KR20160021047A

KR20160021047A - Fabrication of positive molds, membranes fabricated using the molds, and their fabrication methods

Info

Publication number: KR20160021047A
Application number: KR1020150113243A
Authority: KR
Inventors: 정대영
Original assignee: 한국전기연구원
Priority date: 2014-08-14
Filing date: 2015-08-11
Publication date: 2016-02-24

Abstract

The present invention relates to a relief mold production method, a membrane produced by using relief mold, and a production method thereof. According to the present invention, the method comprises: a step of forming a first anode oxide layer by subjecting a metal surface for an intaglio mold to anode oxidation; a step of forming a nanosheet sunken into the metal surface for the intaglio mold, by removing the first anode oxide layer; a step of forming a second anode oxide layer via anode oxide on the nanosheet; a step of forming a nanopattern of increased diameter and depth relative to the nanosheet, by etching the second anode oxide layer in the nanosheet region; and a step of obtaining an anode mold by vapour depositing and demolding an anode- mold material on a metal for intaglio molding on which the nanopattern is formed.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing a positive mold, a membrane manufactured using the positive mold,

The present invention relates to a method for producing a positive mold, a membrane manufactured using a positive mold, and a method for manufacturing the same. More particularly, the present invention relates to a method for producing all the polymers such as PA, PE, PP, PVDF, polyamide, Very low separation selectivity and severe fouling phenomena, such as non-uniform size pores, which are characteristic of all porous metal films such as membranes, metal foams, porous metal sintered bodies, etc., and sponge structures interconnected by these pore channels, Overcome low fluid permeability, overcome limited applications due to large pores and high manufacturing cost of metal mesh or perforated metal, or make high production of metal film using self-assembled nanotechnology using spherical polymer nanoparticles In order to overcome the limited application field by unit price, it is necessary to use the anodic oxidation process and the etching process to remove submicron A negative embossed mold having a porous anodized surface with aligned pore channels with various angles of the surface ranging from a cylindrical nano-sized uniform diameter and an appropriate length to a conical shape was prepared, and then the surface and pore of the alumina negative- High strength inorganic materials such as diamond, SiC and DLC, or high strength metals such as Ni, Cr and W, or high strength alloys thereof are deposited by physical or chemical vapor deposition or electrodeposition or the like and then demolded or alumina mold is removed , A high strength embossed mold in which embossed long embossed patterns are embossed with pores in a negative embossed mold are manufactured and then the embossed mold is used to perforate a polymer film or metal thin plate, Or a casting process, a molding process, or after forming various material layers on the relief mold, After forming a polymer layer, a metal layer, and a polymer / metal composite layer by physical or chemical vapor deposition, the polymer layer is separated from the mold so as to have a shape similar to a column of a high strength positive mold and having a diameter of from sub-micron to nano- A method for manufacturing a positive embossed mold for obtaining a (separating) membrane comprising a polymer membrane or a metal membrane having a linear pore channel of uniform diameter, a membrane manufactured using the embossed mold, and a method for manufacturing the same.

(Cellulose acetate), PAN (Polyacrylonitrile), PA (Polyamide), PC (Polycarbonate), PE (Polyethylene), PES (Polyethersulfone), PP (Polypropylene), PS (Polystyrene), PVDF Most polymer membranes such as polyvinylidene fluoride and polyester are prepared by solvent phase conversion, thermal induction phase separation, stretching, track etching, etc. to form pores. In this method, since the shape and size of the pores formed in the polymer membrane are not constant, the selective separation function of removing impurities of a certain size is poor. In addition, these polymer membranes have a curved pore channel, which is connected internally to form a sponge structure as a whole. The interconnection of the pore channels has a positive effect of improving the permeability of the fluid by selecting a shorter filtration path than when the fluid flows into the pores. However, since the object introduced through the larger pores on the surface is smaller in size It is surrounded by pores and can not escape to the outside, and it causes a serious clogging phenomenon which is trapped in the inside. Since the pores trapped by the object can not participate in the separation or filtration phenomenon, the permeation rate of the membrane is remarkably reduced. Therefore, even if the pores are bent and have a sponge structure connected to the inside, the polymer membrane having a uniform diameter of the pore channels and having no uniform trapping of an object, or a linear uniform pore channel having pores not connected to the inside of the membrane, It has been required to develop a polymer membrane in which the diameter of the channel becomes larger toward the opposite surface and trapping of an object does not occur. However, since it is difficult to fabricate a membrane having a constant pore diameter through a channel length such that the diameter of a bent pore channel such as an electron is always difficult to manufacture, the channel pore is always constant or approaches the other surface The development of thin films has been required. The development of low-energy (separation) membranes with high economical efficiency without the need to apply high pressure for separation or filtration with a small pressure difference across the membranes when the pore channels are straightened without bending, Has come.

