KR101757045B1 - manufacture method of bulletproof glass using ferroelectrics - Google Patents
manufacture method of bulletproof glass using ferroelectrics Download PDFInfo
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- KR101757045B1 KR101757045B1 KR1020150084211A KR20150084211A KR101757045B1 KR 101757045 B1 KR101757045 B1 KR 101757045B1 KR 1020150084211 A KR1020150084211 A KR 1020150084211A KR 20150084211 A KR20150084211 A KR 20150084211A KR 101757045 B1 KR101757045 B1 KR 101757045B1
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- azobenzene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
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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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D47/00—Looms in which bulk supply of weft does not pass through shed, e.g. shuttleless looms, gripper shuttle looms, dummy shuttle looms
- D03D47/28—Looms in which bulk supply of weft does not pass through shed, e.g. shuttleless looms, gripper shuttle looms, dummy shuttle looms wherein the weft itself is projected into the shed
- D03D47/30—Looms in which bulk supply of weft does not pass through shed, e.g. shuttleless looms, gripper shuttle looms, dummy shuttle looms wherein the weft itself is projected into the shed by gas jet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
Abstract
The present invention relates to a method of manufacturing a bulletproof glass using a ferroelectric material. In the method for manufacturing a bulletproof glass according to an embodiment of the present invention, the bulletproof glass includes a plurality of tempered glass joined to a plurality of layers; A plurality of polyethylene film layers laminated and disposed between the plurality of tempered glasses; And a ferroelectric layer disposed between at least a portion of the plurality of tempered glass and the plurality of polyethylene film layers.
Description
The present invention relates to a method of manufacturing a bulletproof glass using a ferroelectric material.
In 1920, this substance was first discovered in the substance called the shelled salt. When an electric field is applied to a material, the dipole moment generally occurs due to the electric field, resulting in electric polarization. However, there is a certain substance that spontaneously undergoes electric polarization even when no electric field is applied. This substance is called a ferroelectric substance.
That is, the ferroelectric (ferroelectrics) are materials that have electrical polarization in the natural state. These materials, which exhibit spontaneous polarization, exclude that the direction of polarization does not change in the electric field, and they exhibit piezoelectricity and superconductivity by changing polarization.
A ferroelectric is a type of dielectric that is an electrically insulating material and has a specific physical property.
Also, unlike ordinary dielectrics, dielectric polarization is not proportional to the electric field, and the relationship between the polarization and the electric field, like the ferromagnetic material, is characterized by hysteresis and saturation. To date, more than one hundred and dozens of ferroelectric materials have been discovered.
These materials are characterized not only by spontaneous polarization but also by the fact that this spontaneous polarization is reversed by an electric field.
There are many materials that have spontaneous polarization among dielectrics, but they can not be said to be ferroelectric unless they can change the direction of polarization by the electric field.
The ferroelectric exhibits a phase transition at the Curie temperature. Under the phase transition temperature, the spontaneous polarization is arranged in a specific direction through the interaction between the electric dipoles, and the spontaneous polarization is lost due to the thermal fluctuation above the temperature.
Under the Curie temperature, the spontaneous polarization is aligned in a certain direction, but a domain is formed together.
The physical properties of the ferroelectric material are piezoelectric and pyroelectric due to the reversal phenomenon of the spontaneous polarization.
Using this characteristic of the ferroelectric, it is possible to develop GPS, which is a position tracking device using a personal portable night vision goggle or satellite, and a device for securing a night vision of a car.
The ferroelectric has a high refractive index and a large nonlinear optical constant because of its excellent optical properties.
Utilizing these characteristics, it can be applied to an optical waveguide, and the frequency of the laser can be doubled.
In addition, the ferroelectric material has a large piezoelectric constant, so it is widely used in acoustic machines and is also used as a dielectric of a small capacitor by using a large dielectric constant.
On the other hand, bulletproof products are products for protecting the human body from bullets and shells, and have good bulletproof performance and good fit feeling. However, in order to improve the bulletproof performance, it was common that the feeling of wearing the bulletproof product was sacrificed to some extent.
On the contrary, it has been common that the improvement in the wearing comfort of the bulletproof article causes a decrease in the bulletproof performance.
It is known to use unidirectional fabrics for lightening bulletproof products and improving bulletproof performance.
US Patent Publication No. US2011 / 0219943 proposes a composite fabric including both high-strength fiber fabrics and unidirectional fabrics of high-strength fibers in order to improve the bulletproof performance. The publication teaches that it is preferred that the fabric of the composite fabric is not coated with a matrix resin, and that when coated, it is preferably coated with a matrix resin having the same or similar chemical structure as the unidirectional matrix resin (See paragraph [0054]), a bulletproof article including both a fabric and a unidirectional fabric may have better bulletproof performance than a bulletproof article including only unidirectional fabrics, as well as further reduce the rearward deformation due to a bullet impact (See paragraph [0054]).
Although the composite fabric proposed by the above publication exhibits excellent anti-bullet properties, there still remains room for improvement in terms of antitrauma.
For this reason, a method has been proposed in which a polypropylene film is adhered to the back surface of a material for improving the rear surface deformation characteristics of the bulletproof material. However, there is a problem in that the armor made of a bulletproof material having a polypropylene film adhered to the polypropylene film due to its rigid characteristics is not good fit.
Accordingly, there is a need for a method for solving the above-mentioned problem through a method for manufacturing a bulletproof glass using a ferroelectric material.
It is an object of the present invention to provide a method of manufacturing a bulletproof glass using a ferroelectric material to a user. Specifically, unlike the conventional method of making a bullet-proof glass by bonding tempered glass and polyethylene through an adhesive, a reinforced glass including a piezoelectric material such as a ferroelectric material is provided to simplify the process, reduce costs, The purpose is to provide users with more effective bulletproof glass.
It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are not intended to limit the invention to the precise form disclosed. It can be understood.
In the method for manufacturing a bulletproof glass according to an embodiment of the present invention for realizing the above-described problems, the bulletproof glass includes a plurality of tempered glass joined to a plurality of layers; A plurality of polyethylene film layers laminated and disposed between the plurality of tempered glasses; And a ferroelectric layer disposed between at least a portion of the plurality of tempered glass and the plurality of polyethylene film layers.
The bulletproof glass may further include carbon nanotubes (CNTs).
Further, the bulletproof glass may further include graphene.
In addition, a layer of a highly transparent polycarbonate film, a layer of a polyester film laminated with the polycarbonate film layer, and a layer of a PVB film (polyvinyl butyral film) formed by bonding to the polyester film layer .
Also, the ferroelectric layer is manufactured through a carbon fiber manufacturing method, and at least one of rolling, extruding, and drawing can be used as the carbon fiber manufacturing method.
Also, the carbon fiber manufacturing method may use an air jet loom in which the stopping angle at the opening of the heald is within a predetermined range at the time of weaving.
Further, in the method for producing carbon fiber, a separate weave is simultaneously formed by using a weft yarn which is formed by weaving a carbon fiber fabric at an end portion of the weaving carbon fiber fabric opposite to the weft insertion side at the same time, The weft yarns may be cut between the carbon fiber fabrics to separate the carbon fiber fabrics from the separate fabrics and twist the separate fabrics.
In addition, the method of manufacturing carbon fibers may guide the separate tissue so that the distance between the separate tissue and the carbon fiber fabric becomes wider after the separate tissue is formed or after being weighed.
Further, in the above-mentioned method for producing a carbon fiber, a tubular body is disposed such that the axis crosses the non-continuous direction of the weft yarn on the side opposite to the weft insertion side of the woven carbon fiber fabric, or a tubular body , The weft yarn inserted to form the carbon fiber fabric can be passed from one opening of the tubular body to the other opening.
Further, in the method of manufacturing carbon fibers, the separate tissue may be passed through a guide having a hole, and the guide may be rotated to twist the separate tissue.
Further, the carbon fiber fabric may be a plain weave, a twill or a water-based weave, and the separate weave may be plain weave, leno weave, or a combination thereof.
In addition, the polyethylene fiber is an ultrahigh molecular weight polyethylene fiber, and the at least one of the polyethylene fiber and the aramid fiber, the ferroelectric layer, and the polybenzoxazole fiber may be used to produce the bulletproof fabric.
The method may further comprise: fabricating the fabric using at least one of the polyethylene fiber and the aramid fiber, the ferroelectric layer, and the polybenzoxazole fiber; Preparing a water repellent agent comprising a fluorocarbon and a hardness-reinforced resin; Applying the water repellent agent to the fabric; And heat treating the raw fabric to which the water-repellent agent is applied.
The hardness-reinforced resin may be a polyvinyl acetate resin, a polyester resin, a polyacrylate resin, a melamine resin, or a mixture of two or more thereof.
Further, the step of applying the water repellent agent to the fabric may be performed by padding, coating, dipping, spraying, or brushing.
Further, before applying the water repellent agent to the fabric, refining the fabric with a scouring agent including a surfactant may be further included.
The water repellent agent may further include a crosslinking agent.
Further, the crosslinking agent may be an isocyanate compound, and the hardness-reinforcing resin may be a polyvinyl acetate resin.
Also, the ferroelectric layer is a PVDF-azobenzene polymer film, and the method of producing the PVDF-azobenzene polymer film includes: a first step of polymerizing PVDF and azobenzene to prepare a PVDF-azobenzene polymer solution; A second step of applying the PVDF-azobenzene polymer solution on a substrate; A third step of evaporating the solvent of the PVDF-azobenzene polymer solution to form a PVDF-azobenzene polymer film; And a fourth step of separating the substrate from the PVDF-azobenzene polymer film.
In the first step, any one of a method of mixing the PVDF solution and the azobenzene solution, a method of dispersing the azobenzene in the PVDF solution, and a method of dispersing the PVDF in the azobenzene solution may be used.
The solvent of the PVDF solution may be at least one of MIBK, MEK, N-methyl-2-pyrrolidone, DMF and DME .
Further, the solvent of the azobenzene solution can be used for polarity use every day.
The solvent of the azobenzene solution may be at least one of ethyl acetate, THF (tetrahydrofuran), butyl alcohol, IPA (isopropyl antipyrine), acetone, and acetonitrile.
In addition, the first step may include dispersing carbon nanotubes (CNTs) in the PVDF-azobenzene polymer solution.
The carbon nanotubes may be present in an amount of 0.01 to 0.1% by weight based on the PVDF-azobenzene polymer solution.
The method may further include, after the first step, irradiating the PVDF-azobenzene polymer solution with visible light.
In addition, the first step may include dispersing metal particles in the PVDF-azobenzene polymer solution.
In the second step, at least one of a method of using an applicator, a method of using a bar coater, and a spin coating method may be used.
In addition, the substrate may be made of a hydrophilic coating-treated material.
In addition, the substrate may be made of glass or polymer.
In addition, in the third step, it is possible to cause a gas flow over the PVDF polymer solution to induce uniform volatilization of the solvent.
Also. The gas may be an inert gas.
Further, after the third step, a step of bonding the support film to the PVDF-azobenzene polymer film may be further included.
In addition, the support film may include at least one of silicone elastomer and polydimethylsiloxane (PDMS).
The support film may be formed by coating at least one of silicone elastomer and polydimethylsiloxane (PDMS) on a PET (polyethylene terephthalate) film.
Further, the method may further include the step of weakening the adhesive force between the PVDF-azobenzene polymer film and the substrate before the fourth step.
Further, in the step of weakening the adhesion between the PVDF-azobenzene polymer film and the substrate, a wetting environment can be provided to the substrate and the PVDF-azobenzene polymer film.
The wetting environment may be water, distilled water, deionized water or IPA (isopropyl alcohol).
Further, after the fourth step, an annealing process may be further performed.
Further, after the fourth step, an electrical poling process may be further performed.
SUMMARY OF THE INVENTION The present invention has been made in order to solve the above problems, and it is an object of the present invention to provide a method of manufacturing a bulletproof glass using a ferroelectric material. Specifically, unlike the conventional method of making a bullet-proof glass by bonding tempered glass and polyethylene through an adhesive, a reinforced glass including a piezoelectric material such as a ferroelectric material is provided to simplify the process, reduce costs, More effective bulletproof glass can be provided to the user.
It should be understood, however, that the effects obtained by the present invention are not limited to the above-mentioned effects, and other effects not mentioned may be clearly understood by those skilled in the art to which the present invention belongs It will be possible.
BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate preferred embodiments of the invention and, together with the description, serve to further the understanding of the technical idea of the invention, It should not be construed as limited.
Fig. 1 is a flowchart for explaining a method for manufacturing a bulletproof glass according to the present invention.
2 to 5 show an example of a cross-sectional view of a bulletproof material manufactured according to the present invention.
6 is an example of a characteristic graph showing voltage-capacitance characteristics of a general organic material.
7A and 7B are graphs showing characteristic graphs showing voltage-capacitance characteristics of the ferroelectric organic material applied to the present invention.
8A and 8B show an example of a characteristic graph showing other voltage-capacitance characteristics of the ferroelectric organic material applied to the present invention.
9 is a plan view showing the positional relationship among various nozzles and tubular bodies in an air jet loom relating to the first embodiment of the ferroelectric fiber production of the present invention.
10 is a schematic vertical cross-sectional view of an RTM molding apparatus according to a second embodiment of the ferroelectric fiber manufacturing method of the present invention.
11 is a schematic view showing an example of a container according to a third embodiment of the ferroelectric fiber production of the present invention.
12 is a view showing a method of manufacturing a metal fiber in which a concave-convex shape is formed using a spur gear according to a fourth embodiment of the ferroelectric fiber fabrication method of the present invention.
13 is a flowchart showing a method for producing a PVDF-azobenzene polymer film according to an embodiment using azobenzene of the present invention.
Figures 14a-14c illustrate the preparation of a PVDF-azobenzene polymer solution according to one embodiment of the present invention using azobenzene.
15A shows the chemical structure of the trans-form azobenzene, and Fig. 15B shows the chemical structure of the cis-form azobenzene.
Figure 16 is a diagram illustrating the application of visible light to a PVDF-azobenzene polymer solution according to one embodiment of the present invention using azobenzene.
Figure 17a shows a PVDF-azobenzene polymer solution applied to a substrate in accordance with one embodiment of the present invention, Figure 17b illustrates the formation of a PVDF-azobenzene polymer solution in a uniform thickness using an applicator according to one embodiment of the present invention Lt; / RTI >
Figure 18 shows that the solvent of the PVDF-azobenzene polymer solution is evaporated according to one embodiment of the present invention using azobenzene.
Figure 19 shows that the support film is bonded to the PVDF-azobenzene film in accordance with one embodiment of the present invention using azobenzene.
Figure 20 shows the creation of a wet environment for separating films according to one embodiment using the azobenzene of the present invention.
FIG. 21A shows that the PVDF-azobenzene polymer film is separated from the substrate according to one embodiment of the present invention, and FIG. 21B shows that the PVDF-azobenzene polymer film prepared according to one embodiment using the azobenzene of the present invention is bonded to the transfer film (TF).
Figure 22 is a chemical structure of PVDF-azobenzene prepared according to one embodiment of the present invention.
23 is another chemical structure of PVDF-azobenzene prepared according to one embodiment of the present invention.
Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. In addition, the embodiment described below does not unduly limit the content of the present invention described in the claims, and the entire structure described in this embodiment is not necessarily essential as the solution means of the present invention.
Prior to a specific description of the present invention, a method for producing a bulletproof glass will be described in detail. A method for manufacturing a bulletproof film to be applied to a bulletproof glass will be specifically described.
For convenience of explanation, it is assumed that the bulletproof film is made of a bulletproof helmet, but the contents of the present invention are not limited thereto.
1 shows an exploded cross-sectional view of a composite fabric according to the present invention.
The present invention relates to a ballasted fiber impregnation step (ST1) for impregnating a phenolic resin with a bulletproof fiber supplied from a supply roller; A step (ST2) of cutting and cutting the anti-armor fiber to cut the anti-armor fiber into a helmet shape so as to form a helmet shape; A step (ST3) of cutting and cutting a bulletproof film to cut the bulletproof film to the same size as the bulletproof fiber and cut it radially so as to form a helmet; An adhesive applying step (ST4) of applying an adhesive to both sides of the ballistic film; A stacking step (ST5) of laminating the anti-armor fibers in a plurality of layers inside the mold so that at least one anti-bulletproof film is sandwiched between the anti-armor fibers to be laminated; A molding step (ST6) for pressing and fixing the bulletproof fiber and the bulletproof film with a presser which dissipates heat at a high temperature so as to fix the bulletproof fiber and the bulletproof film; (ST7) cutting a bottom edge of the bulletproof film and the bulletproof film to produce a semi-finished article; (ST8) of completing a bulletproof helmet by coating the surface of the semi-finished product with a chin-fixing strap and a head-fixing strap secured to the inside thereof.
