WO2016024803A1 - Procédé de production d'un moule en relief, membrane produite en utilisant le moule en relief et procédé de production associé - Google Patents

Procédé de production d'un moule en relief, membrane produite en utilisant le moule en relief et procédé de production associé Download PDF

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WO2016024803A1
WO2016024803A1 PCT/KR2015/008430 KR2015008430W WO2016024803A1 WO 2016024803 A1 WO2016024803 A1 WO 2016024803A1 KR 2015008430 W KR2015008430 W KR 2015008430W WO 2016024803 A1 WO2016024803 A1 WO 2016024803A1
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mold
nano
embossed
metal
embossed mold
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PCT/KR2015/008430
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English (en)
Korean (ko)
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정대영
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한국전기연구원
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Priority claimed from KR1020150113243A external-priority patent/KR20160021047A/ko
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Publication of WO2016024803A1 publication Critical patent/WO2016024803A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/06—Permanent moulds for shaped castings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process

Definitions

  • the present invention relates to a method of manufacturing an embossed mold, (membranes) prepared by using an embossed mold, and a method of manufacturing the same, and more particularly, all polymers such as PA, PE, PP, PVDF, polyamide, PTFE, and the like. Very low segregation selectivity and severe fouling phenomena resulting from non-uniformly sized pores and the sponge structure in which these pore channels are interconnected, which is characteristic of all porous metal membranes such as membranes, metal foams, porous metal sinters, etc.
  • High strength inorganic materials such as diamond, SiC, 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, and then demolded or removed from the alumina mold.
  • the embossed mold After making a high-strength embossed mold with a long embossed pattern of embossed pores in the intaglio mold, the embossed mold is used to drill holes in a polymer film, metal sheet, polymer / metal composite film or sheet After forming various material layers on the process such as, casting process, molding process or the embossed mold, Physical or chemical vapor deposition forms a polymer layer, a metal layer, or a polymer / metal composite layer and separates it from the mold, which is similar in shape and diameter to the pillars of the high-strength embossed mold, from sub-micron to nano-sized.
  • Embossed mold production method for obtaining a (separated) film comprising a polymer film or a metal film having a linear pore channel having a uniform diameter, a film produced using the embossed mold, and a method for producing the same.
  • CA Cellulose acetate
  • PAN Polyacrylonitrile
  • PA Polyamide
  • PC Polycarbonate
  • PE Polyethylene
  • PES Polyethersulfone
  • PS Polypropylene
  • PS Polystyrene
  • PVDF Most polymer membranes, such as polyvinylidene fluoride and polyester, are prepared by solvent phase inversion, thermal induction phase separation, stretching, track etching, and the like to form pores. This method is poor in the selective separation function to remove impurities of a certain size because the shape or size of pores formed in the polymer membrane is not constant.
  • these polymer membranes form a bent pore channel, which is connected to each other to form a sponge structure as a whole.
  • the interconnection of these pore channels has the positive effect of improving the permeability of the fluid by taking a shorter filtration path than when the fluid flows into the pores, but the objects introduced through the larger pores of the surface have a smaller size inside. Surrounding the pores leads to a serious clogging phenomenon that cannot escape to the outside and is trapped inside, so that the pores trapped by the object do not participate in separation or filtration, thereby significantly reducing the separation permeability of the membrane.
  • the polymer membrane has a uniform pore channel diameter and does not capture an object, or a linear uniform diameter pore channel in which the pores are not connected inside the membrane, or
  • a polymer membrane in which the diameter of the channel becomes larger toward the opposite surface so that no entrapment of the object occurs.
  • the membrane having a constant pore diameter always be constant through the channel length, such as the former, is difficult to manufacture in reality, the latter has a pore channel that increases as the channel pores are always constant or approaches from one surface to another. Development of thin films has been required.
  • the pores are composed of various types of pores that are completely open, half open, or completely closed, which are not uniform in size and have a sponge structure in which the pores are connected to each other. Therefore, the separation selectivity is low, clogging is serious, and the price is also expensive because it is manufactured at high temperatures.
  • the porous metal sintered body having pores formed by sintering the particulate metal powder by sintering to the particulate form also has a sponge structure in which pores and pore channels of non-uniform size are connected to each other inside, although the price is somewhat cheaper.