In addition, a metal form used for water treatment, air purification, industrial separation process, protein and virus separation, fuel cell, etc. is manufactured by blowing gas into molten metal liquid. Thereby, the pores are composed of various types of pores which are completely open, semi-open or completely closed, which are not uniform in size and have a sponge structure in which the pores are interconnected in the interior. Therefore, the separation selectivity is low, the clogging of the membrane is serious, and the production is expensive and expensive. Also, the porous metal sintered body having the pores formed by sintering the particulate metal powder and connecting the particle phases through the diffusion has a sponge structure in which the pores and the pore channels of the non-uniform size are interconnected with each other. As a result, the separation selectivity is low and the clogging phenomenon is serious. In addition, a metal mesh produced by crossing a fine line or a fiber and fabricated in the form of a fabric depends on the pore size of the fine wire or fiber used. In the case of a fine mesh metal mesh, the pore size is less than several tens of microns It is hardly developed. In addition, when the fiber is used, the pore size is reduced to several microns, but the size is not constant and the pores are connected to each other, so that the selectivity is low and there is a definite limit of the severe clogging. Also, a perforated metal film of the same type as the present invention can make linear pores have a desired alignment state, but the pore size is limited to a few hundred microns. Therefore, although most of the porous metal films have excellent mechanical strength, impact resistance and heat resistance, they are limited in their pore size compared to the expensive ones, and are used by the clogging due to the nonuniformity of the pore size and the mutual connection of the nonuniform sizes There is a disadvantage in that it is limited or the maintenance is expensive and the service life is limited. Therefore, first of all, a metal film with sub-micron to several nanometer size pores, which can be used in ultrafiltration and microfiltration fields with wider applicability, it also has a uniformly linear asymmetric pore with high selectivity and high transmittance (Separating) film having a high thermal conductivity has been demanded.

One type of anodizing, so-called anodizing, involves immersing a metal such as aluminum in an acidic electrolyte and applying a constant voltage to form an anodized layer of aluminum. As shown in Fig. 1, cylindrical pores are formed at the center of a hexagonal anodic oxide nanoside whose cell size is determined according to the kind of an electrolyte and an applied voltage. In addition to the surface shape in which circular pores are arranged on the surface, A porous structure in which patterns are arranged at regular intervals appears. Fig. 2 is a conceptual diagram clearly illustrating the cross-sectional photograph of Fig. 1 (b), which is an FE-SEM image showing that the end of the nanopattern is clogged by a convex aluminum oxide barrier layer directed downward. In this case, when a certain voltage is applied under the electrolyte, the hexagonal pores are filled in the highest density to self-organize the hexagons. When viewed from the surface, the circular pores show a well-aligned hexagonal shape.

At this time, the size of the nanopattern, that is, the distance of the neighboring space depends on the type of the electrolyte and the applied voltage. When a constant voltage of 195 V is applied to the phosphoric acid electrolyte, 500 nm is applied to the oxalic acid electrolyte, 300 nm when the oxalic acid electrolyte is applied, 100 nm when the 40V is applied, 140 nm when the sulfuric acid electrolyte is applied, and 60 nm when the 25V is applied. However, in the case of aluminum that has been subjected to anodic oxidation for a long time, the pores having relatively well-defined circular shapes are arranged in the vicinity of the lower surface, but the upper surface shows an abnormal state A cell with an irregular shape having an uneven size appears. As a result, the uniformity of the shape and alignment of the pores increases as it approaches from the upper surface to the lower surface. Therefore, in order to obtain an excellent shape of the cell shape on the upper surface after the anodic oxidation, that is, the shape of the pore and the alignment of the cells, the alumina layer formed after one anodic oxidation is removed, and the alignment of the remaining concave grooves is used as the seed, Once more anodic oxidation is carried out in a way that the well-defined hexagonal cells on both the top and bottom surfaces exhibit an aligned shape. The pores located at the center of the hexagonal cell have a circular shape, and these circular pores appear regularly aligned along the hexagon. The porous anodic alumina pores thus produced have a size of about 10% square root of the cell space, that is, about 70% of the neighboring space distance of the neighboring space. As shown in FIG. As shown in Fig. 1, the pore has a convex cylindrical shape at the lower part. The cylindrical wall and the convex lower part are surrounded by a certain thickness of alumina layer. The lower alumina layer is referred to as an oxide barrier layer. As the anodization continues, the barrier layer moves downward and the cylindrical pores become longer in the form of pore channels. The growth rate of the pore channel, that is, the growth rate of the anodic alumina layer is 1 to 3 占 퐉 / hr or 50 to 70 占 퐉 / hr depending on the anodic oxidation system. However, by controlling the duration of the secondary anodization and the etching time after the anodic oxidation The pore diameter ratio to the pore length can be controlled. Further, by repeatedly performing the anodic oxidation process after the etching process, the pores are removed from the convex cylindrical shape of FIG. 2 to the concave shape of FIG. 3, and the concave shape of the concave end of FIG. An alumina mold can be produced.

However, high strength metals such as diamond, SiC, and DLC, high strength metals such as Ni, Cr, W, or the like may be added to the surface and pores of the relief mold having pore channels of various shapes ranging from a convex cylindrical shape to a conical shape and a sharp cylindrical shape. Of the high-strength alloy is filled with various deposition methods such as chemical vapor deposition or electro-deposition, and then mechanical or electrochemical methods are employed to remove the alumina mold, or the alumina mold is removed to form the pore channels of the negative- It is possible to manufacture a high-strength positive mold in which a protruding embossed pattern of embossing is formed.