The bulletproof film is laminated in the form of a helmet.
The anti-armor fiber is formed of at least one of aramid fiber, nylon fiber, polyethylene fiber, or glass fiber.
The bulletproof film is formed of PETG (Polyethylene Terephthalate Glyco) film.
First, if the anti-armor fiber supplied from the supply roller is impregnated with the phenol resin stored in the storage tank, the anti-armor fiber absorbs the phenolic resin.
Herein, the content of the phenolic resin impregnated in the bulletproof fiber can be controlled within a range of 5 to 20% of the weight of the bulletproof fiber, but it is preferable to appropriately adjust it according to the manufacturing method.
It is preferred that the anti-armor fibers use aramid fibers.
As described above, a plurality of the anti-fogging fibers impregnated with the phenolic resin are cut into a predetermined size, and the edges are radially cut so as to easily deform the cut anti-armor fibers into a helmet shape.
Further, after the bulletproof film is cut to the same size as the bulletproof fiber, the edge is radially cut so as to be easily deformed into a helmet shape.
The adhesive agent is applied evenly on both sides of the bulletproof film thus cut.
The adhesive used for the bulletproof film is preferably polyvinyl acetade.
The bulletproof fiber and the bulletproof film were laminated in a helmet-shaped jig. First, seven bulletproof fibers were laminated inside the mold, one bullet-proof film coated with an adhesive was laminated on the bulletproof fiber, Seven sheets are laminated in order.
When the power is applied to the press in a state where the anti-armor fiber and the anti-armor film are laminated inside the mold as described above, the press presses the anti-armor fiber at the upper portion and at the same time, the high temperature heat emitted from the press is absorbed The melted phenolic resin is melted and the bulletproof fiber and the bulletproof film are fixed in a helmet shape.
When the edge parts of the bulletproof fibers and the bulletproof film which are fixed as described above are not cut, the helmet-shaped semi-finished product is completed.
The surface of the semi-finished product is coated with a coating agent so as not to cause gloss, and then the jaw of the wearer is fixed to the inside of the semi-finished product to fix the jaw fixing strap for preventing the bulletproof helmet from moving and the head fixing strap for fixing the head are fixed The manufacture of the bulletproof helmet is completed.
In another embodiment of the present invention, the bulletproof fiber and the bulletproof film are laminated in a helmet-shaped jig, and three bulletproof fibers are laminated first When one bulletproof film is laminated, the bulletproof film is bonded to the bulletproof fiber by an adhesive.
On the other hand, three bulletproof fibers are laminated again on the bulletproof film, and then one bulletproof film is laminated again.
If the above lamination process is repeated one more time, the total number of bulletproof fibers is twelve, and a total of three bulletproof films are laminated therebetween.
In addition, although the above-described anti-armor fiber of the present invention is described as laminating only aramid fiber, the anti-armor fiber may be laminated with aramid fiber and glass fiber at a ratio of 50:50.
First, when three pieces of aramid fibers are laminated in the interior of a jig, and one laminate of a bulletproof film coated with an adhesive on both sides is laminated, the aramid fiber and the bulletproof film are bonded together by an adhesive.
Further, three glass fibers are laminated on the top of the bulletproof film, and then one bulletproof film is laminated again.
When the above lamination process is repeated one after another, the aramid fiber and the glass fiber are sequentially laminated by six sheets, and a total of three bulletproof films are laminated between the aramid fiber and the glass fiber.
If the aramid fiber and the glass fiber are stacked as described above and the power is applied to the press to operate the press, the press will press the aramid fiber, the glass fiber and the bulletproof film at the top, and at the same time, The phenolic resin absorbed by the fibers is melted and fixed in a helmet shape to be molded.
Meanwhile, a method for manufacturing a bulletproof material to be applied to another bulletproof glass which can be applied to the present invention will be described.
2 is a sectional view of a bulletproof material according to a first embodiment of the present invention.
As illustrated in FIG. 2, the
The
The first
According to a first embodiment of the present invention, the network of high strength fibers is an aramid woven fabric comprising aramid fibers in warp and weft. Each of the fabrics has a surface density of 150 to 500 g / m. If the area density is less than 150 g /
On the other hand, since the aramid fiber is vulnerable to moisture, the bulletproof performance may deteriorate with time. To solve this problem, the aramid fabric of the first
The fluorocarbon serves to impart water repellency to the first fibrous layers 110. As the fluorocarbon, hydroxylated perfluoroalkylethyl acrylate copolymer may be used.
On the other hand, the water repellent component such as fluorocarbon is removed from the network of high-strength fibers under harsh environments or after long-term use, which may lead to a drop in the physical properties of the high-strength fibers due to moisture and a sharp drop in the bulletproof performance. Therefore, in order to enhance the bond between the high-strength fiber and the fluorocarbon, the water-repellent agent may further comprise a crosslinking agent such as an isocyanate-based compound such as toluene diisocyanate or methylene diphenyl diisocyanate in addition to the fluorocarbon.
Further, in order to suppress the rear surface deformation of the
Alternatively, the water repellent agent may further comprise an antifoaming agent (for example, dipropylene glycol) and an emulsion stabilizer (for example, malic acid) for defoaming. In this case, the water repellent agent may comprise 0.5 to 10 wt% of fluorocarbon, 0.5 to 10 wt% of hardness-reinforced resin, 0.5 to 5 wt% of a crosslinking agent, 0.1 to 2 wt% of defoamer, 0.1 to 2 wt% of emulsion Stabilizer, and 73 to 98.3 wt% water.
When the content of fluorocarbon is less than 0.5% by weight, the desired water repellency is difficult to expect. When the content exceeds 10% by weight, the water repellency is not increased, and the flexibility of the
When the content of the hardness-reinforced resin is less than 0.5% by weight, improvement in the rear surface deformation properties of the
When the content of the cross-linking agent is less than 0.5% by weight, it is difficult to maintain the desired water repellency. When the content of the cross-linking agent is more than 5% by weight, the effect is not exerted.
Methods such as padding, coating, dipping, spraying, brushing, or film-coating may be used as a method for applying the water repellent agent on the network of high-strength fibers. After the water repellent agent is applied to the network, the heat treatment process may be performed at 120 to 200 ° C for 15 to 150 seconds.
Alternatively, the network of high strength fibers of the first
Alternatively, the unidirectional fabric may be composed of four fibrous layers each comprising an ultra-high density polyethylene fiber or an aramid fiber arranged in one direction. In this case, the four fibrous layers may be cross-bonded such that the rotation angle of their high-strength fibers is 0 ° / 90 ° / 0 ° / 90 °.
The
The
The front face FS of the
According to the present invention, since the carbon fiber network of the
Optionally, the network of carbon fibers may be coated with a composition comprising a phenolic resin and a polyvinyl butyral resin. Specifically, the composition may comprise 20 to 70 wt% of a phenolic resin, 20 to 70 wt% of a polyvinyl butyral resin, and 1 to 10 wt% of a plasticizer. The plasticizer may be dioctyl phthalate (DOP), dioctyl adipate (DOA), tricresyl phosphate (TCP), or diisononyl phthalate (DINP). The phenolic resin of the composition further improves the hardness of the
Examples of the method of coating the network of carbon fibers with the composition include a method of immersing the network in a solution containing the composition and a method of laminating the composition on a network of the carbon fibers in a film form.
First, the immersion method is described. The network of carbon fibers is dipped in the composition diluted with a solvent (for example, methanol) for 10 to 60 minutes. The dipping process may be repeated several times so that the entire network of carbon fibers can be uniformly impregnated with the composition. Then, the diluting solvent is removed by the dipping step through a drying step.
Optionally, prior to the drying step, a further step of squeegeeing the network of carbon fibers impregnated with the composition may be performed. The squeezing process may be performed continuously using a pressure roller, or may be performed discontinuously using a pressure plate.
The polymer film is then laminated onto one side of the network of carbon fibers. That is, the method comprises: placing the polymer film on one side of the network of carbon fibers; drying the network of carbon fibers on which the polymer film is placed at 20 to 60 ° C for 1 to 7 minutes; A network of carbon fibers and a step of applying pressure to the polymer film are sequentially performed. The drying process may be performed continuously using a chamber or the like.
In this case, the network of carbon fibers on which the polymer film rests may be allowed to pass through the chamber (s) maintained at 20 to 60 占 폚 at a rate of 4 to 20 m / min. If the drying temperature is lower than 20 ° C, drying can not be performed smoothly. If the drying temperature is higher than 60 ° C, the composition of the polymer film is hardened, and the adhesion with the
First, a composite sheet is formed by passing a network of carbon fibers coated with the composition, that is, a
Alternatively, the coating step and the composite sheet forming step may be performed simultaneously. That is, the polymer film is inserted between the network of carbon fibers and the
Hereinafter, a bulletproof material according to a second embodiment of the present invention will be described with reference to FIG.
3, the
According to a second embodiment of the present invention, the first and third
Meanwhile, the
The
After passing through the network of the carbon fiber coated with the composition, that is, the
Alternatively, the coating step and the composite sheet forming step may be performed simultaneously. That is, the polymer film of the composition is inserted between the network of carbon fibers and the
Hereinafter, a bulletproof material according to a third embodiment of the present invention will be described with reference to FIG.
4, the
According to a third embodiment of the present invention, the first and fourth
Meanwhile, the second and third fiber layers 320 and 330 include a network of carbon fibers. The network of carbon fibers may be a fabric comprising carbon warp yarns as warp and weft yarns and may be coated with a composition comprising a phenolic resin and a polyvinyl butyral resin.
The
The lamination / bonding method of the first to fourth fiber layers 310, 320, 330 and 340 is similar to the first and second embodiments described above. That is, after the composite sheet of one
In addition, the composition coating process for the carbon fiber networks constituting the second and the second fiber layers 320 and 330 may be performed simultaneously with the formation of each of the composite sheets.
Hereinafter, a bulletproof material according to a fourth embodiment of the present invention will be described with reference to FIG.
5, the
According to a fourth embodiment of the present invention, the first
The
Each of the third and fourth
The third and fourth fiber layers 431 and 432 adjacent to each other are cross-bonded to form an
First, a composite sheet is formed by passing a network of coated carbon fibers, that is, a
Alternatively, the coating step and the composite sheet forming step may be performed simultaneously. That is, a polymer film comprising the composition is inserted between the network of carbon fibers and the
Optionally, one or more unidirectional fabrics may be included between the composite sheet and the first fibrous layers 410.
Although not shown, one first fibrous layer, that is, an aramid fabric, may be further included between the
The
As described above, the
In addition, since the network of carbon fibers is relatively soft compared to a stiff material such as a polypropylene film which has been conventionally proposed for improving the rear deformation property, it is possible to provide a more comfortable feeling to the body armor than a polypropylene film.
However, in the case of the bulletproof glass according to the above-described method, a film must be formed with several layers of reinforced glass, polyethylene, aramid fiber, or the like as a bonding material, resulting in a problem that the energy efficiency is lowered and the thickness of the glass becomes thick.
Therefore, unlike the conventional method of making a bullet-proof glass by bonding tempered glass and polyethylene through an adhesive body, the present invention includes a piezoelectric material such as a ferroelectric material to form a tempered glass, thereby simplifying the process, reducing costs, We want to provide users with bullet proof glass.
The ferroelectric material applied to the present invention will be described in detail.
6 is an example of a characteristic graph showing voltage-capacitance characteristics of a general organic material.
7A and FIG. 2B are graphs showing characteristic graphs showing the voltage-capacitance characteristics of the ferroelectric organic material applied to the present invention, and FIGS. 8A and 3B are characteristic graphs showing other voltage-capacitance characteristics of the ferroelectric organic material applied to the present invention. It is an example.
Examples of the ferroelectric material include inorganic materials such as PZT, SBT and BLT.
However, such an inorganic material has a problem in that the polarity (polarization) characteristic is deteriorated with time and the data holding time is set to be long.
In addition, such an inorganic ferroelectric is expensive, requires high-temperature treatment for forming a thin film, and requires expensive equipment for film formation.
In addition to the above-mentioned inorganic substances, various kinds of organic substances having ferroelectric properties are known. Among them, polyvinylidene (PVDF), a polymer, a copolymer or a terpolymer containing the PVDF may be mentioned, and an odd number of nylon, a cyano polymer, and a polymer or copolymer thereof may be mentioned .
PVDF and polymers, copolymers, and terpolymers of these PVDFs have been extensively studied as materials for organic semiconductors.
Generally, in order to use a ferroelectric organic material as a material for a memory device, the organic material must have hysteresis polarity characteristics with respect to a voltage. However, in the case of the above-mentioned PVDF, as shown in FIG. 6, the capacitance increases according to the applied voltage, and does not have a hysteresis characteristic suitable for use in a memory device.
The inventors of the present application have found that PVDF has four kinds of crystal structures of alpha, beta, gamma and delta, and it has been confirmed that the crystal structure of beta phase has good hysteresis polarity. At this time, in order to determine the phase of the PVDF to be in the? -Phase, the PVDF is rapidly accelerated at a temperature of, for example, 60 to 70 占 폚, preferably about 65 占 폚, And the PVDF is determined to be the? Phase by the cooling method. However, the contents of these temperatures are only exemplary, and the contents of the present invention are not limited thereto.
FIG. 7 is a graph showing polarization characteristics with respect to a voltage of a PVDF thin film produced in accordance with the present invention. This graph shows a polarization characteristic of a PVDF thin film formed according to the present invention. The PVDF thin film has a? -Phase on a silicon substrate, an upper electrode is formed on the PVDF thin film, And the upper electrode are measured by applying a predetermined voltage.
Particularly, FIG. 7A shows a case where the thickness of the PVDF thin film is about 10 nm, and FIG. 7B shows the case where the thickness of the PVDF thin film is about 60 nm. These thin films are subjected to spin coating at 3,000 rpm or less, A PVDF thin film having a predetermined thickness is formed on the hot plate, and then the temperature of the PVDF thin film is monotonically decreased on a hot plate. Then, the PVDF thin film is rapidly cooled, for example, at a temperature of 65 ° C. However, the contents of these temperatures are only exemplary, and the contents of the present invention are not limited thereto.
As can be seen from FIG. 7, the PVDF thin film produced according to the present invention decreases in capacitance value as the applied voltage increases between about 0 V and about 1 V, and falls again between 0 V and -1 V The capacitance value is increased, and the hysteresis characteristic is good.
8A and 8B are graphs showing the measured values of the capacitance of the PVDF thin film formed over time according to the variation of time, and FIGS. 8A and 8B correspond to FIGS. 7A and 7B, respectively.
As can be seen from FIG. 8, it was confirmed that the PVDF thin film produced according to the present invention was kept constant over a certain period of time without changing its capacitance value with time.
Therefore, as shown in FIGS. 7 and 8, the PVDF thin film according to the present invention has the following characteristics.
First, the PVDF thin film according to the present invention exhibits a capacitance value higher than a predetermined value at 0V. This means that the polarization of the PVDF thin film is maintained unchanged even at 0V, where no external voltage is applied. That is, the PVDF thin film according to the present invention can be usefully used as a material of a nonvolatile memory.
Second, the PVDF thin film according to the present invention exhibits memory characteristics even within a range of 1 V or less. That is, data can be recorded and erased at a very low voltage. That is, the PVDF thin film according to the present invention can be advantageously used to implement a memory device operating at a low voltage.
Thirdly, the PVDF thin film according to the present invention has a characteristic in which the capacitance value thereof is kept unchanged with time.
That is, the PVDF thin film according to the present invention has excellent data retention characteristics for maintaining a data value once recorded for a predetermined time or more.
In the above description, it is assumed that the ferroelectric material to which the present invention is applied is PVDF and PVDF is applied to a memory device. However, the present invention is not limited thereto.
The above-mentioned bulletproof glass has been used to provide a bullet-proof function by stacking layers of aramid fiber, polyethylene or the like in layers and connecting them with an adhesive so as to form a multi-layered structure and dispersing impacts due to bullets or the like with thermal energy.
However, considering that the cost of the aramid fibers and polyethylene used in this method is high and the process for treating the fibers is complicated, the present invention proposes a method of reducing the use of aramid fibers and polyethylene and using a ferroelectric instead.
Piezoelectric elements such as ferroelectric are also referred to as piezoelectric elements.