  • the metal mesh fabricated in the form of a fabric by crossing thin wires or fibers depends on the thickness of the fine wires or fibers used, and the pore size of the fine wire meshes is tens of microns or less. Is hardly developed.
  • the pore size is reduced to several microns, but the size is not constant, and because the pores are connected to each other, the selectivity is low and has a significant limitation of severe clogging.
  • the perforated metal (perforated metal) membrane of the form of the present invention can make the linear pores to have the desired alignment state, but the size of the pores has a disadvantage that is limited to several hundred microns. Therefore, most porous metal membranes have excellent mechanical strength, impact resistance, and heat resistance, but they are not only used due to the limitations on the pore size compared to the expensive price, but also due to the membrane clogging due to the non-uniformity of the pore size and the interconnection of the non-uniform size. It has a disadvantage of being limited or paying a lot of maintenance, and also having a limited lifetime.
  • metal membranes with sub-micron pores of several nm size which can be used in ultrafiltration or precision filtration, which have wider application, also have linear asymmetric pores of uniform size with high selectivity and high transmittance.
  • anodizing is by immersing a metal such as aluminum (Al) in an acidic electrolyte and applying a constant voltage to aluminum to oxidize to form an anodization layer.
  • a metal such as aluminum (Al)
  • Al aluminum
  • FIG. 2 is a conceptual diagram clearly illustrating the cross-sectional photograph of FIG. 1 (b), and is an FE-SEM image showing that the end of the nano-pattern is blocked by a convex aluminum oxide barrier layer.
  • the hexagonal pores are self-organizing in a hexagonal manner in the closest filling manner, and when viewed from the surface, the circular pores show a well-aligned hexagonal shape.
  • the size of the nano-pattern depends on the type of electrolyte and the applied voltage.
  • a constant voltage of 195V is applied in the phosphoric acid electrolyte
  • 500nm is applied
  • 300nm is applied when 150V is applied in the oxalic acid electrolyte
  • 100nm is applied when 40V is applied
  • 140nm when 70V is applied
  • 60nm when 25V is applied in the sulfuric acid electrolyte.
  • the cells of the pores having a relatively well defined shape are arranged in a circle near the lower surface, but the abnormal state in the situation where a voltage is applied on the upper surface is observed.
  • Reflected cells appear irregular in size.
  • the shape of the pores and the uniformity of alignment increase as it approaches from the top surface to the bottom surface. Therefore, in order to obtain the shape of the cell on the upper surface after the anodization, that is, the shape of the cell with excellent alignment, the current does not increase rapidly by using the remaining concave groove alignment as a seed after removing the alumina layer formed after one anodization.
  • a more well-defined hexagonal cell on both the top and bottom faces is aligned.
  • the pores in the center of the hexagonal cell have a circular shape, which appears to be regularly aligned along the hexagon.
  • the porous anodized alumina pores thus prepared usually have a cell size, that is, about 10% square root of the neighboring void distance, and when etched with a phosphate solution, about 70% of the neighboring void distance of the diameter You can expand to the size of.
  • the pores have a convex cylindrical shape, and the walls and the convex lower parts of the cylinder are surrounded by an alumina layer having a predetermined thickness.
  • the lower alumina layer is called an oxide barrier layer, and as the anodization continues, the barrier layer moves downwards to lengthen the cylindrical pores into the pore channel shape.
  • the growth rate of the pore channel is 1 to 3 ⁇ m / hr or 50 to 70 ⁇ m / hr depending on the anodization system, but by controlling the duration of the secondary anodization and the etching time after anodization
  • the pore diameter ratio to pore length can be adjusted.
  • the pores are repeated by performing the anodization process after the etching process, the intaglio having a variety of pore channels ranging from the convex cylindrical shape of the end of Figure 2 to the conical shape of Figure 3, the pointed cylindrical shape of Figure 4 Alumina molds can be prepared.
  • high-strength inorganic materials such as diamond, SiC, DLC, high-strength metals such as diamond, SiC, DLC, or the like on the surface and pores of the intaglio mold having various pore channels ranging from convex cylindrical to conical to pointed cylindrical.
  • High-strength alloys are filled by various methods such as chemical vapor deposition or electro-deposition, and then demolded by mechanical or electrochemical methods, or the alumina mold is removed, and the pore channels of the intaglio mold are embossed. It is possible to produce a high strength embossed mold having a converted, long embossed pattern.