When a high strength inorganic material, metal or alloy embossed mold having a column inclined at various angles from the cylindrical shape to the conical shape is applied to various polymer membranes or metal films, It is possible to manufacture asymmetric polymer membranes and metal membranes having a conical shape in which the diameter of the pores is enlarged as one approaches the other surface with a certain diameter on one surface without using a special manufacturing method. Also, it becomes possible to manufacture a symmetric polymer membrane and a metal membrane in which cylindrical pores having a constant pore diameter are engraved, even if they approach the other surface. That is, in the initial or intermediate process of making a metal thin plate or a thin film from a melted metal material, a positive plate having a column or a conical column is used as a template to make a thin plate or a thin film having a lower open pore, (Separating) the polymer film having a linear asymmetric pore and the metal film, by allowing the pillars of the relief mold to penetrate the thickness of the thin plate or thin film by pressing or punching the thin film with a positive mold, A membrane can be produced.

Conventional polymer membranes, metal foraminous membranes, metal sintered membrane membranes, and metal fiber membranes used for water treatment, air purification, industrial separation processes, protein and virus separation, and fuel cells have a sponge structure in which pores having uneven sizes are connected to each other The separation selectivity is very low, the film fouling phenomenon is serious, the permeability of the fluid is low, and the price is also high. Although the metal mesh membrane and the perforated metal membrane are composed of pores having a uniform size, the pores having a pore size of less than several tens of microns are hardly developed and their application fields are very limited. Most high-performance polymer membranes are manufactured by special methods and are expensive to manufacture. Most metal separators have excellent mechanical strength, impact resistance and heat resistance, but they have a disadvantage of high production cost.

Therefore, a separator having a high separation selectivity from a sub-micron to a nano-sized uniform size, a separator having a linear pore with less clogging and a high fluid permeability can be manufactured at a very low manufacturing cost, Development of membranes has been required.

Accordingly, in order to overcome the non-uniformity of the pore size of the conventional metal film, the pore bending, the low selectivity resulting from the sponge structure, the severe membrane plugging, the low fluid permeability, and the limitations of the application due to the relatively large pore size, Manufacture of a positive membrane and a metal membrane with linear pores of uniform diameter in the range of micrometer to several nanometers at a very low manufacturing cost and a method of manufacturing a positive mold for obtaining a low selectivity, low clogging, high permeability (separation) membrane , A film produced using a positive mold, and a method for producing the same.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method of manufacturing a semiconductor device, comprising: anodizing a metal surface for a negative-tone mold to form a first anodized layer; Removing the first anodized layer to form a recessed nano-seed on the metal surface for the negative-tone mold; Forming a second anodization layer on the nano-seed through anodic oxidation; Etching the second anodization layer of the nanoside region to form a nanopattern having increased diameter and depth than the nanoside; And a step of depositing and demolding the material for the relief mold on the metal for the relief mold where the nano pattern is formed to obtain a relief mold.

Here, for alignment of excellent pores, anodic oxidation of the metal surface for the negative-tone mold to form a first anodized layer; Instead of the step of removing the first anodized layer to form a depressed nano-seed on the metal surface for the negative-tone mold, sharp-pointed pillars having a pore distance corresponding to the anodic oxidation process of the anodic oxidation process are aligned Using an imprinting mold to form an array of points having undergone local variations by squeezing a metal surface for an angular mold to be anodized and then forming an anodized layer and forming the second anodized layer of the nano- Forming a nano pattern having increased diameter and depth from the nano-seed by etching; and forming a positive mold by depositing and demolding a material for a relief mold on the metal for the relief mold having the nano-pattern.

Here, the step of forming the anodic oxidation layer is repeated so that the depth of depression of the nanopattern is increased. By repeatedly performing the step of forming the anodic oxidation layer, the nanopatterns have a cylindrical shape with a diameter equal to a hemispherical shape Or by repeating the step of forming the anodic oxide layer, the diameter of the nanopattern is gradually reduced in a conical shape.

An object of the present invention is to provide a method of manufacturing a semiconductor device, comprising: anodizing a metal surface for a negative-tone mold to form a first anodized layer; Removing the first anodized layer to form a recessed nano-seed on the metal surface for the negative-tone mold; Forming a second anodization layer on the nano-seed through anodic oxidation; Etching the second anodization layer of the nanoside region to form a nanopattern having increased diameter and depth than the nanoside; Depositing a material for the relief mold on the metal for the relief mold in which the nano pattern is formed to obtain a relief mold having a long relief pattern formed by embossing; And forming a linear pore channel in the film or the thin film using the positive mold. The present invention also provides a method for manufacturing a pore-channel-formed membrane using the nano-positive mold.

The step of repeating the step of forming the anodic oxidation layer so as to increase the recess depth of the nano pattern and the step of coating the releasing film on the surface of the positive mold to improve the detachability of the film formed with the linear pore channel using the positive mold .

The film or the thin film is preferably a polymer film or a metal thin film.

The object of the present invention is also achieved by an anodic oxidation method for forming a nano-seed by anodizing a metal surface for a negative-tone mold, forming a nanoparticle having an increased diameter and depth by the anodic oxidation and etching of the nanoside, Wherein a straight pore channel of uniform diameter is formed by imprinting a relief pattern formed by embossing and demolding a material for a relief mold on a metal for a relief mold in which a pattern is formed, Is also achieved by a membrane having a pore channel fabricated using the method of the present invention.

