiber according to claim 4, wherein: in the step S31, the rotation 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 30-300 r/min.
6. The method of preparing an elastic electromagnetic shielding fiber according to claim 4, wherein: in step S31, the spinning aperture of the centrifugal spinning is 0.1-1mm, and the collection distance is 7-20 cm; in step S21, the concentration of the skin layer spinning solution is 20 wt% to 30 wt%.
7. The method for preparing an elastic electromagnetic shielding fiber according to claim 4, wherein: 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 vulcanizate; the high magnetic permeability particles comprise one or more of ferroferric oxide nanoparticles, ferric oxide nanoparticles and cobalt oxide nanoparticles; the organic solvent is a good solvent of polyacrylonitrile and elastic materials, and is preferably one or more of N, N-dimethylformamide and N, N-dimethylacetamide.
8. An elastic electromagnetic shielding fiber, characterized in that: the elastic electromagnetic shielding fiber is prepared by the preparation method of any one of claims 1 to 7.
9. An elastic electromagnetic shielding fiber according to claim 8, wherein: the elongation of the elastic electromagnetic shielding fiber is 10-35%, the electromagnetic shielding efficiency of a fabric prepared from the elastic electromagnetic shielding fiber is 30-40dB, and the electromagnetic shielding efficiency is 90-99%.
10. Use of an elastic electromagnetic shielding fiber prepared by the method for preparing an elastic electromagnetic shielding fiber according to any one of claims 1 to 7 or the elastic electromagnetic shielding fiber according to any one of claims 8 to 9, wherein: the elastic electromagnetic shielding fiber is applied to the preparation of electromagnetic shielding materials.
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