  • the embossed mold having a cylindrical or conical column is used as a template to make a thin plate or thin film having open pores up and down.
  • Membranes can be prepared.
  • the separation membrane is formed from the sub-micron to nano-sized uniformly-sized pores, and the separation selectivity is high, and the straight pores have a small blockage and a high fluid permeability. Membrane development has been required.
  • the present invention is to overcome the limitations of application due to the non-uniformity of the pore size of the existing metal membrane and the low selectivity and severe clogging, low fluid permeability, and relatively large pore size resulting from the bending of the pores and sponge structure,
  • an object of the present invention is to anodize a metal surface for an intaglio mold to form a first anodization layer; Removing the first anodization layer to form nanoseeds recessed in the metal surface for the intaglio mold; Forming a second anodization layer on the nanoseed through anodization; Etching the second anodization layer of the nanoseed region to form a nanopattern having a diameter and a depth greater than that of the nanoseed; It is achieved by a nano-embossed mold manufacturing method comprising the step of obtaining an embossed mold by depositing and demolding the embossed mold material on the metal for the intaglio mold on which the nanopattern is formed.
  • the step of anodizing the metal surface for the intaglio mold to form a first anodization layer instead of removing the first anodization layer to form a nanoseed recessed on the metal surface of the intaglio mold, the pillars having pointed distances having the inter-pore distance corresponding to the anodization system of the anodization process are arranged.
  • the step of forming the anodization layer is repeated to increase the depth of depression of the nano-pattern
  • the nano-pattern is a cylindrical shape the same diameter
  • the bottom is hemispherical shape by repeating the step of forming the anodization layer It is preferable that the nano-pattern is gradually reduced in diameter into a conical shape through the depression or repeatedly performing the step of forming the anodization layer.
  • An object of the present invention is to anodize a metal surface for an intaglio mold to form a first anodization layer; Removing the first anodization layer to form nanoseeds recessed in the metal surface for the intaglio mold; Forming a second anodization layer on the nanoseed through anodization; Etching the second anodization layer of the nanoseed region to form a nanopattern having a diameter and a depth greater than that of the nanoseed; Depositing and demolding an embossed mold material on the indented mold metal on which the nanopattern is formed to obtain an embossed mold having an embossed long protrusion pattern; It is also achieved by a method for producing a membrane formed with a pore channel using a nano-embossed mold, characterized in that it comprises the step of forming a linear pore channel on the film or thin film using the embossed mold.
  • the step of forming the anodization layer is repeated to increase the depth of depression of the nano-pattern, and coating a release film on the surface of the embossed mold to improve the detachability of the film having the linear pore channel using the embossed mold. It is preferable to further include.
  • the film or thin film is preferably a polymer film or a metal thin film.
  • the present invention provides a low selectivity and a serious membrane clogging property, a low fluid permeability, resulting from 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 therein.
  • polymer membranes having linear pore channels of uniform diameter in the sub-micron to several nm range By providing a membrane having a uniform diameter linear pore channel such as a metal membrane, a polymer / metal polymer / ceramic, a metal / ceramic composite membrane, high selectivity, low membrane clogging, and higher fluid permeability can be provided.
  • the nano-membrane is manufactured by a simple process of perforation regardless of the material or material used, it is possible to manufacture a film of various materials at a much lower production cost than a conventional polymer or metal film manufactured by a special manufacturing method. have.
  • the present invention has a higher fluid permeability than conventional polymer membranes or metal membranes, and thus will have higher processing efficiency than conventional metal membranes.
  • New membranes, such as oil and food and beverages, drug purification, and separation of proteins and viruses which can result in significantly reduced maintenance costs, longer lifespans, and greater filtration selectivity as the cleaning cycles are significantly reduced due to their low water clogging. Not only can be applied to, but also it is possible to separate the fine dust which is a recent environmental problem at a lower cost, there is an effect of extending the scope of the (separation) film very.