The present invention based on the above-mentioned constitution has the following advantages. That is, it is possible to provide a porous membrane having a low selectivity due to a non-uniformity of pore size in a conventional polymer membrane or a porous metal membrane and a sponge structure in which bent pores are interconnected with each other, In order to overcome the limitations of applications due to relatively large pore size and the limitations of metal meshes and perforated metal pore sizes exceeding tens of microns, polymer membranes with linear pore channels of uniform diameter in the sub-micron to several nm range It is possible to provide high selectivity, low film clogging, and higher fluid permeability by providing a film having linear pore channels of uniform diameter such as a metal film, a polymer / metal polymer / ceramic, and a metal / ceramic composite film. In addition, since this nano-separator is manufactured by a simple process of perforation regardless of materials or materials used, it is advantageous to manufacture a membrane of various materials at a much lower production cost than a conventional polymer or metal membrane manufactured by a specific manufacturing method have. Accordingly, the present invention has a higher fluid permeability than conventional polymer membranes or metal membranes, and thus has a higher treatment efficiency than conventional metal membranes. In addition, since the pressure drop across the membrane through linear channel pores is small, And the cleaning cycle is greatly reduced as the membrane is less clogged. As a result, the maintenance cost is remarkably reduced, the life span is lengthened, and the filtration of the oil, food and beverage, purification of the drug, The present invention has an effect of greatly expanding the application range of the (separating) membrane, such as separating fine dust, which has recently become an environmental problem, at a smaller cost.

Fig. 1 shows (a) a photograph of the upper surface FE-SEM showing a linear pore channel alignment in the porous anodic alumina prepared by anodizing aluminum and (b) a linear pore channel structure near the upper surface It is a cross-sectional photograph taken at an angle to show,
FIG. 2 is an FE-SEM image showing the shape of the lower part of the pore channel after anodic oxidation in a 0.3M oxalic acid electrolyte for 20 hours and a 0.5% phosphoric acid solution as an etching solution for 30 minutes, Lt; RTI ID = 0.0 > a < / RTI > convex aluminum oxide barrier layer,
FIG. 3 is a schematic view of an anodic alumina intaglio mold having a long cylindrical shape with a sharp end as an embodiment of the present invention. FIG. 3 (a) shows an aluminum plate having a very low surface roughness, (b) is a state in which an aluminum plate (a) is pressed with an imprint to form aligned pores so that the pores are aligned well, and then pores are formed through a plurality of anodic oxidation, (c) (C) is subjected to anodic oxidation to form a pore having a certain length (c) at a lower portion of the pore in (c) (E) is an appearance of an oblique pore wall in which the angular portions between the pores having different diameters are softened by etching (d), (f) is anodic oxidation again (e) at the bottom of the pore in (e) (F) is etched so that the angular portion between the pores having different diameters at the end of the pore is softened and the end of the pore is softened A long cylindrical pore channel having a sharp cone shape is formed,
Fig. 4 is a schematic view showing a manufacturing process of a nickel-embossed mold as an example of the manufacture of a high-strength positive-relief mold, wherein (a) is anodic oxidation alumina (B) is a view showing a nickel embossed in a pore and an alumina surface in (a), (c) a nickel embossed mold demolded in a intaglio alumina mold of (b)
FIG. 5 is a graph showing the results of measurement of a polyamide separator having a linear asymmetric pore channel by piercing a polyamide polymer thin film using a plate-like embossed nickel mold having alignment of a conical column, (B) a schematic diagram of a polyamide separator having a linear asymmetric pore channel fabricated using a positive mold (a), and
Fig. 6 is a schematic view of an anodic alumina intaglio mold having a conical pore channel according to another embodiment of the present invention, in which (a) shows an aluminum plate before anodizing, (b) (B) is etched for a certain period of time to form pores in (b) and (c) in FIG. 5 (b), and the pores are formed through a plurality of anodic oxidation steps so that aligned pores are formed by pressing the aluminum surface with imprint for excellent alignment of pores. (C) is again anodized to form a new pore having a smaller diameter than that of (c) at the bottom of the pore in (c), and (e) (D) is etched, and then anodic oxidation and etching are repeated once again to form an inclined pore wall where the angular portions between the pores having different diameters are softened. (F) After the etching is repeated once, FIG. 2 is a conceptual view of a concave alumina mold in which a long conical linear pore channel is aligned by anodic oxidation,
Fig. 7 is a schematic view showing a manufacturing process of a embossed diamond mold as an example of manufacturing a high-strength embossed mold, in which (a) is an intaglio alumina mold in which a long conical linear pore channel of Fig. 6 (f) (A) shows a state in which diamond is deposited on the inside of pores and on the surface of alumina by chemical vapor deposition (CVD) method, (c) shows a diamond mold of embossed shape demolded in the intaglio alumina mold of (b)
FIG. 8 shows an embodiment of the present invention in which (a) a titanium (Ti) thin film is pierced using a plate-shaped embossed diamond mold having an array of conical columns to penetrate the thickness of the thin film to form a linear asymmetric pore channel, (B) a schematic view of a titanium separator having a linear asymmetric pore channel produced by using a positive mold (a), and
FIG. 9 is a graph showing the results of the measurement of the mechanical strength of the Ni-Cr alloy prepared by the electrodeposition method of FIG. 4, which is superior in mechanical strength to the anodic alumina mold having a long conical linear pore channel, (A) and cross-sectional view (b) on the upper surface of the adhesive bonded together with the peeled strips to bond the plate-shaped embossed Ni-Cr molds to the cylinder, and (b) Is a schematic cross-sectional view of the embossed Ni-Cr roll mold (c) wound around the cylinder while removing the separating strip,
FIG. 10 shows an embodiment of the present invention, in which a heated PP thin film is punched using the embossed roll mold of FIG. 9 (c) while supplying the PP thin film in a roll-to-roll process to form a PP polymer membrane having uniform asymmetric linear pore channels Fig.