Piezoelectricity is a phenomenon in which positive and negative electric charges proportional to external force appear on both sides of a plate when pressure is applied to certain types of crystal plates in a certain direction. In 1880, Jacque Curie and Pierre Curie (1859-1906) ) Brother first discovered it. After that, it is known that the piezoelectricity appearing on a single crystal plate is weak, but the amount of piezoelectricity is greatly increased when a plurality of sheets are stacked while inserting a metal foil.
It has also been found that there is inherent vibration in the crystal plate, and when the elastic vibration and the electric vibration are in agreement, they are combined with the piezoelectric vibration, resulting in stronger vibration. And there have been many inventions taking advantage of these phenomena.
As a result, crystals and barium titanate are widely used as piezoelectric elements in the pick-up of a microphone or a full-axis, a speaker of a telephone or a radio, an ultrasonic detector, a vibrator of a quartz watch, a broadcasting device, and a telecommunication circuit.
A device with a piezoelectric effect (a phenomenon where a voltage is generated when a mechanical pressure is applied and a mechanical deformation occurs when a voltage is applied), that is, when an external force is applied, electric polarization occurs and a potential difference is generated. .
Therefore, when a ferroelectric having such a piezoelectric effect is applied to fabricate a fiber, it is possible to provide a bulletproof function.
That is, the present invention proposes a method of using a ferroelectric material which reduces the use of aramid fibers and polyethylene and provides a bulletproof function by using a piezoelectric effect instead.
The present invention also proposes a method of manufacturing a ferroelectric substance that provides a piezoelectric effect.
Particularly, the present invention proposes a method of manufacturing a ferroelectric layer applied to a bullet-proof glass using a fiber manufacturing method.
The ferroelectric layer fabrication method proposed by the present invention can be explained by four examples.
(1) First embodiment: Manufacturing method of ferroelectric layer using carbon fiber manufacturing method
(2) Second embodiment: Method of manufacturing ferroelectric layer using FRP manufacturing method
(3) Third embodiment: Method of manufacturing ferroelectric layer using graphite fiber manufacturing method
(4) Fourth embodiment: A method for manufacturing a ferroelectric layer using a metal fiber manufacturing method
Best Mode for Carrying Out the Invention Hereinafter, each embodiment proposed by the present invention will be described with reference to the drawings.
1st Example
The first embodiment proposed by the present invention relates to a method of manufacturing a ferroelectric layer using a carbon fiber manufacturing method.
9 is a plan view showing the positional relationship among various nozzles and tubular bodies in an air jet loom relating to the first embodiment of the present invention.
In the present invention, when an unidirectional carbon fiber fabric is woven using a carbon fiber yarn having a fineness of 400 to 6,000 tex as a warp yarn and an auxiliary fiber having a fineness of 1/5 or less of the carbon fiber yarn as a weft yarn, Can be used.
In the case of producing a carbon fiber fabric using a shuttle loom or a looper loom, (1) when a shuttle loom or a looper loom is used, there is an upper limit of the physical speed for the weft insertion by the shuttle or rapier, 2) With regard to the insertion of the weft yarn, there was a problem that when the weft yarn was weighed at a high speed, the shuttle or the rapier and the warp yarn were in direct contact with each other, and the carbon fiber yarn was easily fuzzled.
However, by using an air jet loom, it is not affected by the physical speed of a shuttle, a rapier, or the like, and scratches with the warp, shuttle, rapier, or the like are essentially not generated.
If a water jet loom is used here, there is a possibility that the sizing agent (mostly water-soluble resin composition) previously attached to the carbon fiber yarn, which is a direct carbon fiber yarn, is unevenly separated and adhered, There is a problem.
In weaving using such an air-jet loom, the stopping angle of the handle at the opening of the handle is within a range of 0 to 50 degrees, preferably 0 to 25 degrees, more preferably 0 degrees. The smaller the stop angle, the better.
The heel stop angle means a position at which the movement (displacement) of the opening and closing port of the heddle is successively changed to the displacement when the one cycle of the repeated operation of the loom for inserting the weft yarn is divided by the rotation angle of the motor main shaft (crank) It refers to the angle of motionless range.
When a shuttle loom or a rapier loom is used, a shuttle or rapier, which is a weft inserting means, and a warp yarn group are locally contacted with each other, and the tension applied to each of the warp yarns loaded at the time of weaving can not be made uniform .
In addition, in order to insert a shuttle, reef, or the like into the lower part, the opening of the hood must be large and the hood must be kept open while the shuttle or lever is moving. Therefore, for example, in a general rapier loom, the stopping angle of the hand becomes 150 to 220 deg. As a result, the movement of the weaving becomes intermittent (discontinuous) motion, and the warp becomes unstable due to the tension or loosening of the warp, and it becomes one of the causes for making the tension in each warp uneven.
Because of this point, the difference in the length of the warp yarns in the resulting carbon fiber fabric is not more than 0.15%, and the coefficient of variation of the warp length is not more than 8%, and the stopped warp yarns start to move Since the carbon fiber yarn and the scratches of the heald are so large that a lot of fluffs are generated, it is difficult to obtain a durable fabric.
On the other hand, in the air jet loom, it is not necessary to keep the open state of the handle long. That is, by using the air jet loom, there is no physical contact between the weft inserting means and the warp group, and there is no need to stop the heald for a long time in order to maintain the open state. And the tension applied to each of the warp yarns loaded at the time of weaving can be made more uniform. As a result, a carbon fiber fabric having a difference in length of the warp yarn of 0.15% or less and a variation coefficient of the warp length of 8% or less can be easily obtained. More preferably, the difference in length of the warp yarn is 0.1% or less, more preferably 0.05% or less. A more preferable coefficient of variation is 6% or less, more preferably 4% or less. The difference in the lengths and the variation coefficient of the warp in the above range can suppress the irregularities of the fabric when the fabric is stretched on the floor to a minimum so that the appearance quality is excellent and when the obtained fabric is molded into CFRP, do. The difference in length of the warp yarns and the variation coefficient of the warp yarn length are measured in the following order.
(a) The carbon fiber cloth is allowed to stand at an unsprung time of 5500 mm to prevent loosening of the fabric.
(b) As a measurement standard, cut one place vertically to the longitudinal direction of the fabric.
(c) From the measurement standard, measure 5,000 mm for each of the warp yarns at both ends in the fabric width direction, and cut with a line connecting the points. At the time of measurement, the fabric is placed under an unsprung weight so that the fabric is not loosened, and the length of 5000 mm is measured with a long scale.
(d) While disassembling the fabric, the warp yarns are sequentially pulled out at intervals of 5 from the entire width of the fabric.
(e) Measure the length of the warp yarn to 0.1 mm. At the time of measurement, the tension is applied to the warp so that the warp yarn can not be warped.
(f) Calculate the difference between the maximum value and the minimum value of the warp length. The value obtained by dividing the calculated difference by 5000 mm and multiplying by 100 is taken as the difference in the warp length (unit:%).
(g) Calculate the standard deviation and mean value of all the values of the warp length measured. The calculated standard deviation is divided by the average value and multiplied by 100 is used as the coefficient of variation (unit:%).
Originally, air jet looms have been used in the industrial manufacture of bi-directional fabrics of glass fibers, but this is not the only reason why the glass fiber used has a high elongation at break of about 4%, which makes it difficult for fluff. In addition, since the fabric of the glass fiber used has a fineness of, for example, 8 to 100 tex and has a straight density (number of warp yarns, number of weft yarns), the amount of air injected from the weft yarn is minimized (FUTURE TEXTILES, p81-84, Horita-ruo, Textile Co., Ltd.), and the condition that the weaving of the weft (curvature) does not become present. On the other hand, in the present invention, the carbon fiber yarn used has a tendency to be fluffy as compared with glass fibers, and also has a stepwise fineness, and the fabrics to be produced are unidirectional fabrics. do.
Nevertheless, in the present invention, the unidirectional carbon fiber fabric is weaved with an air jet loom, and further, the unfavorable obstacle described above is solved to realize the weaving with an air jet loom.
In the carbon fiber fabric produced in the present invention, it is preferable that the warp density is 1 to 8 / cm and the weft density is 0.4 to 8 / cm.
More preferably a warp density of 2 to 6 yarns / cm, a weft yarn density of 1 to 6 yarns / cm, more preferably a warp density of 3 to 5 yarns / cm and a weft density of 2 to 5 yarns / cm . If the warp density is too small, not only the morphological stability of the carbon fiber fabric is deteriorated but also the warp gap becomes too large and the weft insertion efficiency of the air jet loom is excessively lowered.
On the other hand, if the warp density is too large, the number of fluffs due to scratching of the carbon fiber yarn increases, and the quality of the carbon fiber fabric may be deteriorated. In addition, if the weft density is too small, the morphological stability of the carbon fiber fabric is deteriorated, and the handleability of the resultant fabric tends to deteriorate. On the other hand, if the weft density is too large, it may be difficult to make the production speed of the carbon fiber fabric at a high speed, and sometimes the warp of the weft yarn can not be completely suppressed.
The method of producing a carbon fiber fabric of the present invention is suitable for producing a carbon fiber fabric having a warp gap of 0.1 to 0.8 mm, preferably 0.15 to 0.6 mm, more preferably 0.2 to 0.5 mm. If the clearance between the warp yarns is too small in the resulting fabric, there is a case where the napping due to scratching of the carbon fiber yarn is increased and the quality of the carbon fiber fabric is deteriorated. In addition, the carbon fiber fabric is woven, , The impregnation property of the matrix resin may be hindered when CFRP (carbon fiber reinforced plastic) is molded.
In the case of using an air jet loom, a sub nozzle (which will be described later in detail) protruding between carbon fiber yarns at the time of weaving is peeled from the carbon fiber yarn, .
On the other hand, when the clearance between the warp yarns is too large, the napping is suppressed, but the weft insertion efficiency is lowered. Further, when CFRP is molded, the resin rich portion is formed to be large and the mechanical properties of CFRP There may be a case where it is lowered.
In the present invention, a tubular body having both open ends is disposed on the side opposite to the weft insertion side (hereinafter referred to as " semi-weft insertion side ") of the woven carbon fiber cloth, It is preferable to let the uneven weft yarn pass from one opening of the tubular body to the other opening. The loosening of the weft can be prevented by the friction between the weft and the inner wall of the tubular body. The tubular body may be one in which the axis is curved in addition to the straight line, and the tubular body in which the axis is straight is arranged such that the axis intersects (does not become parallel to) the direction of the weft.
The
Here, the main nozzle is a nozzle which is disposed at the weft insertion side of the weaving machine and which first applies pressure to the weft yarn to be weighed. In order to further continuously highlight the weft yarn being displayed by the main nozzle, .
As the air jet loom used in the present invention, one main nozzle 12 is disposed on the weft insertion side A and a plurality of sub nozzles 12 are provided between the weft insertion side A and the half weft insertion side B 2a, 2b, ...) are arranged at intervals of one fabric width of 2 to 15 cm.
The preferred spacing of sub-nozzles is one per fabric width of 3-12 cm, and more preferably one per fabric width of 4-10 cm. The total number of sub nozzles varies depending on the fabric width, but is preferably in the range of 7 to 30 when the fabric width is 100 cm and in the range of 23 to 105 when the fabric width is 350 cm.
The arrangement of the plurality of sub nozzles 2a, 2b, ... is such that the width of the body inlet of the air jet loom is wide like the range described below (within the range of the body inlet width of 100 to 350 cm) It is desirable to make the distance between the sub nozzle at the shortest end of the half weft insertion side B and the sub nozzle adjacent thereto shorter than the distance between the sub nozzle at the shortest end in the side A and the sub nozzle adjacent thereto Do.
More specifically, the arrangement intervals L2 and L3 of the sub-nozzles are not widened toward the semi-weft insertion side B from the arrangement interval L1 between the sub-nozzles on the weft insertion side A .
More preferably, it is preferable to dispose the subnozzles so that the intervals between the subnozzles are shortened in accordance with the weft insertion direction. When the plurality of sub nozzles 2a, 2b, ... are arranged in this manner, not only the air from the main nozzle 12 can be utilized efficiently but also the weft in the weft insertion side B is stabilized And the weft insertion itself can be performed stably for a long period of time. Of course, the relationship between the arrangement distances L1 to L3 of these sub-nozzles is appropriately selected in accordance with the fabric width. For example, L1> L2> L3 or L1> L2 = L3.
In the present invention, as the air jet loom, a plurality of main nozzles arranged on the weft insertion side may be used. For example, it is preferable to use another main nozzle (auxiliary main nozzle 13) on the upstream side of the main nozzle 12 arranged on the weft inserting side A in the weft direction. More preferably, air is sprayed substantially simultaneously from each of the main nozzles 12 and the auxiliary main nozzles 13 to desirably weft the wefts. By using such an auxiliary main nozzle 13, there is no need to spray sudden air to the weft waiting for waiting for the next insertion. In other words, in the case where there is only one main nozzle, it is inevitable to increase the air pressure in order to spray air at one place of the weft. However, when the auxiliary main nozzle 13 is used in combination and a plurality of main nozzles are used, the air is sprayed at a plurality of points of the weft yarn, so that the air pressure can be lowered. As a result, it is possible not only to suppress the weft yarn breakage, the weft split, the scattering, the fuzz of the weft yarn, etc., but also the weft yarn which is difficult to be visually inspected, and can freely choose the weft yarn. In addition, spraying air at substantially the same time means spraying air within a range of 20 占 within the main axis (crank) angle of the loom.
Further, in the air jet loom, it is preferable that each sub nozzle is arranged so that the center of the sub nozzle and the center of the body blade are on substantially the same straight line parallel to the longitudinal direction of the fabric. In other words, the center of the
Further, in the present invention, the fact that the center of the sub nozzle and the center of the body wing are on substantially the same straight line parallel to the longitudinal direction is not limited to the state that they exist on the same straight line completely parallel to the longitudinal direction, Incidentally, as shown in Fig. 7, it is also assumed that there is a slight deviation as long as it does not cause a problem as shown in Fig. More specifically, it indicates that the center D1 of the
The body wing thickness of the body is preferably in the range of 0.1 to 2 mm, preferably 0.3 to 0.8 mm, more preferably 0.4 to 0.7 mm. If the thickness of the body wing is too small, the difference in the physical dimensions of the
It is preferable that the body stroke stroke amount D2 in the air jet loom is in the range of 50 to 150 mm, preferably 60 to 130 mm, and more preferably 70 to 90 mm. If the body stroke stroke amount D2 is too small, there is a case that a space for weft insertion can not be formed.
On the other hand, if the body stroke stroke amount D2 is too large, the motion of the body stroke itself becomes too large, which may impede the speeding up of the present invention. In addition, the carbon fiber yarn and the body wing tend to be scratched, The lint from the yarn can not be suppressed in some cases. The body stroke stroke amount D2 refers to the straight line distance between the most advanced body position (at body scoring) and the most retracted body position (at the time of weft insertion).
Further, it is preferable that the handle opening amount D3 in the air jet loom is in the range of 10 to 75 mm, preferably 20 to 65 mm, more preferably 30 to 60 mm. When the helical opening amount D3 is in this range, scratches between adjacent warp yarns are minimized at the time of weaving at a high rotation speed, and fluffing of the carbon fiber yarn can be suppressed.
More specifically, if the opening amount is too large, the absolute value of the warp tension becomes high, so that the napping period of the carbon fiber yarn becomes large, and if the opening amount is too small, the formation of the bottom (space for passing the weft) Not only the insertion can be stably performed but also the warp of the warp yarn and the weft yarn become relatively strong and fluff may be generated. The hand opening amount D3 refers to a straight line connecting the position of the mail at the top of the opening with the position of the mail at the bottom of the closed bottom dead center.
In the air jet loom, it is preferable to provide a push bar that at least partly restrains the opening of the warp yarn introduced into the head. The push bars 8a and 8b are provided between the evacuation rolls 11a and 11b and the heald 6 so that the warp yarns 5a and 5b introduced into the heald 6 through the evacuation rolls 11a and 11b And the opening of the warp yarn 5c is smaller than the opening formed by the original apostles 9a and 9b in the absence of the push bars 8a and 8b. In other words, the opening by the warp yarn is suppressed to be smaller. By suppressing at least partly the opening of the warp yarns introduced into the heald, it is possible to further reduce the scratches between adjacent warp yarns 5c due to the opening movement.