  • FIG. 1 shows (a) the top surface FE-SEM photograph and (b) the linear pore channel structure near the top surface, showing the alignment of the linear pore channels in the porous anodized alumina prepared by anodizing aluminum. Is a cross-sectional picture taken at an angle to show,
  • Figure 2 is an FE-SEM image showing the bottom portion of the pore channel after etching for 30 minutes using 0.5% phosphoric acid solution as an etching solution after anodizing in 0.3M oxalic acid electrolyte for 20 hours, the end of the straight pore channel Is a picture showing that it is blocked by a convex aluminum oxide barrier layer,
  • FIG. 3 is an embodiment of the present invention, as a schematic diagram of a long cylindrical anodized alumina intaglio mold having a pointed tip, (a) shows an aluminum plate having a very low surface roughness due to the polishing before anodization, ( b) is an aluminum plate (a) by imprinting the surface of the aluminum by imprint for excellent alignment of the pores to form a pore formed by a plurality of anodization, and (c) is (b) After etching for a certain time, the diameter of the pores in (b) is enlarged, and (d) is anodized (c) again, and the diameter of the pores in (c) is smaller than that of (c).
  • New pores are formed, and (e) is an etched (d) with a slanted pore wall with angled sections between pores of different diameters, and (f) anodized (e) again. at the bottom of the pores in (e) (G) shows the formation of new pores of a certain length with a diameter smaller than the most pores, and (g) etches (f) to soften the angled portions between the pores of different diameters at the end of the pores. It is a drawing that forms a long cylindrical pore channel having a pointed cone shape,
  • Figure 4 is a schematic diagram showing the manufacturing process of nickel embossed mold as an example of the production of high-strength embossed mold,
  • (a) is anodized alumina in which the long cylindrical pore channels are arranged in the shape of a pointed cone of Figure 3
  • (f) is a state in which nickel is deposited on the inside of the pores and the surface of the alumina in (a)
  • (c) is a view showing the nickel embossed mold demodulated from the intaglio alumina mold in (b)
  • FIG. 5 is an embodiment of the present invention, (a) a polyamide separator having a straight asymmetric pore channel by perforating the polyamide polymer thin film using a plate-shaped relief nickel mold having an alignment of conical pillars and penetrating the thin film thickness. (B) A conceptual diagram of a polyamide separation membrane having a straight asymmetric pore channel prepared using an embossed mold (a),
  • FIG. 6 is a further embodiment of the present invention, a schematic diagram of the production of anodized alumina intaglio mold having a conical pore channel,
  • (a) is an aluminum plate before anodization
  • (b) is an aluminum plate
  • the pores were formed through a plurality of anodizing steps to form aligned pores by pressing the aluminum surface by imprint for excellent alignment of the pores, and
  • (c) is etched (b) for a predetermined time to The diameter of the pores is enlarged,
  • (d) is anodized (c) again to form new pores of a certain length smaller in diameter than (c) at the bottom of the pores in (c), and
  • (e) Is anodized and etched again after etching (d), and the angled part between pores of different diameters has a slanted pore wall, and
  • (f) is again anodized and Repeat the etching once and finally
  • This is a conceptual diagram of a negative engraved a
  • FIG. 7 is a schematic view showing a manufacturing process of an embossed diamond mold as an example of manufacturing a high strength embossed mold, wherein (a) is a negative alumina mold in which the long conical linear pore channels of FIG. 6 (f) are aligned, and (b) (A) shows the deposition of diamond on the inside of the pores and the surface of the alumina by chemical vapor deposition (CVD) method, (c) shows the embossed diamond mold demodulated from the negative alumina mold of (b),
  • CVD chemical vapor deposition
  • FIG. 8 is an embodiment of the present invention, (a) using a plate-shaped embossed diamond mold having an alignment of conical pillars to perforate the titanium (Ti) thin film to form a straight asymmetric pore channel by penetrating the thickness of the thin film uniformly Conceptual process of manufacturing a titanium separator having a straight pore channel and (b) A conceptual diagram of a titanium separator having a straight asymmetric pore channel manufactured by using an embossed mold (a),
  • FIG. 9 is an excellent mechanical strength of Ni-Cr alloy having excellent mechanical strength in the intaglio anodized alumina mold having a long conical linear pore channel prepared through the process of FIG. (B)
  • a cross-sectional view (a) and a cross-sectional view (b) of the plate-shaped embossed Ni-Cr mold with the adhesive strip attached to the cylinder to adhere it to the cylinder (b) Is a cross-sectional conceptual view of an embossed Ni-Cr roll mold (c) wound on a cylinder while removing the separation band,
  • FIG. 10 is an embodiment of the present invention, a large amount of PP polymer (separation) membrane having a uniform asymmetric linear pore channel by punching using the embossed roll mold of Figure 9 (c) while supplying the heated PP thin film in a roll-to-roll process Schematic diagram of manufacturing process to produce.