Hereinafter, a method of manufacturing a positive embossed mold according to an embodiment of the present invention, a thin film produced using a positive embossed mold, and a method of manufacturing the same will be described in detail with reference to the drawings.

In order to accomplish the above object, the present invention provides a method of manufacturing a nanostructured membrane having a linear pore channel of uniform diameter, comprising the steps of: (a) forming an aluminum plate having a uniform diameter from a sub-micron to a nanometer size using an anodic oxidation process and an etching process; A porous alumina anodic alumina surface layer having porous pores having various angles ranging from a cylindrical shape having an appropriate length to a conical shape was prepared and then an alumina negative mold was produced. High strength inorganic materials such as SiC and DLC or high strength metals such as Ni, Cr, and W, or high strength alloys thereof are deposited by physical or chemical vapor deposition or electrodeposition or the like and then demolded or anodized In the anodic oxide intaglio mold, the embossed pores become the pillar of the embossed, To produce a high-strength mold embossed turn is formed.

After that, the embossed mold is used as it is, or the embossed mold is wound on the surface of the cylinder to form a cylindrical mold, and then the polymer film precursor in the process of forming the polymer film or in the manufacturing process or the initial or intermediate process , The metal foil in the final step, the polymer / metal or polymer / ceramic or metal / ceramic composite film or thin plate which has already been formed or being formed can be pressed or perforated by using this mold, It is possible to obtain a membrane having a symmetric or asymmetric linear pore channel of uniform diameter by producing a composite membrane having a linear pore channel of one size, a metal separator, a polymer / metal, a polymer / ceramic, and a metal / ceramic.

The aluminum for attaining the above is a high purity of 99.99% or more or a high purity of at least 99.99% It may be desirable to include one or more of the elements.

The metal surface for the negative mold is cleaned using an alcohol, acetone, or aqueous solution before anodic oxidation, and then the surface roughness is adjusted to 10 탆 to 0.1 ㎚ using one or more of electrolytic polishing, mechanical, chemical, .

The anodic oxidation of the metal is maintained at a temperature of -50 ° C to 300 ° C by using one of phosphoric acid, oxalic acid, sulfuric acid, malonic acid, tartaric acid, citric acid, malic acid, While applying a voltage of 1 to 500 V for 1 minute to 1 week to perform anodic oxidation. The anodic oxidation is preferably repeated twice or more for better pore alignment.

The anodic oxidation is performed by using an imprinting mold in which sharp-pointed columns having pore-to-pore distances corresponding to the anodic oxidation system of the anodizing process are aligned for the alignment of excellent pores, To form an array of points that have undergone local variations, and then anodic oxidation is preferably performed.

When an imprinting mold is used or two or more times of anodic oxidation are used, it is preferable to form pores in the center of nanosides formed by etching after initial anodic oxidation or points subjected to mutation through compression.

The pore channels having the uniform diameter of the sub-micron to nano size and the pore walls of the various slopes ranging from the cylinder of the proper length to the conical shape have the same diameters at both ends and the middle part, It is preferable to have a shape in which the diameter is reduced, or the shape of the two may be combined several times.

The end of the pore is preferably sharpened for better punching or drilling through forging in the future, and the cylindrical pore channel forms an aline pore of desired length by anodizing the aluminum surface for a certain period of time , It is preferable that the pore diameter is enlarged to a desired size by etching for a predetermined time. The diameter ratio to the length of the cylindrical pore channel is preferably adjusted by controlling the anodization time and the etching time.

A pore channel having a conical shape or a pore wall having various slopes may be formed by anodizing a metal surface for a predetermined period of time to form a linear pore having a predetermined length and then etching it to enlarge the pore diameter, A step of forming a pore having a smaller diameter in the end portion of the previously formed pore and then etching the pore to enlarge the pore with the previously formed pore to make the pore wall oblique. .

The diameter ratio and the cone angle to the length of the conical pore channel are preferably controlled by adjusting the anodization time, the etching time, the number of repetitions of the anodic oxidation and the etching process, and the anodic oxidation In the last step of the etching process, it is preferable not to perform the etching after the anodic oxidation.

It is preferable that the diameter of the conical pore channel from the cylinder is in the range of 1 to 900 nm, the pore clearance of the channel pore is in the range of 1 to 900 nm, and the proper length of the channel pore is in the range of 1 nm to 1 mm.

The high strength ceramics may be any high strength ceramic such as diamond or DLC (diamond-like coating, SiC), and the high strength metal may be Ni, Cr, Ti, V, Mn, Fe, Co, Zr, Nb, Mo, , Rh, Pd, Hf, Ta, W, Re, Os, Ir or a combination of two or more of these metals or a trace amount of other elements such as C, H, O, N and S in the metal or alloy Do.