The push bars 8a and 8b may be any ones capable of suppressing the openings. Examples of the push bars 8a and 8b include free rolls (especially those having a surface checkerboard pattern), fixed rollers And the like. From the viewpoint of minimizing the scratches on the warp and pushing bars, it is preferable that the free-rotation rolls have a checkered shape.
Further, in order to maximize the above effect, it is preferable to provide an easing mechanism that absorbs the tension fluctuation of the warp during intermination. Even when the warp length D4 from the position where the warp starts to the heald to the heald is shortened in order to reduce the scratches between the adjacent warp yarns 5c due to the opening motion, It is possible to realize a uniform warp tension. This effect is particularly remarkable when the warp length D4 from the point where the warp starts to the heald to the heald is 10 times or less the opening amount of the heald. It is more preferable that the number of the eccentric mechanisms is the same as the number of the hands, and the eccentric mechanism is separately used for the respective hands. This easing mechanism may be a negative pole type in which the easing rolls 11a and 11b are caused to move by the tension of the warp by means of a spring or the like, but it is preferable that the eccentric type is an active mode in which the loom is forcibly moved by loom driving power or a separate motor. If it is an aggressive system, it can contribute to lint reduction even at a higher speed.
In the present invention, the width of the body inlet of the air jet loom is preferably 100 to 350 cm. More preferably in the range of 130 to 310 cm, and more preferably in the range of 150 to 260 cm. When a shuttle loom or a looper loom is used in general, there is a limit to the width of the loom, that is, the width of the body inlet of the loom, because a shuttle or looper, which is a weft insertion means,
On the other hand, in the air jet loom, since the weft yarns are inserted by air, the width of the body inlet can be easily widened simply by adding the sub nozzle in the width direction. That is, in order to maximize the effect of using an air jet loom, it is preferable to weave the fabric with a width as wide as the above range.
When the width of the body inlet of the air jet loom is as wide as the above range, ear structures 19c are formed in the body inlet widths other than both ends of the body inlet width to form a plurality of carbon fiber fabrics 18a, 18b ... . Generally, the ear tissue is formed only at both ends of the body entrance width to obtain a carbon fiber fabric of one width. However, ear tissues 19c ... are also formed within the body entrance widths other than both ends, , 18b, ...) are simultaneously obtained, the productivity can be further improved. More preferably, it is in the range of 2 to 12 widths, and more preferably in the range of 3 to 7 widths. (For example, an ear tissue device, a duplex device, a "cloker" device, and the like) for forming the ear tissue within the width of the body entrance is required, In some cases, the device arrangement may be restricted.
Further, in weaving using an air jet loom, after the weft is inserted and the weft is opened and closed to weave the carbon fiber fabric, the weft yarn can be tuck-in in the fabric width. By folding the yarn back into the fabric width with the jaw device, it is possible to obtain a yarn-free fabric as if woven with a shuttle loom. The unidirectional carbon fiber fabric having the taut ear structure is used for repairing and reinforcing concrete, for example, when the unidirectional carbon fiber fabric is applied by applying the resin to the concrete, the amount of the resin to be applied is minimized can do.
In the present invention, the unidirectional carbon fiber fabric having the warp yarns and the auxiliary fibers as the weft yarns is woven into a carbon fiber yarn having a fineness of 400 to 6,000 tex. If the fineness of the carbon fiber yarn used in the present invention is too small, the warp density of the warp yarn becomes too dense, the number of fluffs of the carbon fiber yarn becomes large, and the quality of the carbon fiber fabric is deteriorated. On the other hand, if the fineness of the carbon fiber yarn used is too large, the gap of the warp yarn becomes too large, and the weft insertion efficiency of the air jet loom is lowered.
From another viewpoint, if the fineness of the carbon fiber yarn is in the above range, the carbon fiber yarn can be obtained at low cost. Weaving with an air jet loom using this range of carbon fiber yarn means further improving the productivity, and the effect of the present invention is greatly exerted.
The auxiliary fibers used in the present invention have a fineness of 1/5 or less, preferably 1/20 to 1/500, and more preferably 1/100 to 1/250, of the fineness of the carbon fiber yarn as the warp yarn. If the fineness is too large, the mechanical properties are lowered by bending the carbon fiber yarn in the unidirectional fabric. On the other hand, if the fineness is too small, it means that the strength of the auxiliary fibers is too low, and the weft yarn breakage often occurs at the time of weaving.
When the weft insertion is performed by an air jet loom, when a carbon fiber yarn is used in the weft yarn, the carbon fiber yarn easily fuzzles and the generated napping may clog the loom components such as nozzles. If the unidirectional fabric using such auxiliary fibers is used as the weft yarn, the problem does not occur even when the weft insertion is performed by the air jet loom, and the productivity of the carbon fiber fabric is not deteriorated.
Examples of such auxiliary fibers include inorganic fibers such as glass fibers and metal fibers (excluding carbon fibers), aramid fibers, PBO fibers, nylon fibers, polyester fibers, polyvinyl alcohol fibers, polyethylene fibers, polypropylene fibers , Polyphenylene sulfide fibers, and cotton fibers. Of these, inorganic fibers other than carbon fibers are preferable, which can minimize the shrinkage in the width direction of the carbon fiber cloth, In order to minimize the occurrence of fuzz, glass fibers are particularly preferable.
As the auxiliary fiber, a spun yarn, a twist yarn, an entangled yarn, or a covering yarn (composite yarn wound around the yarn) is preferable from the viewpoint of the non-elongation of the yarn by the jet of air. As specific examples, it is preferable that the yarn is a spun yarn of glass fibers and / or organic fibers, or an entangled yarn of a glass fiber and / or an organic fiber (preferably a tassen yarn). By using such an auxiliary fiber, it is possible to stably fix the birefringence caused by the air jet in comparison with a simple filament yarn.
Further, the coefficient of friction with the carbon fiber yarn after weaving can be increased, and the weft yarn as the problem of the present invention can be minimized. As another specific example, a covering yarn covered with a filament yarn of an organic fiber by inspecting a glass fiber is also preferable. In covering yarns, even if both the glass fiber and the organic fiber are in filaments, it is possible to suppress the yarn splitting and the weft lint of the weft yarn by the covering process, and to stabilize the birefringence by the air jet.
Preferable examples of the organic fiber used herein include low melting point polymer fibers (fibers composed of copolymerized polyamide, copolymerized polyester, polyolefin, and copolymer polyolefin). When such a low melting point polymer fiber is used, it is possible to fill the carbon fiber cloth and the auxiliary fiber by heating the obtained carbon fiber cloth, and the obtained carbon fiber cloth has an excellent form in which the weft is straight without being warped It is easy to maintain.
From another viewpoint, in the present invention, it is preferable to use a carbon fiber yarn having a measured tensile strength of 4,000 MPa or more, preferably 5,000 MPa or more. If the tensile strength is in this range, it is possible to produce a carbon fiber fabric which is less prone to fuzz and is of high quality.
There is no upper limit to the tensile strength, and it is preferable that the upper limit is high, but it is considered that the upper limit of 7,000 MPa is considered in the present technical range.
Conventionally, in the shuttle weaving machine or the looper weaving machine, which has been used for manufacturing carbon fiber fabrics, since the weft yarn is directly pulled and inserted, tension can be applied to the weft yarn itself. In an air jet loom, which is relatively difficult to present but can not impart tension directly to the weft in the weft insertion, this problem is likely to become present. However, in the present invention, it is preferable to solve such a problem by imparting tension to the weft yarn before and / or after weaving.
At first, a separate structure 19b is formed by the same weft yarn 14 as the weft yarn constituting the carbon fiber fabric, at the same time, at the end of at least the half-weft insertion side B of the woven carbon fiber fabric. At this time, the woven carbon fiber fabric or the separate fabric 19 is continuously conveyed downstream, and on the downstream side, the weft yarn is cut between the separate fabric 19b and the carbon fiber fabric 18b, The carbon fiber fabric is partially separated and twisted to separate tissues. Of course, like the half-weft insertion side B, a separate weave 19a is formed by weaving the same weft yarn 14 as the carbon fiber fabric at the end of the weft insertion side A and, at the same time, Other tissues may be weighed within other body inlet widths and twisted to separate tissues. By firing these separate pieces 19a, 19b ..., tensile force can be applied to the weft yarns 14 in the carbon fiber fabrics 18a, 18b, 18c ..., and the weft- Can be obtained more easily.
As a method of applying a twist to the separate tissue, for example, a guide having a hole is used and the guide is rotated by passing another tissue through the hole, or the upper and lower surfaces of separate tissues are sandwiched by the endless belt, Or the like can be exemplified. Among them, the former is preferable from the standpoint that the apparatus is simple and easily mounted on the air jet loom.
In order to apply the tension to the weft yarn 14, the weft yarns 14a and 14b may be separately formed so as to widen the distance between the separate fabrics 19a and 19b and the carbon fiber fabrics 18a and 18b, It is desirable to guide the organization.
As such a method of guiding the separate tissues, there is exemplified a method of increasing the kink in the downstream side or guiding the separated tissues separated from the downstream side in the direction of retracting from the carbon fiber cloths 18a, 18b . In order to exhibit the effect more efficiently, the distance between the separate tissues 19a and 19b and the carbon fiber fabrics 18a and 18b is preferably set so that the distance between the separate tissues and the carbon fiber fabric is widened before the weft is cut The method of increasing the twist is desirable.
Further, in this embodiment, it is preferable that the unidirectional carbon fiber fabrics 18a, 18b, 18c, ... are of a plain weave, twill or water weave structure, and the separate weave structures 19a, 19b ... are plain weave, . Particularly, in order to impart tension to the weft yarns as described above, it is preferable that the
In addition, when the above-described fibers described as auxiliary fibers, instead of carbon fiber yarns, are used as
In order to impart tension to the weft yarns before and / or after the weaving operation, the tubular bodies 15a and 15b having open ends at both ends are inserted into the weft insertion side of the woven carbon fiber fabric, It is preferable to pass the inserted weft yarn 14 from one opening (inlet) of the tubular body 15a (b) to the other opening (outlet).
Specifically, the curved tubular body 15a is disposed on the other side (the side where the weft yarn is not inserted) of the body 7, and the stretch nozzle 16 (not shown) is attached to the weft yarn 14, ) And the like, air is emitted from the side of the body to the side, and the weft yarn 14 passes through the inside of the tubular body 15a. The straight tubular member 15b is disposed on the side of the body to be observed (the side on which the weft is inserted) so as to intersect with the noncontiguous direction of the weft (that is, not parallel to the noncontiguous direction) The weft yarn 14 passes through the tubular body 15b by blowing air toward the outlet of the tubular body by using a stretch nozzle (not shown) or the like to the weft yarn 14 which has reached the end of the weft yarn. In this tubular body, not only the jetting of air by the stretch nozzle, but also the pressure in the tubular body is reduced, the weft can be passed through the tubular body more efficiently and reliably.
In order to impart tension to the weft yarns before and / or after weaving, the weft yarns inserted may be directly held by clamp means (not shown) disposed on the half-weft yarn insertion side (B). It is preferable that such a clamping means moves in synchronization with a signal from a detector which detects that the weft is inserted. In addition, a force in a direction to return to the weft insertion side (A) may be imparted to the weft yarn inserted immediately before closing movement of the heald. According to this aspect, it is also possible to impart tension to the weft yarn before and / or after weaving. As a method for imparting a force in the direction of returning to the weft, there is a method in which the guide position for passing the weft, which is disposed on the weft insertion side, is moved in the direction in which the weft is returned for every bobbin thread, And a method in which tension is always given in the direction in which the weft yarn is returned, except when the weft yarn is invisible. From the point that the device is simplified, the former is preferable.
Further, in the present invention, it is preferable to bond the resin to the carbon fiber fabric to be produced in a linear or point-like form.
If the resin adheres to the fabric, the shape of the carbon fiber fabric can be stabilized and the handling property of the carbon fiber fabric can be improved.
The resin may be adhered to and adhered to the carbon fiber fabric in any form such as fiber form, particle form, emulsion form dissolved or dispersed in water, or dispersion form. Among them, it is preferable to use a solid fiber type or solid particle type resin from the viewpoint of easy adhesion and from the viewpoint of the above-described functional development, and to adhere it to the fabric. In the case of such a fiber form, the carbon fiber yarn or the auxiliary fiber may be aligned and woven together and adhered, or the composite yarn may be formed by using a carbon fiber yarn, auxiliary fibers, covering, They may all be woven and bonded. Particularly, in the case of improving the handling of fabrics, it is effective to insert the fibers in the form of a weft in a straight manner, or to insert the composite yarn into a composite yarn by covering or combining with carbon fibers or auxiliary fibers. In the case of using a resin in the form of a particle, a solid particulate resin may be applied to the surface of the woven carbon fiber fabric and adhered. Alternatively, the dispersion may be applied and adhered in a state of being dispersed in a liquid such as water do.
The resin to be adhered to the carbon fiber fabric is not particularly limited as long as it improves the handling properties of the carbon fiber fabric and / or improves the mechanical properties of the composite material using the carbon fiber fabric. A thermosetting resin and / or a thermoplastic resin may be suitably selected Can be used. From the standpoint of improving the handling of fabrics, it is preferably at least six kinds selected from epoxy, unsaturated polyester, vinyl ester, phenoxy, polyamide, polyester, polyvinylformal and polyolefin, , And polyamide are particularly preferable. It is preferable that such a resin has a melting point (Tm) (glass transition point + 50 deg. C) measured at a temperature raising rate of 20 deg. C / min from the absolutely free state by DSC (differential scanning calorimetry) at 150 deg. On the other hand, the melting point (Tm) is preferably 50 ° C or more from the viewpoint of handleability in handling the carbon fiber fabric under normal circumstances.
As a method of adhering such a resin, the carbon fiber cloth may be heated in contact with a heat source, or the adhered resin may be adhered to the fabric by heating the carbon fiber cloth and the heat source without contacting them. For example, when a carbon fiber fabric is produced at a high speed of 1 m / min or more, it is preferable to heat the carbon fiber fabric and the heat source in contact with each other. More preferably, the method of heating by bringing into contact with a heat source and the method of heating without contacting are preferably used together. Since the present invention uses carbon fibers having excellent thermal conductivity, it is possible to efficiently bond the resin even at a high speed of 1 m / min or more, for example, by disposing a plurality of the heat sources successively in the manufacturing process of the carbon fiber fabric . Examples of such a heat source include a heating roll and a hot plate when brought into contact with each other. When not in contact, a radiation heat heater such as far-infrared rays or near-infrared rays can be used.
Further, in order to further increase the productivity, the woven carbon fiber fabric is wound once with a predetermined length L1, the wound carbon fiber fabric is divided into a product length L2 which is not more than half of the predetermined length L1, desirable. Since the carbon fiber fabric obtained in the present invention is mainly used as a reinforcement material of CFRP, if it is packed in a box without being wound, wrinkles or bending are generated, thereby damaging the carbon fiber yarns or disrupting the arrangement (straightness) . For this reason, it is preferable to make the rolled aspect into a product form.
On the other hand, on the assumption that winding is carried out, even if a high production speed is attained by the present invention, if the winding length is short, it is necessary to frequently stop the loom, and the effect of the present invention can not be effectively exhibited. Therefore, as described above, the predetermined length L1 having a length twice or more of the length L2 of the product is continuously woven, and once wound on an intermediate core (for example, a core tube or a steel tube) different from the product core . By doing so, the periodic frequency of the loom can be minimized and a higher production speed (number of rotations of the loom) can be achieved. It is preferable that the carbon fiber cloth of the predetermined length L1 wound once is divided into the product length L2 which is not more than half of the predetermined length L1 in the separate process and is wound again.
The predetermined length L1 is more preferably at least three times the product length L2, and more preferably at least five times. From another viewpoint, the predetermined length L1 is preferably 300 m or more, more preferably 500 m or more, and more preferably 700 m or more.
In the present invention, it is preferable that the warp yarns are guided to the loom directly by arranging the warp yarns as the warp yarns from each bobbin. When the warp yarns are guided to the loom by arranging the warp groups on the sheet after the bobbins are regularly or partially sifted (after beading), in particular, when the yarns are of the fineness of 400 to 6,000 tex, Thickness irregularity in the fiber yarn is likely to occur, and there is often a difference in yarn length between yarns. Due to this, the loosened carbon fiber yarn may be distorted during the weaving process to disturb the arrangement (straightness). In addition, unevenness may be generated in the obtained fabric itself, and the quality of the fabric may be lowered. The above problem is solved by directing the carbon fiber yarns from the bobbins to the loom directly and without weaving the regular diameter or partial regular diameter.