  • the present invention in order to manufacture a nano-membrane having a straight pore channel of uniform diameter, using an anodizing process and an etching process on the surface of the aluminum plate and a uniform diameter of nano-sized from sub-micron
  • An alumina engraved mold was prepared by having a porous anodized alumina surface layer having pore channels of various angles ranging from pointed cylinders to cones of appropriate length, and then diamonds on the surface and pores of the anodized engraved mold.
  • high-strength inorganic materials such as SiC, DLC, or high-strength metals such as Ni, Cr, and W, or high-strength alloys thereof by physical or chemical vapor deposition or electro-deposition, and then demold or remove anodized negative molds. Embossed pores in the anodized engraved mold turned into embossed pillars To produce a high-strength mold embossed turn is formed.
  • 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 initial or intermediate process of the polymer film precursor or the already formed polymer film or metal sheet manufacturing process in the process of forming or manufacturing the polymer film.
  • a membrane having a uniform size of linear pore channel can be obtained with a uniform diameter symmetrical or asymmetric linear pore channel.
  • the aluminum for achieving this is at least 99.99% high purity, or Cu, Mn, Si, Mg, Cr, Zn, Li, V, Mo, Ga, Ge, Fe, Cr, Co, Ni, C, O, N, S It may be desirable to include one or more of the elements.
  • the metal surface for the intaglio mold is cleaned with an alcohol, acetone, and aqueous solution prior to anodizing, and then the surface roughness is subjected to a surface roughness of 10 ⁇ m to 0.1 nm using one or more of electropolishing, mechanical, chemical and physical polishing processes. Is preferably reduced.
  • 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, organic acid, and a mixed solution of these acids as an electrolyte. It is preferable to anodize while applying a voltage of 1 ⁇ 500V for 1 minute ⁇ 1 week. The anodization is preferably repeated two or more times for better pore alignment.
  • the anodization is used to squeeze the surface of the metal to be anodized by using an imprinting mold in which pointed pillars having a distance between the pores corresponding to the anodization system of the anodizing process are aligned for excellent pore alignment. It is desirable to form an array of points that have undergone local variation and then subjected to anodization.
  • the pore channel having a uniform diameter of the sub-micron to nano-sized and pore walls of various inclinations ranging from cylinders of appropriate length to conical shapes have the same diameter at both ends and the middle portion, or as they go from one end to the other. It is desirable to have a shape of decreasing diameter or to combine the shapes of the two times several times.
  • the end of the pores is preferably pointed for a smoother drilling or drilling through forging in the future, the cylindrical pore channel is anodized the aluminum surface for a certain time to form a straight pore of the desired length It is preferable to etch it for a predetermined time to enlarge the pore diameter to a desired size.
  • the diameter ratio to the length of the cylindrical pore channel is preferably adjusted by adjusting the anodization time and the etching time, respectively.
  • a pore channel having a conical shape or pore walls of various slopes is anodized for a certain period of time to form linear pores of a certain length, which are then etched to enlarge the pore diameter, and then anodize the previously formed pores. Smaller diameter pores are formed at the end of previously formed pores and then etched to produce pores with the previously formed pores enlarged so that the walls of the pores are tilted. It is desirable to.
  • the diameter ratio and the angle of the horn with respect to the length of the conical pore channel are preferably controlled by controlling the anodization time, the etching time, and the number of repetitions of the anodization and the etching process, respectively. It is preferable not to perform etching after anodization at the last step of the repeated etching process.
  • the diameter of the cylindrical conical pore channel is in the range of 1 to 900 nm
  • the pore space of the channel pores is in the range of 1 to 900 nm
  • the proper length of the channel pores is in the range of 1 nm to 1 mm.
  • the high-strength ceramic may be any high-strength ceramic such as diamond or diamond-like coating (SiC), and the high-strength metal may be Ni or Cr, Ti, V, Mn, Fe, Co, Zr, Nb, Mo, Tc, Ru , Rh, Pd, Hf, Ta, W, Re, Os, Ir or two or more kinds of alloys thereof, or a small amount of ellipses such as C, H, O, N, and S may be contained in this metal or alloy. Do.