The deposition method is an electrodeposition method, a poling method. Any high vacuum deposition method such as electroless plating method, rf sputtering method, dc sputtering method, evaporation method, CVD, MOCVD, laser ablation and the like may be used. The high strength positive mold having the embossed long projection pattern may be flat plate or cylindrical, May be wound around a circular drum, and any method such as physical, chemical, or mechanical methods may be used to demold the high strength boss.

The polymer film may be any polymer material such as CA, PA, PAN, PC, PE, polyester, PES, PP, PS, PVDF, PTFE, or a synthetic material of two or more of these polymer materials, Or a certain amount of nanoparticles such as CNT, TiO ₂ , and ZrO ₂ may be mixed with the polymer film. The film manufacturing process may be embossing, casting, or injection molding.

The metal thin plate may be made of a metal such as Mg or Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, H, O, Sb, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, Po, Ce and the like or alloys of two or more of these metals, , N, S, and the like.

The metal thin plate is preferably a thin plate having a thin thickness such as a plate, a thin film, and a foil. The thin metal plate may be formed by stacking two or more layers of the metal material, followed by lamination or lamination. The composite thin plate of a polymer / metal, a polymer / ceramic, and a metal / ceramic may be a composite of the polymer film with a metal and a ceramic material of any material, and the metal plate may be complexed with a polymer or ceramic of any substance.

It is preferable that a certain amount of nanoparticles such as CNT, GRP, TiO ₂ , and ZrO ₂ are mixed for a specific purpose for a polymer film, a polymer (separation) membrane, a metal sheet and a metal separation membrane, The metal thin plate manufacturing process may be any one of the above methods including melting, molding, injection, extrusion, drawing, rolling, forging, and vapor deposition of metal.

It is preferable that the shape of the linear pore channel of uniform diameter of the metal film has an asymmetric linear pore channel whose diameters are the same at the both ends and the middle part or whose diameters decrease from one end to the other end.

Here, it is preferable that the diameter of the pores of the metal film is in the range of 1 to 900 nm, the space distance of the metal film is in the range of 1 to 900 nm, and the metal film has the porosity of 1 to 85%. It is also preferable that the optimum length of the linear channel pores of the metal film is in the range of 1 nm to 1 mm, the thickness of the metal film in the range of 1 nm to 1 mm, the width of 10 nm to 100 m, and the length of 10 nm to 1,000,000 km.

The metal film may be formed by coating or laminating any material layer on the surface and the pore wall, or on the surface or the pore wall, for imparting a certain function or for a specific purpose.

Hereinafter, embodiments of the present invention will be described in more detail.

&Lt; Example 1 >

In order to manufacture a metal (separation) film having a linear pore channel of uniform diameter according to the present invention, an anodic oxidation process and an etching process are performed on the surface of the aluminum plate. That is, the following process is performed to fabricate a negative-shaped mold having a porous alumina surface having pore channels of various angles ranging from a sub-micron to a nano-sized uniform diameter and an appropriate depth from a cylinder to a conical shape.

The aluminum plate with a purity of 99.999% is cleaned using alcohol, acetone, aqueous solution, and then machine-polished using sand paper and alumina powder. After that, a mixed solution of hypochlorous acid and alcohol in a weight ratio of 1: 4 is applied as an electrolyte at -2 V at 20 V for 10 minutes, electrolytically polished, and dried for 1 hour to reduce the surface roughness to 5 nm or less. Then, an anodic oxidized 30-micrometer-thick layer was removed by using a mixed solution of chromic acid and phosphoric acid, followed by anodizing by applying a voltage of 195 V for 20 hours while maintaining a temperature of -1 ° C. using a 0.1 M phosphoric acid solution An aluminum sheet surface having nano seeds was prepared.

3 (g), using an anodic oxidation and etching repeating process shown in FIG. 3, an aluminum plate having a nano-seed is first prepared in order to produce a nano-patterned alumina mold having sharp-pointed cylindrical pores 0.01M phosphoric acid solution for a second anodic oxidation. At this time, the concentration of the phosphoric acid solution was increased from 0.01M to 0.1M for 2 minutes, and the concentration of 0.1M was maintained until the anodic oxidation was completed. Then, the anodized plate was immersed in 0.1 M phosphoric acid solution and etched for 60 minutes. Then, the resultant was immersed in phosphoric acid solution in the same manner, anodized for 15 minutes, and then etched for 30 minutes. Thereafter, the substrate was immersed in a phosphoric acid solution in the same manner for 15 minutes, then immersed in a phosphoric acid solution and etched for 20 minutes. As a result, as shown in FIG. 3 (g), a long cylindrical pore having a pointed end with a depth of about 3.0 μm Anodic oxide intaglio molds were prepared.

At this time, the diameter of the conical pores was about 350 nm at the upper part, the diameter of the part where the conical tip of the lower part started was 340 nm, the cone depth was 0.6 탆, and the distance between the pores was 500 nm. Then, nickel is deposited on the surface and pores of the alumina negative mold of FIG. 3 (g) by electrodeposition method to form a nickel embossed mold according to the process shown in FIG. 4, followed by demolding or removing the alumina mold. A cylindrical nickel-embossed column of 3.0 μm in length and 350 nm in diameter with a sharp pointed upper end, as shown in FIG. 4 (c), with one end of an alumina mold turned into a nickel- To prepare well - aligned plate - like embossed molds. 5 (a), pores having a space distance of 500 nm and a pore diameter of 350 nm were aligned in a hexagonal shape by using a plate-shaped nickel mold in the same manner as in Fig. 5 (separated) film of (b).