As described above, the method of manufacturing carbon fibers has been described in detail above, but such a method can be applied to the ferroelectric layer manufacturing method.
That is, in order to determine the phase of PVDF to be in the? -Phase, the PVDF is rapidly heated at a temperature of, for example, 60 to 70 占 폚, preferably about 65 占 폚, And the PVDF is determined to be in the? -Phase by a cooling method. By applying this method to the carbon fiber manufacturing method described above, the ferroelectric layer can be easily manufactured. However, the contents of these temperatures are only exemplary, and the contents of the present invention are not limited thereto.
Second Example
The second embodiment proposed by the present invention relates to a method of manufacturing a ferroelectric layer using an FRP manufacturing method.
10 is a schematic longitudinal sectional view of an RTM molding apparatus according to a second embodiment of the present invention.
10, the
The molding die 23 is heated and cooled, for example, by a heating medium flowing through the heating
The
An
Although not shown, a plurality of
When injection of resin from each of the
The resin expanding from the inside of the
An air trap region 244 is generated in a portion where the resin is hardly spread even in the product region, and an undesirable flow of air as indicated by an arrow is generated, so that air tends to be trapped in the molded product.
The RTM molding apparatus 2101 includes a top mold 2104 and a bottom mold 2105 as a molding die 2103 forming the cavity 2102. The top mold 2104 is pressed by a press mechanism 2106, Open. The cavity 2102 is made of a reinforcing fiber base material, and is made of, for example, a laminate of a reinforcing fiber base material. For example, a preform 2107 previously shaped into a predetermined shape is disposed. The upper mold 2104 is clamped with respect to the lower mold 2105 while the preform 2107 is disposed in the cavity 2102 and the FRP 2107 is moved from the runner 2108 provided around the preform 2107 toward the preform 2107. [ And a suction port 2109 as a suction path is provided in the cavity 2102 so that the injection resin is impregnated into the reinforcing fiber base material constituting the preform 2107 through suction. The supply of the resin to the runner 2108 is performed through the resin injection port 2110 opened in a suitable portion of the runner 2108. [ The suction port 2109 is opened and closed by a valve body 2111 on the pin and the periphery of the runner 2108 with respect to the cavity 2102 is sealed with a sealant 2112. The molding die 2103 is heated and cooled, for example, by a heating medium circulated in the heating medium circulation path 2113, and is heated when the resin is injected to achieve good impregnation of the resin. After resin impregnation, Cooling can be also performed), and the injected and impregnated resin is cured to produce a predetermined FRP molded article.
For example, the suction port 2109 is disposed at a central portion of the preform 2107, and a portion corresponding to the periphery of the suction port 2109 of the preform 2107 itself flows from the periphery of the portion to the portion Flow resistance region 2121 that makes it difficult to flow in the portion. The high flow resistance region 2121 is formed at a position outside of the product to be molded or at a position where the appearance of the product to be molded is not required for the product to be molded. In this embodiment, The thickness of the preform 2107 is formed by partially reducing the thickness of the preform 2107 in the high flow resistance region 2121 by the mold 2103 (two-phase mold 2104 and lower mold 2105). However, as described above, the high flow resistance region may be formed by increasing the density of the reinforcing fibers in the preform in the high flow resistance region in advance.
The outer shape 2123 of the product to be molded is set in the preform outer circumferential portion 2122 and the runner 2108 is formed around the preform 2107 so as to extend over the entire circumference along the preform outer circumferential portion 2122. [ Is installed.
As for the runner 2108, the resin is supplied from the resin injection port 2110 which is opened at a suitable portion of the runner 2108 as described above. A resin detection sensor 2124 for detecting the resin flowing into the high flow resistance region 2121 is provided near the mounting portion of the suction port 2109 in the high flow resistance region 2121.
In the method of manufacturing an FRP according to the present invention, which is performed using the RTM molding apparatus 2101 thus configured, the resin supplied from each resin injection port 2110 into the runner 2108 flows through the runner 2108, Is injected from the periphery of the preform 2107 toward the preform 2107 from the periphery of the preform 2107. When the injection is started from the runner 2108 toward the preform 2107 from the periphery of the preform 2107, the shape of the flow front end 2131 indicating the front end of the flow of injected resin flows from the preform outer periphery 2122 to the preform 2107 As shown in Fig. Although the inner region of the flow front end 2131 indicates the resin-impregnated region 2132, as the flow front end 2131 proceeds, the non-impregnated region 2132 is gradually narrowed to the irregular shape. Finally, a part of the flow front end 2131 reaches the high flow resistance region 2121, and the flow resistance of the resin suddenly increases at the reaching end, so that the expansion of the flow front end 2131 is temporarily suppressed. The portion of the flow front end 2131 that has not reached the high flow resistance region 2121 sequentially reaches the high flow resistance region 2121 and the entire portion of the flow front end 2131 reaches the high flow resistance region 2121 , And the non-impregnated region 2132 is within the range of the high flow resistance region 2121. When it is detected by the resin detection sensor 2124 that the resin reaches the vicinity of the suction port 2109, the suction port 2109 is closed by the valve body 2111 described above, , The impregnation is stopped. The flow of the resin against the suction port 2109 proceeds so that the air gap region 2133 along the air trap is substantially in contact with the suction port 2109. As a result, Lt; / RTI > The region including the void region 2133 and the high flow resistance region 2121 may be removed after molding because it becomes, for example, the product outside region 2134, or, in the case where there is no problem in appearance, Can be left.
In the process of enlarging the flow front end 2131 in which the resin flow is intentionally controlled as described above, the resin spreading from the outer peripheral portion of the preform 2107 toward the inside of the preform 2107 is expanded in the range of the area of the product to be molded Air is sufficiently trapped without being trapped over the entirety of the area within the area where the desired surface quality is required, and is impregnated into the reinforcing fiber base material of the preform 2107. In accordance with the expansion of the preform 2107, Even air (two air bubbles) mixed in the resin is extruded to the side of the high flow resistance region 2121 which is located outside the range of the region, and further to the installation portion of the suction port 2109 Goes. Thus, it becomes possible to achieve a desired molding state without air trap, in which air is not selectively mixed over the entire target product area, and the injection resin is preferably impregnated into the reinforcing fiber base material of the preform.
As described above, the method of manufacturing FRP has been described in detail above, but such a method can be applied to a method of manufacturing a ferroelectric layer.
That is, in order to determine the phase of PVDF to be in the? -Phase, the PVDF is rapidly heated at a temperature of, for example, 60 to 70 占 폚, preferably about 65 占 폚, And the PVDF is determined to be in the? -Phase by a cooling method. By applying this method to the above-mentioned FRP manufacturing method, the ferroelectric layer can be easily manufactured. However, the contents of these temperatures are only exemplary, and the contents of the present invention are not limited thereto.
Third Example
The third embodiment proposed by the present invention relates to a method of manufacturing a ferroelectric layer using a graphite fiber production method.
11 is a schematic view showing an example of a container according to a third embodiment of the present invention.
The polymer film that can be used in the present invention is not particularly limited, but may be polyimide (PI), polyamide (PA), polyoxadiazole (POD), polybenzoxazole (PBO), polybenzobisoxazole (PBBO), polythiazole (PT), polybenzothiazole (PBT), polybenzobisthiazole (PBBT), polyparaphenylenevinylene (PPV), polybenzimidazole (PBI), polybenzobisimidazole PBBI), and a thermostable aromatic polymer film containing at least 710 species selected therefrom is preferable because the thermally conductive property of the finally obtained graphite increases. These films may be produced by a known production method.
Among these, polyimide is preferred because various types of raw materials monomers can be selected to have various structures and properties.
Further, the polyimide film tends to become graphite excellent in crystallinity and thermal conductivity, because carbonization and graphitization of the film tend to proceed more than polymer films made of other organic materials.
When the polyimide film is treated to 1000 deg. C under an inert gas, decomposition starts slowly at about 500 deg. C, and most shrinkage of the film occurs at 500 deg. C to 700 deg. C at which cracking gas is generated. Shrinkage of the film does not occur. Low-molecular organic gases such as carbon monoxide, carbon dioxide, nitrogen and ammonia, and low-molecular organic substances such as benzene, aniline, phenol and benzonitrile are observed as decomposition gases. When the temperature is around 900 DEG C, generation of these decomposition gases is almost completed, and after the treatment is finally carried out up to 1000 DEG C, a carbonaceous film having a weight reduced by about 60% is obtained. In addition to the above components, many low-molecular-weight substances that are difficult to identify are observed, and these organic components are recovered as nonvolatile tar components after the carbonization treatment.
This tar component exists as a gaseous phase or a fine combustion phase immediately after being generated as decomposition gas from the film. When the film and the film are in close contact with each other, that is, when the raw film is wound around the core, gas may remain between the films. The gas component staying in the film is agglomerated to become tar, and this tar acts like an adhesive, and solidifies and fuses together with the temperature rise. Carbonation treatment in a reduced-pressure atmosphere may be carried out in order to suppress aggregation of gas components. By carrying out the carbonization treatment under a reduced pressure, aggregation of the decomposition gas can be prevented and occurrence of fusion bonding can be greatly suppressed. The inhibition effect is higher when the decompression degree is larger. For example, when a wide polyimide film is sandwiched between a graphite plate and a carbonization treatment, it is predicted that fusion is more likely to occur because the gas is longer than the narrower polyimide film. Even in such a case, the occurrence of fusion can be suppressed by carrying out the carbonization treatment by further increasing the degree of vacuum. On the other hand, in order to obtain a graphite film having a high thermal diffusivity, it is necessary to orient the graphite in layers in the graphitization step. In order to obtain a high-quality graphite film equipped with such a graphite layer, it is preferable that the carbonization process proceeds smoothly in the carbonization process, which is the entire process of the graphitization process, and the carbon plane is developed and oriented to some extent at the time after the carbonization process .
Therefore, when the decompression degree is increased, more gas is generated from the inside of the film. However, when the decompression degree is excessively increased, a carbonaceous film in which the planar structure of carbon is partially broken is easily obtained, and it is effective to control the decompression degree to some extent to be.
The range of reduced pressure in the present invention is not particularly limited as long as it is -0.01 kPa or more, but is preferably -0.01 kPa or more to -0.08 MPa or less, more preferably -0.1 kPa or more to -0.06 MPa or less, -0.04 MPa or less.
When the decompression degree is -0.01 kPa or more, the fusion-inhibition effect is sufficiently exhibited, and when it is -0.08 MP or less, a graphite film having a good thermal diffusivity can be obtained. Here, "reduced pressure of -0.01 kPa" means that the pressure of the gas in the heating apparatus is 0.01 kPa lower than the pressure of the gas other than the heating apparatus (usually considered to be the atmospheric pressure). Similarly, the "reduced pressure of -0.08 MPa" means that the pressure of the gas in the heating device is lower than the pressure of the gas other than the heating device by 0.08 MPa.
The lower limit of the temperature range for depressurizing is preferably 400 DEG C, more preferably 500 DEG C, and the upper limit of the temperature range for depressurizing is preferably 800 DEG C Deg.] C, and more preferably 700 [deg.] C. It is particularly preferable that the heat treatment is performed in a temperature region where carbonization thermal decomposition occurs or at 500 ° C to 700 ° C. However, the contents of these temperatures are only exemplary, and the contents of the present invention are not limited thereto. By performing depressurization in a temperature region where a large amount of decomposition gas is generated, it is possible to effectively prevent the decomposition gas from staying between the films, and as a result, fusion can be suppressed. Further, as the carbonization progresses, the glass is in a fragile state. Therefore, when a certain force is applied to the fragile state, it tends to crack. Thus, in the temperature range after the progress of the carbonization thermal decomposition, a film with less cracking can be obtained by gentle heat treatment at normal pressure or a small decompression pressure. Further, when the pressure is changed from the atmospheric pressure or the pressurized state to the reduced pressure during the heat treatment, the gas staying between the films is pulled out of the system by the reduced pressure and is extruded by the gas filling the inside of the furnace.
Therefore, by switching to a reduced pressure in a temperature region where a large amount of gas is generated by carbonization thermal decomposition, fusion bonding can be prevented more effectively.
When the number of turns in the winding core increases, the adhesion between the films increases, and the fusion bonding tends to occur during the carbonization treatment. Particularly, a portion close to the core is more likely to cause fusion because it takes more force than the outer portion. When a polyimide film having a certain length or longer is processed, fusion is liable to occur. In such a case, adhesion can be more effectively prevented by performing the treatment under reduced pressure and introducing an inert gas. The inert gas is introduced from one side of the fired portion and the exhaust gas is simultaneously blown out from the other side to generate an inert gas flow path in the fired portion so that the decomposed gas staying between the films can be removed quickly from the system. At this time, it is important to adjust the flow rate of the inert gas (3V1 (unit: L / s)) and the displacement (V2 (unit: L / s)) to maintain the inside of the furnace at an appropriate reduced pressure. The larger the amount of the inert gas to be introduced, the higher the effect is, but the more the use of the inert gas is, the higher the cost becomes. When the volume of the treated product is V, the volume of the treated product and the required amount of the inert gas can be represented by a proportional relation. Here, the volume (V) of the processed product refers to the total volume of all the members arranged and heated in the heating apparatus, such as a polyimide film to be processed and a container of polyimide film. The value (unit: s) of the value (V / V1) obtained by dividing the volume V of the treated product by the flow rate V1 of the inert gas is preferably 0.01 or more and 1000 or less, more preferably 0.1 or more and 100 or less, Is 1 or more and 10 or less. When the value of V / V1 is less than 0.01, the amount of the inert gas to be introduced is too large for the treated product, which is not preferable. If the value of V / V1 is larger than 1000, the amount of the inert gas is too small, so that fusion bonding can not be sufficiently prevented. Here, the "amount of inert gas (V1)" refers to the introduction rate (L / s) of the inert gas in the pressure of the gas other than the heating device (usually considered to be the atmospheric pressure).
As for the kind of the inert gas to be used, nitrogen, argon, helium and the like can be mentioned. If the inert gas is used, no gas is used, the film is not affected during the carbonization treatment, and the same quality is obtained. Of these, nitrogen is preferably used from the viewpoint of cost.
Regarding the above-mentioned atmospheric condition, it is not always necessary to carry out the treatment under the above-mentioned atmospheric condition during the carbonization treatment, and at least 400 to 750 DEG C, preferably 400 DEG C to 700 DEG C, Condition is good. By flowing the inert gas in the temperature region where the decomposition gas is generated, it is possible to effectively prevent the decomposition gas from staying between the films, and as a result, fusion can be prevented. For example, there is a method in which a treatment is performed under a reduced pressure without introducing an inert gas to around 400 DEG C, and thereafter the predetermined reduced pressure is maintained while an inert gas is introduced, or a method in which the flow rate of the inert gas is reduced I think how to do it. With this treatment method, there is no need to continuously flow the inert gas during the treatment, and the amount of consumption of the inert gas can be reduced.
In the case where a large number of polyimide films are processed, it is presumed that the gas is temporarily brought into an atmospheric pressure or a pressurized state. Prediction of the amount of decomposition gas and keeping the processing atmosphere in a reduced pressure state as much as possible is also a point for improving foreign matter and fusion bonding. Therefore, in order to further exert the effects of the present invention, it is preferable to optimize the inert gas flow path in the furnace. It is more effective to design the inert gas introducing port and the exhaust port in accordance with the shape of the fired portion or the container to be fired or to make the container itself into which the polyimide film is inserted to have a structure having improved air permeability.
The larger the thickness of the raw polyimide film is, the larger the amount of decomposition gas generated in the carbonization treatment becomes, and the more the fusion is likely to occur. The thermal diffusivity of the graphite film itself is expressed by the thermal conductivity (unit: W / (mK)), but the ability to actually transport heat is the value obtained by multiplying the value of the thermal conductivity by the thickness of the graphite film. For example, even if the graphite film has a thermal conductivity of 1000 W / (m 占)) having the same thermal conductivity in the plane direction, the graphite film having a thickness of 25 占 퐉 and 40 占 퐉 has a high heat-transporting ability. That is, when the same area is used, the graphite film of 40 mu m is more likely to diffuse heat from the heat source. From the viewpoint of carrying out a large amount of heat transport with a minimum area, it is very useful to produce a thick graphite film.