&Lt; Example 2 >

In order to manufacture a metal (separation) film having a linear pore channel of uniform diameter according to the present invention, an anodic oxidation process and an etching process are performed on the surface of the aluminum plate. That is, the following process is performed to fabricate an angular mold having a porous alumina surface having pore channels of various angles ranging from a sub-micron to a nano-sized uniform diameter and an appropriate depth from a cylinder to a circle.

Then, in order to produce an alumina mold having a nanopattern having conical pores according to FIG. 6, first, an aluminum plate having a nanoside was immersed in a 0.01 M phosphoric acid solution and subjected to a second anodic oxidation for 1 hour. At this time, the concentration of the phosphoric acid solution was increased from 0.01M to 0.1M for 2 minutes, and the concentration of 0.1M was maintained until the anodic oxidation was completed. Then, the anodized plate was immersed in 0.1 M phosphoric acid solution, anodized for 1 hour, and then etched for 30 minutes. Then, it was immersed again in phosphoric acid solution in the same manner, anodized for 1 hour, and then etched for 30 minutes. Thereafter, the substrate is immersed in a phosphoric acid solution for 1 hour, immersed in a phosphoric acid solution for 20 minutes, and finally immersed in a phosphoric acid solution for 10 minutes to anodically oxidize the substrate to a depth of about 10 Anodic oxidized anticorrosive molds having a long conical linear pore at one end with a diameter of 탆 were prepared.

At this time, the diameter of the conical pores was about 350 nm at the top, and the distance between the pores was 500 nm. Thereafter, diamond is deposited on the surface and pores of the alumina negative mold by a CVD method as shown in FIG. 7, followed by demolding or removing the alumina mold. The hexagonal shape of a long cone-shaped diamond embossed column with one end pointed at one end and a long cone-shaped embossed pore-like diamond shaped embossed column, about 10 ㎛ in depth and 350 nm in diameter at the bottom Shaped plate-like embossed mold was prepared. Thereafter, using a plate-shaped diamond embossed mold, a titanium thin plate having a thickness of 5 mu m was perforated by a perforation method as shown in Fig. 8 to form a titanium metal layer of the titanium metal of Fig. 8 (b) having a space distance of 500 nm and a pore diameter of about 350 nm (Separation) membrane.

&Lt; Example 3 >

Then, according to FIG. 6, the nano-seeded aluminum plate was immersed in 0.01 M phosphoric acid solution and subjected to a second anodic oxidation for 1 hour. At this time, the concentration of the phosphoric acid solution was increased from 0.01M to 0.1M for 2 minutes, and the concentration of 0.1M was maintained until the anodic oxidation was completed. Then, the anodized plate was immersed in 0.1 M phosphoric acid solution and etched for 30 minutes. Then, it was immersed in a phosphoric acid solution in the same manner, and anodized for 1 hour and then etched for 30 minutes. Thereafter, the substrate was immersed in a phosphoric acid solution for 30 minutes, immersed in a phosphoric acid solution for 20 minutes, finally immersed in a phosphoric acid solution for 10 minutes to anodically oxidize the substrate to a depth of about 17 Anodic oxidized anticorrosive molds having a long conical linear pore at one end with a diameter of 탆 were prepared. The length of the pore channel was 624 nm and the width was 500 mm. The diameter of the lower part of the cylindrical pore was approximately 350 nm, and the distance between pores was 500 nm. Thereafter, Ni-Cr alloy is deposited on the surface and pores of the alumina negative mold by electrodeposition, and then demolded or alumina mold is removed. The long conical Ni-Cr embossed column with one end pointed at one end and a pointed long cylinder shaped embossed pore turned into the same shaped embossed column with a depth of about 17 μm and a lower diameter of 350 nm was hexagonal A flat plate shaped embossed mold was prepared. 9 (c), the sheet was rolled into an aluminum alloy cylinder having a diameter of 200 mm and a width of 500 mm as shown in Fig. 9, and a 10 탆 thick polypropylene ( PP) film, a 500 mm wide PP polymer membrane (separation membrane) with well-aligned pores with a pore spacing of 500 nm and a pore diameter of about 350 nm was prepared in large quantities.

Claims

A method of manufacturing a nano-bossed mold,
Forming a first anodized layer by anodizing the metal surface for the negative mold;
Removing the first anodized layer to form a recessed nano-seed on the metal surface for the negative-tone mold;
Forming a second anodization layer on the nano-seed through anodic oxidation;
Etching the second anodization layer of the nanoside region to form a nanopattern having increased diameter and depth than the nanoside;
And a step of depositing and demolding a material for a relief mold on the metal for the relief mold where the nano pattern is formed to obtain a relief mold having a long relief pattern formed thereon.

The method according to claim 1,
Forming a first anodized layer by anodizing the metal surface for the negative mold; Instead of removing the first anodic oxide layer to form a depressed nanoside on the metal surface for the negative-tone mold,
Using an imprinting mold in which sharp-pointed columns with pore-to-pore spacing corresponding to the anodic oxidation scheme of a later anodizing process are used, the metal surface to be anodized is squeezed to form an array of locally mutated points Wherein the nano-embossed mold is manufactured by a method comprising the steps of:

The method according to claim 1,
And repeating the step of forming the anodic oxidation layer so that the depression depth of the depressed nano patterns is increased.