Generally, when a film having a thick finished thickness is produced by the polymer graphite method, it is necessary to use a thick polyimide film as a raw material. As described above, the polyimide film having a large thickness tends to cause fusion more easily in the carbonization treatment. For example, a separator (a sheet or a film sandwiched between raw films, for example, a graphite film or a graphite sheet) may be used to solve this problem. Further, since the thickness of the polyimide film having a large thickness is thin, the processing length in the same volume is lowered. Therefore, it is preferable that the separator and the like sandwiching the film are not used as much as possible. By using the carbonization method under reduced pressure of the present invention, even a thick polyimide film can be carbonized without using a separator.
Even in this case, the decompression carbonization treatment while flowing the inert gas is very effective. In the case of processing a polyimide film having a large thickness, the flow rate of the inert gas may be increased more than when the film is thin.
The thickness of the polymer film used in the present invention is preferably 10 占 퐉 to 250 占 퐉, more preferably 20 占 퐉 to 200 占 퐉, 20 占 퐉 to 100 占 퐉, further preferably 30 占 퐉 to 150 占 퐉, Most preferably not less than 30 μm and not more than 80 μm. If the thickness of the polymer film is 10 占 퐉 or more, the heat dissipation capability of the finished graphite film becomes sufficiently high. Further, when the thickness is 250 m or less, it becomes possible to form a highly oriented graphite layer. At the time of control of fusion control of the film, the thickness of the polymer film is preferably 10 mu m to 100 mu m, more preferably 10 mu m to 80 mu m, further preferably 10 mu m to 60 mu m, desirable.
The method of producing the graphite film by winding the polymer film on the core of the present invention has the advantage of being able to produce a long and large graphite film which is difficult to manufacture as a sheet type. However, if a polymer film of a certain length is not used, the area of the raw film that can be processed in the same volume may be reduced as compared with the sheet type. Therefore, the length of the raw film to be used is preferably 10 m or more, more preferably 20 m or more, and further preferably 50 m or more. It is needless to say that as the length wound on the core increases, the raw films tend to melt and bond during the carbonization treatment, and the production method of the present invention becomes more effective at that time.
With respect to the exhaust method, all known methods can be used provided that the safety of the calciner itself is not impaired, such as a method using a vacuum pump or an exhaust fan. In particular, various types of vacuum pumps are commercially available from each company, and they are used in the present invention (3 favorably) in view of simplicity of operation. Examples of the vacuum pump that can be used in the pressure range (-0.01 kPa to -0.08 MPa) of the present invention include an aspirator (three-flow pump), a dry vacuum pump, a mechanical booster pump, ) Pump, and an ejector pump.
The degree of decompression can be adjusted by attaching a valve to the exhaust part of the vacuum pump and regulating the exhaust amount. Here, "pressure -0.01 kPa" means that the pressure is reduced by 0.01 kPa with a vacuum pump, and "pressure -0.08 MPa" means that the pressure is reduced by 0.08 MPa with a vacuum pump.
The decomposition gas of the polyimide film contains various low molecular weight substances in addition to the above-mentioned components. When the polyimide film is subjected to the carbonization treatment, these substances are obtained as nonvolatile tar substances. When a large number of sheets of polyimide film are carbonized at one time, the treatment of the resulting tar is a problem. Many components of tar are toxic, so it is necessary to treat effluent gas efficiently considering the trouble of cleaning and the risk to human body. There is also a concern that deterioration may be promoted if the continuous operation is continued with the tar adhered to the heater or the heat insulating material. In this respect, it is necessary to induce the decomposition gas at the time of carbonization to the outside of the furnace quickly after the generation. In this case, in order to induce the outflow gas well out of the furnace, it is preferable to introduce an inert gas from one side and exhaust the air from one side to make the flow of the inert gas in the furnace. As a result, the exhaust gas generated is quickly discharged to the outside, and the risk of polluting the inside of the furnace is greatly reduced. In the carbonization treatment method of the present invention, treatment of decomposition gas can also be effectively performed.
For example, when a polyimide film having a length of 50 m is heat-treated to 500 캜, its elongation is about 1 m. For this reason, the polymer film initially tightly wound on the core becomes elongated and loosens near the temperature at which carbonization shrinkage occurs.
Thereafter, as the carbonization progresses, the film length finally shrinks to about 80% of the initial length. Thus, when the long polymer film is carbonized by winding on a core, the outer circumferential end of the film is initially loosened by stretching of the film, and if there is nothing bound to the outer circumferential end, it is stretched. Thereafter, as the carbonization progresses, the polymer film shrinks. Since the number of windings of the film is reduced by the shrinkage, the outer peripheral edge of the film greatly retreats the outer peripheral surface of the wound film, thereby reducing the number of windings. As described above, since the outer peripheral end of the polymer film moves largely during the carbonization process, cracks are likely to occur, and since the films do not adhere to each other, friction between the films does not act and consequently, A carbonaceous film having a large wave at the end portion of the carbonaceous film is obtained. Therefore, when the long polymer film is carbonized by winding on the core, the outer end of the film is bound to the outer circumferential surface without interfering with the movement, so that the long carbonaceous film can be obtained as a film in which cracking or waviness is suppressed. As described above, as the means for capturing the outer circumferential end of the film, an outer tube for accommodating the polymer film wound around the core, one or a plurality of ring-shaped members 381 partially surrounding the outer circumferential surface of the
In the present specification, the container is referred to as a container including a core and an outer tube.
Further, when at least a part of the carbonization step is performed under a reduced pressure and the capturing means is provided at the outer peripheral end of the long polymer film, the fusion of the film can be suppressed in addition to cracking and waved needle.
As described later, in the production of the carbonaceous film, problems of waving and fusion of the film are likely to occur. As a method for solving these problems, in the present invention, a value obtained by dividing the inner diameter (3R) of the outer tube by the diameter (r) of the core is 2 (mm), the thickness of the polymer film is b The value of b divided by a (b / a) becomes an important factor.
From the viewpoint of both the prevention of waviness and adhesion of the carbonaceous film, the value of (3b / a) is preferably 0.2 to 0.9.
If it is 0.2 or more, even if the film is loosened, it is supported on the outer cylinder, so that it is difficult to remain loosened, and a long carbonaceous film free from waviness and wrinkles can be obtained. If it is 0.9 or less, gaps between the film and the film are avoided, and the films are hardly fused together. Hereinafter, the wave needles and fusion will be described in detail.
When the polyimide film cut to a size of 200 mm is heat-treated at a temperature of 1000 캜 without fixing the film at all, a wavy carbonaceous film can be obtained. This wavy needle is solved by applying a pressing load of a certain load from above to heat-treat the film. However, even in this case, it is difficult to obtain a carbonaceous film having a wrinkle- Do. On the other hand, it is possible to obtain a long carbonaceous film free from waved needle or wrinkle by selecting a treatment method well as a long type in which a polymer film is wound around a core and heat treatment is performed. The mechanism will be described below.
When the long raw film wound on the core is carbonized, the friction between the films acts on the film in the longitudinal direction and against the force of the shrinkage in the opposite direction. As a result, a constant tension is generated on the film. It is possible to obtain a long carbonaceous film having high planarity and having a surface free from wrinkles or distortion in the film by progressing carbonization and shrinkage of the film with constant tension. In B and C equipped with the constraining means for constraining the outer circumferential end portion, since the film is in contact with a certain extent, it is preferable that friction occurs in the contact range. In the sheet type, even when the films are laminated and carbonized, no tension is applied on the film because no frictional force acts between the films at the time of shrinking (or, even if they work, they become separate vectors). Further, in order to generate tensile force, even if carbonization treatment is carried out by fixing the end portion of the raw film, the carbonaceous film is in a glass phase, so that the film is split at the time of contraction. In the case of the long type, since the wound films can move with each other at the time of shrinkage, the film is not insulated by shrinkage, and a certain tensile force acts on the film, thereby making it possible to obtain a carbonaceous film free from wrinkles and waviness.
When a polymer film such as a polyimide film is carbonized to 1000 deg. C, the length of the polymer film shrinks to about 80% as described above. However, because the polymer film undergoes thermal expansion along with heating, It will grow. For example, when a polyimide film 50 m having a coefficient of linear expansion of 40 ppm / ° C is heat-treated to 500 ° C, its elongation is about 1 m. Therefore, the raw film initially tightly wound around the core becomes elongated and loosens near the temperature at which the carbonization shrinkage occurs. On the other hand, in the case where the polyimide film is wrapped around the cylindrical core and the heat treatment is performed in the transverse direction, even if the raw film is wrapped tightly around the core at first, the film is stretched just before the thermal decomposition shrinkage, It is loosened and becomes a state of being stretched. When the carbonization treatment is carried out in this way, frictional force does not act between the films because the films are not in close contact with each other, and as a result, a long carbonaceous film with wavy needles is obtained. Further, in the case of a long film, shrinkage of the film in the longitudinal direction is hindered by wrinkles or wavy streaks entered during carbonization, and as a result, there is a possibility that the films are thermally insulated from each other.
Further, after the carbonization treatment, the carbonaceous film can be further converted to a graphite film by treatment at 2400 DEG C or higher. The graphite layer is lifted by the generation of N2 that does not form a graphite skeleton at the final stage (2600 DEG C or more) of the graphitization process and internal gas such as a filler (phosphoric acid series) added to the raw film, and the film is foamed. A graphite film excellent in flex resistance can be obtained by subjecting the graphitized expanded graphite film to compression treatment. The reason why the foamed material is obtained by removing the foaming by compressing the foamed graphite film is that since there is a small space between the layers of the graphite after compression, distortion of the graphite layer applied at the time of bending (three folding) can be avoided Because. However, if the carbonaceous film contains waviness or wrinkles in the carbonization treatment process, the waviness and wrinkles remain after the graphitization. Even if the compression treatment is performed after that, the waviness and wrinkles are not solved Deep wrinkles get in.
Next, the case where the
In order to support the loosened film and closely adhere the films, it is necessary to appropriately select the inner diameter of the outer tube.
If the inner diameter of the outer tube is too large, the film becomes loose and only the wavy film is obtained.
If the ratio (b / a) is 0.2 or more, even if the film is loosened, it is supported on the outer tube, so that it is difficult to remain loosened and a long carbonaceous film free from waviness and wrinkles can be obtained.
From the viewpoint of waving the carbonaceous film, the value of (b / a) is more preferably 0.5 to 0.8. If it is 0.5 or more, the degree of adhesion between the film and the outer cylinder is increased, and a long carbonaceous film free from waviness and wrinkles can be obtained. If it is 0.8 or less, it is possible to obtain a smooth carbonaceous film free from distortion and without distortion due to the contact of the loosened film with the outer passage.
As described above, the polyimide film generates various decomposition gases at the time of thermal decomposition, and becomes a non-volatile tar component after the carbonization treatment, and functions as an adhesive to fuse the films together. In the case of carbonization treatment in which the polymer film is wound around the core, since the films adhere closely to each other, fusion is likely to occur. Further, in order to obtain a long carbonaceous film, when the number of turns of the raw film is increased, fusion is more likely to occur. Normally, as described above, an inert gas is flowed at the time of treatment to seize the decomposition gas to prevent fusion. However, in the case where the polyimide film wrapped around the core is covered with the outer tube and the gas permeability of the entire container is deteriorated as in the present invention, even if the carbonization treatment is performed while flowing the inert gas, the outgassing gas stays in the vessel, There is a possibility that fusion is caused. This problem is solved by providing a gap between the inside of the container and the outflow gas, that is, by increasing the inner diameter of the outer tube.
(b / a) is 0.9 or less, the gap between the film and the exit gas from the film is secured, and the films are hardly caused to adhere to each other. From the viewpoint of prevention of fusion bonding of the carbonaceous film, it is more preferably 0.3 to 0.7. If it is 0.7 or less, the gap between the film and the exit gas from the film is sufficiently secured, and the films are hardly fused together. If the ratio is 0.3 or more, the film is loosened and is not well supported by the outer tube, so that the film is excessively wavy and can be prevented from being welded due to contact between the wavy films.
As for the shape of the outer tube, there is no particular limitation. However, since the loosened film is supported on the inner surface of the outer tube, the shape of the inner surface is an important factor for determining the surface of the carbonaceous film. If there is unevenness on the inner surface of the outer cylinder, the surface of the obtained carbonaceous film may be uneven. In order to clean the shape of the carbonaceous film, it is preferable that the inner surface of the outer cylinder is as close to a cylinder as possible. However, it is not necessary to have a cylindrical shape and it may have the same shape as an elliptical column. In the case where the cross section is not circular like the ellipse, when the center of the crimper is the point A, and the intersection point of the waterline from the point A and the outer passage is the point B, the distance between the point A and the point B, Can be set.
In order to prevent fusion of the films, it is effective to increase the inner diameter of the outer tube to take a space inside the container and to improve the gas escape. At this time, it is more preferable to provide a hole for ventilation in the outer cylinder to improve the gas escape. However, the shape of the inner surface of the outer cylinder may be transferred to the surface of the carbonaceous film. Therefore, if a large ventilation hole is taken out, large unevenness may be transferred to the film surface, or the carbonaceous film may be caught and cracked. When the vent hole is formed, the area of each hole is made small, so that the uneven transfer to the film can be minimized, and cracking due to the engagement can be prevented. The area is preferably 20 mm or less, more preferably 10 mm or less, and further preferably 5 mm or less. There is no particular limitation on the shape of the hole, but it is more preferable that the shape of the hole is less circular than the square. The upper portion of the
The shape of the winding core is required to be a cylindrical shape in the present invention, but the shape of the winding core need not necessarily be a circle, but may be a slightly oval shape, a distorted shape, or a shape having a groove. As the weight of the container increases, the load on the heater increases. Therefore, it is effective to make the inside of the core a hollow structure from the viewpoint of reducing the weight of the entire container or to make a small hole in the core. When the carbonization is carried out by using a small-diameter core, and subsequently the graphitization treatment is carried out, the winding property and the winding property are improved. Is obtained. The graphite film having such properties has a problem that wrinkles tend to enter in the following compression softening step. This problem can be solved by using a winding having a certain diameter, and it is possible to perform softening without wrinkles in the subsequent compression step. Examples of the method for softening the film include a method of rolling the film and a method of compressing the film. In particular, since graphite tends to be easily torn, a method of compression is preferable in order to obtain long graphite having no thickness irregularity without tearing. Particularly, as a compression method, a method of interposing with a polymer film and compressing it in a plane is preferable. The compression is not applied with a shearing force such as rolling, and the graphite can be softened without causing tearing or thickness unevenness of the graphite.
The diameter of the winding core is preferably 70 mm or more, more preferably 80 mm or more, and even more preferably 90 mm or more. When the diameter is larger than 70 mm, the property of winding the obtained carbonaceous film is difficult to be obtained. Although there is no upper limit on the diameter, the diameter of the winding core is preferably 300 mm or less, and more preferably 200 mm or less, in order to secure a throughput per unit volume. In such a case, it is possible to effectively utilize the space by inserting the core into the hollow and further inserting the core in the inside, thereby making it possible to increase the throughput one time.
As a condition of the material of the winding core used in the present invention, those resistant to the continuous use environment at 500 DEG C or higher can be cited. Examples of the material of the container that satisfies this condition include isotropic graphite materials such as extruded products, molded products and cold isostatic pressing products, and alumina (Al2O3), zirconia (ZrO2), quartz (SiO2), silicon carbide (SiC) (MgO), silicon nitride (Si3N4), aluminum nitride (AlN), yttria (Y2O3), mullite (3Al2O3.2SiO2), cordierite (2MgO.2Al2O3.5SiO2), stearate SiO2) and forsterite (2MgO.SiO2), and composite C / C com- posite in which graphite is reinforced with carbon fiber. Among them, carbon is used in a satisfactory manner in view of ease of processing, manufacturing cost, and versatility.
There is a possibility that the carbonaceous film which has been treated at a temperature of 1000 ° C or higher once again is subjected to the heat treatment The carbonaceous film may be changed to another container made of a material resistant to the graphitization temperature after the carbonaceous film is prepared and graphitized. The graphitization process may be carried out after the carbonization process is performed after the temperature is lowered and the container is taken out, and the graphitization may be continuously performed without removing it.
In order to make the carbonization treatment method of the present invention effective, the direction of the container set in the furnace becomes very important. When heating is performed from the outside of the container as in the present invention, for example, when the container is set in the longitudinal direction, it is natural that the outer tube can not support the loosely unwound raw film, and only the wavy carbonaceous film is obtained . Further, when the container is placed in the longitudinal direction, the heat from the heater is conducted from the lower portion of the container, so that temperature unevenness occurs at the lower end portion and the upper end portion of the film, and wrinkles or cracks are likely to occur.
In addition, since the outflow gas from the lower portion of the film is difficult to escape, fusion is liable to occur as compared with the case where the film is placed in the transverse direction. On the other hand, when the film is placed in the transverse direction, the temperature difference in the film is less likely to occur than in the longitudinal direction, and wrinkles and cracks are unlikely to occur. Further, when the film is set in the longitudinal direction, there is a fear that the lower part of the film may be rubbed against the container and may be separated at the time of contraction of the film. Even when the container is placed horizontally, both ends of the film are not brought into contact with the container as much as possible, which is a point for preventing fusion of the film without causing cracking and facilitating release of the outgas. From the above, it is preferable to arrange them in a horizontal arrangement rather than a vertical arrangement. Here, the horizontal arrangement refers to a state in which the winding core is placed almost horizontally, and the vertical arrangement refers to a state in which the winding core is disposed substantially vertically.
When the container is placed on a flat surface, the outer shape of the outer tube is advantageous in that the rectangular parallelepiped is more stable than the cylinder and has good thermal contact. However, in the case of a rectangular parallelepiped shape, since the weight of the container is larger than that of the cylindrical shape, the load on the heater may increase. Considering the workability and the weight of the container, the outer cylinder is preferably cylindrical.
When the polyimide film wrapped around the core is directly subjected to carbonization treatment in an electric furnace, a carbonaceous film having a wider end and a wider end than the core is obtained as described above. In a furnace which is heated by energizing the heater, there is a possibility that the expanded film comes into contact with the heater and may cause a short-circuit. Therefore, it is preferable to carry out the carbonization by inserting the winding core into the outer cylinder for preventing contact.
As described above, the graphite fiber production method has been described in detail above, but such a method can be applied to the ferroelectric layer production method.
That is, in order to determine the phase of PVDF to be in the? -Phase, the PVDF is rapidly heated at a temperature of, for example, 60 to 70 占 폚, preferably about 65 占 폚, And the PVDF is determined to be in the? -Phase by a cooling method. By applying this method to the graphite fiber production method described above, the ferroelectric layer can be easily manufactured. However, the contents of these temperatures are only exemplary, and the contents of the present invention are not limited thereto.
Fourth Example
The fourth embodiment proposed by the present invention relates to a method of manufacturing a ferroelectric layer using a metal fiber manufacturing method.
12 is a view showing a method of manufacturing a metal fiber in which a concave-convex shape is formed using a spur gear according to a fourth embodiment of the present invention.
According to one embodiment of the present invention, metal fibers having irregularities formed at regular intervals, specifically 0.3 mm to 50 mm intervals, in the longitudinal direction of the metal fibers are provided. It is preferable that the irregularities for the metal fibers are formed at uniform intervals along the length direction of the metal fibers so as to exhibit uniform friction force between the metal fibers and excellent high porosity in yarns and fabrics including metal fibers. That is, the irregular shape may be repeated at intervals of 0.3 mm to 50 mm along the longitudinal direction of the metal fiber.
The concavo-convex shape of the metal fibers may be specifically formed at an interval of 0.3 mm to 50 mm, preferably 0.3 mm to 30 mm, more preferably 0.5 mm to 18 mm.
If the irregularities are formed at intervals of less than 0.3 mm, it is not preferable because stable stretching can not be performed due to the increased frictional force between the metal fibers due to many irregularities. If the concavoconvex shape is formed at an interval exceeding 50 mm, the metal fibers may escape from the metal fiber yarn since the frictional force and entanglement between the metal fibers are insufficient.
The concavoconvex shape is not limited to this, but it can be formed by passing a bundle of metal fibers through the gear. The types of gears are not particularly limited, and irregularities can be formed on any kind of metal fibers. The metal fiber bundle which is to pass through the gear to form a concave-convex shape in the longitudinal direction of the metal fiber may be made of any number of metal fibers, and the number of metal fibers is particularly limited in the bundle of metal fibers forming the concave- It is not.
A method of forming a convexo-concave shape in a metal fiber by passing a bundle of metal fibers through a gear, and a metal fiber bundle in which a convexo-concave shape is formed.
For example, the metal fiber bundle may be passed through a spur gear and passed through a helical gear to form a concave-convex shape on the metal fiber, though it is not limited thereto. When the metal fiber bundle 12 is passed through the spur gear 11, a metal fiber bundle in which the concavo-convex shape is formed is obtained. That is, the shape of the concave-convex side surface of the metal fiber is formed perpendicular to the longitudinal direction of the metal fiber. When the metal fiber bundle 32 is passed through the helical gear 31, a metal fiber bundle in which the concavo-convex shape is formed is obtained.
The concavo-convex shape of the metal fiber having the irregular shape according to the present invention may vary depending on the shape of the gear through which the metal fiber is passed, and the specific shape of the concavo-convex shape is not limited. For example, , Can be any shape.
The concave-convex shape may be formed on any metal fiber generally known in the technical field and / or metal fiber produced by any method. In one embodiment, the metal fiber may be a metal fiber of any kind of Fecralloy alloy, which is an iron-chrome-aluminum-based alloy. The Fecralloy alloys are generally known, for example, 18-27% by weight of chromium (Cr), 3-7% by weight, preferably 5-7% by weight of aluminum (Al) .
Further, an improved Fecralloy may be used, which additionally contains 0.05-0.5 wt%, preferably 0.1-0.3 wt% of zirconium (Zr), yttrium (Y) or the like in the Fecralloy alloy composition. In another embodiment, stainless steel metal fibers, specifically stainless steel 316L metal fibers, may be used as the metal fibers.
Further, although not limited thereto, for example, irregularities may be imparted to the metal fibers produced by the cutting method, the drawing method and the melt extraction method.
The surface of the metal fiber formed by the cutting method or the mechanical working method of the drawing method is smooth without projections. Therefore, the metal fiber having such a smooth surface has no frictional force between the metal fibers, and thus it has been difficult to fabricate the metal fiber in the prior art.
In addition, although the surface of the metal fiber produced by the conventional melt extraction method has a height of micron level, specifically, a large number of protrusions, there is a problem that the metal fiber is escaped from the metal fiber yarn due to insufficient frictional force between the metal fibers.
On the other hand, when the metal fiber yarn is produced using the metal melt produced by the conventional melt extraction method, the friction force between the metal fibers is insufficient, so that one strand of the yarn should be made of a relatively large number of 50 to 100 metal fibers, Even in this case, there is a problem that the shape of the metal fiber yarn is not maintained because the metal fiber is missing from the metal fiber yarn.
However, as in the present invention, since the metal fibers produced by the melt extraction method as well as the metal fibers produced by the mechanical working method such as the cutting method or the drawing method are provided with sufficient frictional force and entanglement by forming the concave- Not only the metal fiber yarn can be produced but also the metal fiber does not fall out from the metal fiber yarn and the number of the metal fibers used for forming one yarn is not limited. Specifically, it can be easily produced with a yarn comprising any number of metal fibers, more specifically about 10 to 250 strands or more, of metal fibers. In addition, in the production of metal fiber yarns, yarns can be produced without using a separate binder and / or polymer.
Further, the metal fiber yarn made of the metal fiber having the irregular shape according to the present invention is excellent in porosity due to the uneven shape, and also has many very fine and uniform pores formed in the metal fiber yarns and fabrics do.
Further, due to the weak frictional force, entanglement and workability (specifically, workability in the metal fiber yarn) of the metal fiber yarn in the conventional metal fiber yarn, the diameter and the length of the metal fiber that can be used in the production of the metal fiber yarn are limited .
Specifically, conventional metal fiber yarns have been made of metal fibers having diameters in the range of 10 탆 to 100 탆, preferably in the range of 30 탆 to 100 탆, and lengths of 10 cm to 100 cm. However, the diameter and the length of the metal fiber which can be used for forming the metal fiber yarn due to the friction force, the entanglement property and the workability increase between the metal fibers are not particularly limited. That is, metal fiber yarns having a diameter of less than 10 mu m and metal fibers having a diameter of more than 100 mu m can be easily manufactured, as well as metal fibers having a diameter of 10 mu m to 100 mu m. In addition, metal fiber yarns can be easily produced using not only metal fibers having a length of 10 cm-100 cm, but also metal fibers having a length of less than 10 cm and metal fibers having a length of more than 100 cm.
However, in terms of excellent fine and uniform pore formation of fabrics made of metal fiber yarns and metal fiber yarns, it is preferred that in the same equivalent diameter yarns, a number of fine metal fibers are used instead of yarns comprising a small number of coarse metal fibers Is preferred. Specifically, for example, in a number of fine and uniform pore-forming planes fabricated from fabrics, yarns of 200 yarns (20 microns in diameter) having a diameter of 20 microns (yarn diameter of about 0.1 mm) Fabrics made with a yarn diameter of about 0.1 mm are preferred.
Further, the metal fiber having the concavo-convex shape according to the present invention has excellent elasticity due to the concavo-convex shape. Due to the elasticity, the metal fiber yarn and the metal fabric using the metal fiber yarn can be easily processed, The fabricated metal fiber yarns and the metal fabrics using them have a smooth texture.
The metal fiber on which the irregular shape according to the present invention is formed can be stretched and twisted to produce a metal fiber yarn. On the other hand, conventional metal fiber yarns are insufficient in frictional force and entanglement between metal fibers and can not be made of false twist yarns, and can be produced only by twisting yarns. However, in the case of using the metal fiber on which the concavo-convex shape is formed according to the present invention, due to the increased frictional force and entanglement between the metal fibers, it can be made into a twist yarn as well as a twist yarn. In the twist yarn and false twist yarn made of the metal fiber according to the present invention, the separation of the metal fibers is prevented and the shape of the yarn is stably maintained.
The metal fiber according to the present invention improves the frictional force between the metal fibers and has excellent entanglement, so that the twist ratio is not particularly limited in the production of the yarn. On the other hand, as is generally known in the art, false twists are produced by stretching and twisting metal fibers to produce metal fiber yarns and then twisting.
As described above, the twist rate of the metal fiber yarn in the production of the metal fiber yarn according to the present invention is not particularly limited. Depending on the use of the metal fiber fabric produced from the metal fiber yarn, the porosity and pore distribution A twist can be imparted.
For example, in the case of using a metal fiber yarn to produce a metal fiber fabric to be used as a burner material, the metal fiber yarn comprising the metal fiber according to the present invention may be used for ejecting, For example, 3-5 turns / m at the time of production into a yarn, though it is not limited thereto, in consideration of differential pressure, combustion efficiency, and the like.
As another example, when a metal fiber yarn used as a filter material is to be manufactured using metal fiber yarns, the metal fiber yarn comprising the metal fibers according to the present invention is preferably used for filtering and / But may be made of a twist yarn or a twist yarn, though not limited thereto, in consideration of a differential pressure increase due to the accumulation of dust and / or foreign matter in the pores. It is also possible to produce, for example but not limited to, twisted yarns at the time of production, for example, at 1-15 turns / m, preferably at 10-15 turns / m.
As the pores of the metal fiber yarn and / or the fabric become smaller, the filtration performance and the combustion efficiency of the fine dust and / or the foreign substance are improved, but the differential pressure and the differential pressure increase rate increase as dust and / or foreign matter accumulates. Depending on the application of the metal fabric, specifically the use of the metal fabric to the burner material and / or the filter material, so as to ensure filtration performance and combustion efficiency as well as to minimize the differential pressure rise rate, To produce a twist yarn or a twist yarn.
The metal fiber yarn according to the present invention preferably has a length of 0.45 m-10.0 m (0.45 Nm-10.0 Nm) per 1 g. If the length per 1 g of the yarn is less than 0.45 m, the thickness of the yarn becomes thick, which is not preferable from the viewpoint of porosity. If the length exceeds 10.0 m, the yarn is not formed.
The metal fiber yarn can be produced by continuously and finely stretching metal fibers having a concavo-convex shape formed thereon and twisting them. On the other hand, a false twist yarn is produced by stretching a metal fiber, twisting it, and then twisting it.
The metal fiber yarn 81 made of the metal fiber 82 having the concavoconvex shape is well entangled with each other due to the irregular shape of the metal fiber and the fiber is not pulled out from the yarn due to the increased frictional force between the metal fibers, But also a plurality of fine and uniform pores are formed between the metal fibers constituting the yarn due to the concavo-convex shape of the metal fibers constituting the yarn, thereby exhibiting excellent and high porosity. Further, the metal fiber having the irregular shape according to the present invention is not only easy to be processed subsequently due to elasticity, but also has a smooth texture.
Meanwhile, the metal fiber yarn of the present invention can be produced by weaving the fabric by a general method known in the art.
As a specific example, but not limited thereto, the fabrics according to the present invention can be produced by weaving warp yarns and weft yarns perpendicular to each other using metal fiber yarns as warp yarns (B) and weft yarns (B '). The metal fiber fabric may comprise from 5 to 30 strands (5 to 30 strands / inch) of metal fiber yarns as warp and weft yarns per inch of fabric. If the number of metal fiber yarns in the metal fabric is less than 5 strands / inch, if the diameter of the yarn is small, pores of the fabric are too large. If the number of metal fiber yarns is more than 30 strands / inch, It is not preferable in terms of blocking too much.
During weaving, wefts (A, A ') are formed on both sides of the weft yarn (A, A') with weft yarns and warp yarns arranged substantially vertically and with two weft yarns parallel to two parallel yarns. Dyeonggong refers to a part of the fabric that is slightly concave at the bottom and top. The slit has a width to height ratio of 10: 1 or less, preferably 1: 1-10: 1. If the ratio of the longitudinal length to the longitudinal length of the air gap is more than 10, there is a problem that the structure of the fabric is loosened due to the formation of the air holes through the lower yarn of 3 to 4 strands. On the other hand, as long as the porosity is not an issue, it can be produced with a fabric having a pore size of 10: 1 or less in any transverse to longitudinal length ratio.
As described above, since the metal fiber yarn is produced using the metal fiber having the irregular shape according to the present invention, the thickness and / or the length of the metal fiber used for the production of the metal fiber yarn are not limited, It is possible to use metal fibers that are thinner than the metal fibers used in the production of the metal fiber yarns and can also form morphologically stable metal fiber yarns even when a smaller number of metal fibers are used. Thus, the metal fiber yarn produced using a small number of metal fibers and / or fine metal fibers can be used to fabricate a low density metal fiber fabric having a lower density than the conventional one.
Low density metal fiber fabrics have the advantage of being capable of ultra low load combustion, especially when used as a burner material. For example, although not limited thereto, the density of the fabric may be 4.0 kg /
When the fabric is used as a burner material or a filter material, the lower limit of the fabric density is not particularly limited because the smaller the fabric density is, the smaller the fabric pressure is, the lower the pressure difference. However, if the fabric density is less than 0.1 kg / The gap between the fiber yarns is too wide and the smooth combustion or dust filtration performance may be insufficient, so that the density of the fabric is more preferably 0.1 kg /
The fabric according to the present invention can be used as a filter material and / or a burner material, specifically, a membrane for a surface combustion burner, a pre-filter for water treatment, and a filter for a soot reduction device.
On the other hand, when a conventional metal fiber fabric is used as a burner material or a filter material, a metal mesh is placed on both sides of the metal fiber fabric, and the metal fiber fabric is processed into a corrugated form Has been used. However, there has been a problem that the metal mesh, which is sandwiched on both sides of the metal fiber fabric, is easily damaged when the fabric is processed.
Therefore, in the production of the metal fiber fabric according to the present invention, the metal fiber yarn is woven together with the metal wire by using a metal wire instead of the metal fiber yarn used as the warp and / or weft, Can be manufactured. The metal wire may be used for warp and / or weft. That is, the fabric according to one aspect of the present invention is characterized in that the metal wire is used in both at least one of a plurality of warps and wefts, at least one weft or at least one warp, and at least one weft, metal wire. < / RTI > The number of the metal wires that can be used in the production of the metal fiber fabric is not particularly limited and may be selected from the range of inclination and / or thickness in consideration of physical properties required when used as a burner material or filter material, such as combustion performance, Or any location in the weft, at any interval and / or in any number of ways. The metal wire is made of the same kind of metal as the metal fiber yarn.
The metal wire preferably has a diameter of 0.07 mm to 3 mm. When the diameter of the metal wire is less than 0.07 mm, the diameter is small and the tensile force is weak. Therefore, there is no great difference between the metal wire and the metal fiber. When the diameter is more than 3 mm, the diameter of the metal wire is large. The metal fiber fabric including the metal wire does not require a separate metal mesh that is conventionally required when used as a burner material or a filter material because the fabric itself includes a metal wire. Therefore, there is no fear of breakage of the material due to the breakage problem of the metal mesh at the time of shaping into the burner material or the filter material, so that the formability into the material is improved. Also, the strength of the metal wire in the metal fiber fabric improves, and the combustion efficiency of the burner material and the filtration efficiency of the filter material are further improved due to the dense pores in the metal fabric due to the metal wire.