The method of claim 3,
Wherein the step of forming the anodic oxide layer repeatedly performs the step of repeating the step of forming the anodic oxide layer so that the recessed nano patterns are cylindrically shaped and the bottoms are recessed in a hemispherical shape.

The method of claim 3,
Wherein the step of forming the anodic oxidation layer gradually reduces the diameter of the concave nano patterns in a conical shape.

The method according to claim 1,
Wherein the intaglio nano pattern has a ratio of diameter to depth of 1: 1 to 1: 1,000.

The method according to claim 1,
Wherein the engraved nano pattern is recessed to a length of 1 to 10,000 times longer than the nano-seed.

The method according to claim 1,
Wherein the intaglio nano pattern is recessed at a depth of 1 nm to 1 mm, a diameter of 1 to 900 nm, and a period of 1 to 900 nm.

The method according to claim 1,
Wherein the material for the relief mold is selected from the group consisting of diamond, diamond-like coating (DLC), SiC, AlN, Ni, Al, W, Ti, Hf, Nb, Zr, and mixtures thereof. Gt;

The method according to claim 1,
The anodic oxidation uses a solution selected from the group consisting of phosphoric acid, oxalic acid, sulfuric acid, selenic acid, malonic acid, phosphoric acid, tartaric acid, citric acid, etidronic acid and a mixture thereof in a concentration of 0.001M to 5M as an electrolyte, Wherein a voltage of 1 to 500 V is applied for 1 second to 1 week while maintaining the temperature at 300 ° C.

The method according to claim 1,
Wherein the positive mold is a flat plate shape having an elongated protrusion pattern formed on the surface of the plate through anodic oxidation, etching, high-strength material deposition and demolding.

The method according to claim 1,
Wherein the positive mold is rolled into a cylindrical shape having a long protrusion pattern formed on the surface of the plate through anodic oxidation, etching, high-strength material deposition and demolding, and is roll-shaped.

A method of manufacturing a membrane having a pore channel formed using a nano-embossed mold,
Forming a first anodized layer by anodizing the metal surface for the negative mold;
Removing the first anodized layer to form a recessed nano-seed on the metal surface for the negative-tone mold;
Forming a second anodization layer on the nano-seed through anodic oxidation;
Etching the second anodization layer of the nanoside region to form a nanopattern having increased diameter and depth than the nanoside;
Depositing a material for the relief mold on the metal for the relief mold in which the nano pattern is formed to obtain a relief mold having a long relief pattern formed by embossing;
And forming a linear pore channel on the film or sheet using the positive mold to obtain a membrane. The method of claim 1, wherein the membrane is a flat membrane.

14. The method of claim 13,
Wherein the step of forming the anodic oxidation layer is repeatedly performed so as to increase the recess depth of the nano pattern.

14. The method of claim 13,
After obtaining the embossed mold,
Further comprising the step of coating a releasing film on the surface of the positive mold to improve the detachability of the film having the pore channel formed by using the positive mold having the long protrusion pattern of the embossed pattern, .

14. The method of claim 13,
Wherein the film or the thin plate is a polymer film or a metal thin plate.

17. The method of claim 16,
In the polymer film,
polyamide (PA); polystyrene (PS); polycarbonate (PC); polyurethane (PU); polyimide (PI); polyacrylates including polymethylmethacrylate (PMMA); polyesters including polybutylene terephthalate (PBT), polyethylene terephthalate (PET); polyalkylene including polyethylene (PE), polypropylene (PP); vinyl polymers including polyvinyl chloride (PVC) and polyvinylidene fluoride (PVdF); polydimethylsiloxane (PDMS), and mixtures thereof. < Desc / Clms Page number 24 >

17. The method of claim 16,
The thin metal plate may include:
Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Hf, Wherein the pores are selected from the group consisting of Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, Po, Ce and mixtures thereof.

17. The method of claim 16,
Wherein the metal thin plate is further added with a group consisting of C, H, O, N, S, TiO ₂ , ZrO ₂ , CNT, graphene and a mixture thereof. Way.

17. The method of claim 16,
Wherein the metal thin plate is formed by laminating a plurality of metal layers.

17. The method of claim 16,
Wherein the metal thin plate is a metal, a metal-ceramic composite or a metal-polymer composite film.

1. A membrane having a pore channel formed by using a nano-embossed mold,
Forming a nano-seed by anodizing the metal surface for the negative-tone mold, forming a nano-pattern having an increased diameter and depth than the nano-seed by anodizing and etching the nano-seed, And a pore channel is formed by imprinting the embossed mold obtained by depositing and demolding the material for the positive mold in the nano-embossed mold.

23. The method of claim 22,
Wherein the pore channel is a cylindrical shape having a uniform diameter or a conical shape having a gradually decreasing diameter, wherein the linear pore channel is formed by using the nano-positive mold.

23. The method of claim 22,
Wherein the pore channel has a shape in which both ends are opened, or one end is opened and the other end is blocked, wherein the linear pore channel is formed by using the nano-embossed mold.