On the other hand, although not limited thereto, a fabric in which a metal wire is used as a warp (C) instead of a metal fiber yarn, and a fabric in which a metal wire is used as a warp (C ') in place of the metal fiber yarn.
The metal fiber fabrics made of yams containing metal fibers having irregularities according to the present invention include many uniform and uniform micropores, and are therefore suitable as filter materials for filtering fine dust and / or foreign matter. In addition, since the fuel gas is ejected finely and uniformly through the micropores, the flow rate of the gas between the metal fibers increases even when a small amount of fuel is supplied, so that the gas is stably burned. Furthermore, the fine pores between the metal fibers having the concavoconvex shape formed therein act as fine spheres, thereby exhibiting a wide range of combustion characteristics over the entire region of high load-low load, and further improved heating due to uniform flame distribution and flame splitting effect Effect. It also shows improved differential pressure performance (differential pressure reduction).
As described above, the method of manufacturing a metal fiber has been described in detail above, but such a method can be applied to a method of manufacturing a ferroelectric layer.
That is, in order to determine the phase of PVDF to be in the? -Phase, the PVDF is rapidly heated at a temperature of, for example, 60 to 70 占 폚, preferably about 65 占 폚, And the PVDF is determined to be in the? -Phase by a cooling method. By applying this method to the above-described method of manufacturing a metal fiber, a ferroelectric layer can be easily manufactured. However, the contents of these temperatures are only exemplary, and the contents of the present invention are not limited thereto.
additional information
Rolling, extrusion, drawing, and the like may be used for the method of manufacturing the carbon fiber used for manufacturing the ferroelectric layer.
First, rolling is performed by using the plasticity of a metal material having a high temperature or a room temperature passing between two rotating rolls to form a plate, a rod, a pipe, a shape, and the like , Which is faster than casting or forging and has a low production cost
Next, it is said that the extrusion was made by J. Brahma of England in 1797 by melting the lead and pumping it out to make the lead pipe. Then in England, Th. Birr actually manufactured the linkage in 1820 using an extrusion process. Generally, a material (material) is put into a container (container) and is pushed out from a hole of a die to make a product having a sectional area smaller than a material and having a constant length.
This processing method is largely divided into a positive extrusion method and a reverse extrusion method. The former is the case where the direction of the metal to be extruded is the same as the direction in which pressure is applied from the outside, and the latter is the opposite direction.
Since the shape of the product section is the same as the shape of the hole of the die, it is possible to make a round bar, a square bar, a shape member, a pipe or any other by changing the hole shape of the die appropriately. However, pushing the metal material out of the hole requires a very large force, which is not only a large-scale machine, but also has the drawback of using tools that withstand high temperatures and high pressures.
Hot extrusion is performed at a high temperature, and cold extrusion is performed at a room temperature. During the Second World War, cold extrusion processing technology of hard metal was rapidly developed in Germany, and cold extrusion of special steel was used to mass produce high dimensional precision products and to produce military materials.
Finally, drawing refers to a processing method in which a rod or tube is passed through a die having a smaller cross-sectional area than that of the die or pipe, thereby obtaining a cross-sectional product having the same shape as the die bore. Drawing of thin-walled wire is especially called drawing. Generally, there are many cold draws. It applies to most of carbon steel, alloy steel and nonferrous metals. In some cases, nickel or copper plating or copper plating is performed on the rods or pipes before drawing. There is an effect of improving the lubricity and preventing the oxidation of the material during normal processing.
The rolling, extrusion, and drawing methods described above can be used variously to produce the ferroelectric layer, and the manufacturing method of the rod invention is not limited by any one method.
Azobenzene How to use
On the other hand, the ferroelectric material PVDF is very inexpensive, chemically inert and able to withstand high temperatures, but only the transflective? Phase of the four different crystalline phases (?,?,?,?) Exhibits the best ferroelectricity .
In general, PVDF is made at room temperature, and since it is crystallized in the nonpolar phase, it is fairly rough and has no ferroelectric properties. (PVDF-TrFE) with trifluoroethylene, which is difficult to fabricate, is very costly, loses ferroelectricity at temperatures above 80 ° C and functions as a memory device can not do.
On the other hand, azobenzene is a molecule in which two benzene rings are linked by -N = N-bond. Due to the nonspecific electron pair of nitrogen, azobenzene has two geometric isomers, cis and trans. Thermodynamically, at room temperature trans-form azobenzene is relatively more stable and trans-form azobenzene predominates in the normal state. However, irradiation of ultraviolet light to trans-azobenzene causes isomerization to cis-azobenzene. This is because the cis-type azobenzene is more stable in the transition state. This isomerization reaction is reversible by light.
Therefore, in the present invention, azobenzene having a geometric isomer is used to form a trans-type? -Phase PVDF film exhibiting ferroelectricity. That is, a ferroelectric PVDF film which is difficult to implement by a general method is proposed to easily produce a ferroelectric film by using azobenzene.
That is, PVDF forming azobenzene and polymer is prepared, and azobenzene having a trans-type structure at room temperature is used to make PVDF a trans-type structure.
Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. In addition, the embodiment described below does not unduly limit the contents of the present invention described in the claims, and the entire configuration described in this embodiment is not necessarily essential as the solution means of the present invention.
13 is a flowchart showing a method for producing a PVDF-azobenzene polymer film according to an embodiment of the present invention.
A PVDF-azobenzene polymer solution is prepared (S110).
(I) a method of mixing
14A-14C illustrate the preparation of a PVDF-
First, FIG. 14A shows (i) mixing
Next, Fig. 14B shows (ii) dispersing azobenzene in the
14C is a diagram (iii) in which PVDF is dispersed in the
As the solvent for making the
The solvent for making the
However, according to the paper (Studies on the Isomerization Reaction Rates of Azobenzene Derivatives, The Chemical Society of Korea, 1994), pull-push azobenzene causes a more rapid isomerization reaction from cis to trans form in polar solvents .
It is preferable to use a polar solvent when the azobenzene solvent is used. Examples of the polar solvent include ethyl acetate, THF (tetrahydrofuran), butyl alcohol, IPA (isopropyl antipyrine) Acetone and acetonitrile.
If such a polar solvent is used, the azobenzene in the cis form will be isomerized to the trans form more rapidly. As a result, when azobenzene is formed into a trans-form, PVDF combined with azobenzene will also be formed into a trans-form, so that it is advantageous to prepare a trans-form azobenzene using a polar solvent.
On the other hand, carbon nanotubes (CNTs) can be added to the PVDF-
Therefore, when carbon nanotubes (CNTs) or metal particles are added to the PVDF-
On the other hand, it is preferable that the carbon nanotubes are dispersed in a ratio of 0.01 to 0.1% by weight with respect to the PVDF-
In addition, the transparency (transmittance) of the PVDF-
When the carbon nanotubes are dispersed, they can be uniformly dispersed in the solution through ultrasonic treatment. However, the dispersion method is not limited thereto.
Next, the PVDF-
Figure 16 is a diagram illustrating the application of visible light to a PVDF-azobenzene polymer solution according to one embodiment of the present invention, wherein the solution can be irradiated with visible light as in Figure 16.
As described above, azobenzene has photosensitivity to react with light.
That is, at room temperature, trans-type azobenzene as shown in FIG. 10A predominantly exists. However, when this azobenzene is irradiated with ultraviolet rays, an isomerization reaction occurs to the cis-form azobenzene as shown in Fig. 15B. When cis-azobenzene is irradiated with visible light, it is transformed into trans-form azobenzene.
By irradiation of light having a wavelength of 345 to 380 nm, the trans form changes into a cis form, and isomerization from a trans form to a cis form occurs by irradiation of light having a wavelength of 400 to 460 nm.
In the present invention, since it is the purpose of forming a β-phase PVDF having a trans-type structure, it is possible to make PVDF also have a trans-type structure by irradiating visible light to make the azobenzene have a trans-type structure.
Next, the PVDF-
The
FIG. 17A shows a PVDF-azobenzene polymer solution applied to a substrate according to one embodiment of the present invention, and FIG. 17B illustrates a method of forming a uniform PVDF-
The PVDF-
Next, the solvent of the PVDF-
FIG. 18 illustrates that the solvent of the PVDF-azobenzene polymer solution is evaporated according to one embodiment of the present invention, and the solvent is evaporated as shown in FIG. 18 to form a
When the solvent is evaporated as described above, the PVDF-
The supporting
FIG. 19 illustrates that the support film is bonded to the PVDF-azobenzene film according to one embodiment of the present invention, and the
The
Next, the adhesion between the PVDF-
Figure 20 illustrates the creation of a wetting environment for separating films according to one embodiment of the present invention and is illustrated in a wet environment to weaken the interface bonding force between the film and the
Next, the
The support film and the PVDF-azobenzene polymer film can be easily separated from the substrate as shown in FIG. 21A. Thus, as shown in FIG. 21B, the
Next, an annealing process is performed (S180).
The above annealing process can be added to improve the crystallinity of the PVDF-
In addition, an electrical poling process may be added to the PVDF-
Hereinafter, PVDF-azobenzene prepared by the above-mentioned method will be described.
Figure 22 is a chemical structure of PVDF-azobenzene prepared according to one embodiment of the present invention.
According to the above-described PVDF-azobenzene polymer film production method, PVDF-azobenzene has a trans-type structure as shown in FIG. 22, and the crystalline phase of PVDF becomes a? Phase and exhibits good ferroelectricity.
As it is known, ferroelectric PVDF has piezoelectric superconductivity and can be used in various industrial fields such as memory device, sensor, film speaker and so on.
In addition, PVDF-azobenzene undergoes cis-trans isomerization by light irradiation. That is, the chemical structure of PVDF-azobenzene having the chemical structure shown in FIG. 22 can be changed as shown in FIG. 23 due to exposure to ultraviolet rays.
Therefore, PVDF-azobenzene has properties different from those of the structure as shown in FIG. 22, and it can be utilized as an optical memory device, an optical switch, a display device, and a sensor by using this property, It can cause effects.
Other Example
Also, according to the present invention, a method of additionally including carbon nanotubes may be used to increase the strength.
Carbon nanotubes are a new material with six carbon hexagons connected together to form a tube.
Its electrical conductivity is similar to that of copper, its thermal conductivity is the highest in nature, and its strength is 100 times better than steel. Carbon fibers can be broken even if they are deformed by only 1%, while carbon nanotubes can withstand 15% deformation.
Since the discovery of carbon nanotubes, devices using carbon nanotubes such as semiconductors, flat panel displays, batteries, super-strong fibers, biosensors, and television cathode-ray tubes have been developed extensively, and nanotubes that can transfer nano- .
Further, according to the present invention, the performance of the bulletproof glass can be further improved by further including graphene.
Graphene is a thin film of carbon atoms, one atom thick.
It is 100 times more electricity than copper, and it can move electrons more than 100 times faster than monocrystalline silicon, which is mainly used as a semiconductor. Strength is more than 200 times stronger than steel, and has twice the thermal conductivity than diamonds with the highest thermal conductivity. It is also excellent in elasticity and does not lose its electrical properties even when stretched or bent.
Because of these properties, graphene is regarded as a material that goes beyond carbon nanotubes, which are regarded as the next generation of new materials, and is called 'dream nanomaterial'. Graphene and carbon nanotubes have very similar chemical properties and can separate metallic and semiconducting materials through post-processing. However, because carbon nanotubes have more uniform metallic properties, they are more likely to be applied industrially. The addition of such graphene can further enhance the performance of the bulletproof glass.
The present invention can also be embodied as computer-readable codes on a computer-readable recording medium. A computer-readable recording medium includes all kinds of recording apparatuses in which data that can be read by a computer system is stored. Examples of the computer-readable recording medium include a ROM, a RAM, a CD-ROM, a magnetic tape, a floppy disk, an optical data storage device, and the like, and may be implemented in the form of a carrier wave (for example, transmission over the Internet) . In addition, the computer-readable recording medium may be distributed over network-connected computer systems so that computer readable codes can be stored and executed in a distributed manner. In addition, functional programs, codes, and code segments for implementing the present invention can be easily inferred by programmers of the technical field to which the present invention belongs.
The method of manufacturing the PVDF-azobenzene polymer film described above is not limited to the configuration and method of the embodiments described above, but the embodiments may be modified so that all or some of the embodiments are selectively As shown in FIG.
Claims (34)
The bulletproof glass is a bullet-
A plurality of tempered glass joined to the plurality of layers;
A plurality of polyethylene film layers laminated and disposed between the plurality of tempered glasses; And
And a ferroelectric layer disposed between at least a portion of the plurality of tempered glass and the plurality of polyethylene film layers,
The ferroelectric layer is a PVDF-azobenzene polymer film,
The method for producing the PVDF-azobenzene polymer film comprises:
A first step of polymerizing PVDF and azobenzene to prepare a PVDF-azobenzene polymer solution;
A second step of applying the PVDF-azobenzene polymer solution on a substrate;
A third step of evaporating the solvent of the PVDF-azobenzene polymer solution to form a PVDF-azobenzene polymer film; And
And a fourth step of separating the substrate from the PVDF-azobenzene polymer film.
In the first step,
A method of mixing a PVDF solution and an azobenzene solution, a method of dispersing azobenzene in a PVDF solution, and a method of dispersing PVDF in an azobenzene solution are used.
The solvent of the PVDF solution is at least one of MIBK (methyl isobutyl ketone), MEK (methyl ethyl ketone), NMP (N-methyl-2-pyrrolidone), DMF (dimethylformamide) and DME , ≪ / RTI >
Wherein the solvent of the azobenzene solution is a polar solvent.
Wherein the solvent of the azobenzene solution is at least one of ethyl acetate, THF (Tetrahydrofuran), butyl alcohol, IPA (isopropyl antipyrine), acetone and acetonitrile. Gt;
In the first step,
And dispersing carbon nanotubes (CNTs) in the PVDF-azobenzene polymer solution.
Wherein the carbon nanotubes are present in an amount of 0.01 to 0.1% by weight based on the PVDF-azobenzene polymer solution.
After the first step,
Further comprising the step of irradiating the PVDF-azobenzene polymer solution with visible light.
In the first step,
And dispersing metal particles in the PVDF-azobenzene polymer solution.
In the second step,
Wherein at least one of a method using an applicator, a method using a bar coater, and a spin coating method is used.
Wherein the substrate is made of a hydrophilic coating-treated material.
Wherein the substrate is made of glass or polymer.
In the third step,
To produce a flow of gas over the PVDF-azobenzene polymer solution to induce uniform volatilization of the solvent.
Wherein the gas is an inert gas.
After the third step,
And bonding the support film to the PVDF-azobenzene polymer film.
Wherein the support film comprises at least one of silicone elastomer and polydimethylsiloxane (PDMS).
Wherein the support film is formed by coating at least one of silicone elastomer and polydimethylsiloxane (PDMS) on a PET (polyethylene terephthalate) film.
Before the fourth step,
Further comprising the step of weakening the adhesion between the PVDF-azobenzene polymer film and the substrate.
In the step of weakening the adhesion between the PVDF-azobenzene polymer film and the substrate,
Characterized in that the substrate and the PVDF-azobenzene polymer film are provided with a wetting environment.
Wherein said wetting environment is water, distilled water, deionized water or IPA (isopropyl alcohol).
After the fourth step,
Characterized in that a further annealing step is carried out.
After the fourth step,
Wherein the method further comprises performing an electrical poling process.
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| JP5099596B2 (en) * | 2007-05-18 | 2012-12-19 | 日本電気硝子株式会社 | Laminated glass and manufacturing method thereof |
| KR101258388B1 (en) * | 2012-07-15 | 2013-04-30 | 김일순 | A method for manufacturing bulletproof panel |
| KR101411374B1 (en) * | 2013-04-29 | 2014-07-04 | 권화중 | Dual electric heated bullet roof resistant glass |
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| JP5099596B2 (en) * | 2007-05-18 | 2012-12-19 | 日本電気硝子株式会社 | Laminated glass and manufacturing method thereof |
| KR101258388B1 (en) * | 2012-07-15 | 2013-04-30 | 김일순 | A method for manufacturing bulletproof panel |
| KR101411374B1 (en) * | 2013-04-29 | 2014-07-04 | 권화중 | Dual electric heated bullet roof resistant glass |
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