  • SiC diamond or diamond-like coating
  • Electroless plating method rf sputtering method, dc sputtering method, evaporation method, CVD, MOCVD, laser ablation, etc. can be any vapor deposition method. May be wound on a circular drum, and any method such as physical, chemical or mechanical methods may be used for demoulding the high strength embossed mold.
  • the polymer film is any polymer material such as CA, PA, PAN, PC, PE, polyester, PES, PP, PS, PVDF, PTFE, or a composite material of two or more kinds of these polymer materials or two or more kinds of films are laminated.
  • a film may be used, and a certain amount of any nanoparticles such as CNT, TiO 2 , or ZrO 2 may be mixed with the polymer film.
  • the film manufacturing process can be any method such as embossing method, casting process or injection process.
  • the metal sheet is Mg or Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, Po, Ce, or two or more alloys of these metals, or C, H, O
  • a small amount of elliptical elements such as N, S and the like may be included.
  • the thin metal plate is preferably a thin plate 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, or may be continuous or concurrent with the lamination.
  • the polymer film may be complexed with metal and ceramic material of any material, and the metal sheet material may be complexed with polymer or ceramic of any material.
  • the polymer film or the polymer (separation) membrane, the metal plate and the metal (separation) membrane, the composite thin film and the composite separator is preferably mixed with a certain amount of certain nanoparticles, such as CNT, grepin, TiO 2 , ZrO 2 for a specific purpose,
  • the metal sheet manufacturing process may be any method including one or more of the above methods, such as melting, molding, injection, extrusion, drawing, rolling, forging, and deposition of metal.
  • the shape of the uniform diameter linear pore channel of the metal film preferably has an asymmetric linear pore channel whose diameter is the same at both ends or the middle part, or decreases in diameter as it goes from one end to the other end.
  • the pore diameter of the metal film is in the range of 1 to 900 nm
  • the pore space distance of the metal film is in the range of 1 to 900 nm
  • the porosity of the metal film is preferably 1 to 85%.
  • the proper length of the linear channel pores of the metal film is preferably 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 coated or laminated with any material layer on the surface and the pore wall, or each of the surface or the pore wall, for the purpose of providing some functionality or for any particular purpose.
  • anodizing and etching are performed on the surface of the aluminum sheet. That is, the following process is performed to manufacture a negative mold having a porous alumina surface having a pore channel of various angles ranging from a sub-micron to a nano-sized uniform diameter and a cylinder having a proper depth to a conical shape.
  • the 99.999% pure aluminum sheet is cleaned using alcohol, acetone, aqueous solution, and then mechanically polished with sand paper and alumina powder. Then, using a mixed solution of hypochlorous acid and alcohol in a 1: 4 weight ratio as an electrolyte, electrolytic polishing by applying 20V at -2 ° C for 10 minutes, drying for 1 hour to make the surface roughness less than 5nm. Anodized by applying a voltage of 195V for 20 hours while maintaining a temperature of ⁇ 1 ° C. using a 0.1 M phosphoric acid solution, and then removing the 30 micron thick layer using a mixture of chromic acid and phosphoric acid. An aluminum plate surface having nanoseeds was prepared.
  • the diameter of the conical pores was about 350nm in the upper part
  • the diameter of the starting point of the cone pointed at the lower end was 340nm
  • the depth of the cone was 0.6 ⁇ m
  • the distance between the pores was 500nm.
  • nickel is deposited on the surface and pores of the alumina engraved mold of FIG.
  • a long cylindrical engraved pore with one end of the alumina mold turned into a nickel-shaped embossed pillar of the same shape, and a nickel embossed pillar of 3.0 ⁇ m in length and 350 nm in diameter with a pointed cylindrical end as shown in FIG.
  • a plate-shaped embossed mold was prepared which was well aligned with.
  • a metal (separation) film having a linear pore channel having a uniform diameter In order to manufacture a metal (separation) film having a linear pore channel having a uniform diameter according to the present invention, anodizing and etching are performed on the surface of the aluminum sheet. In other words, the following process is carried out to produce a negative mold having a porous alumina surface having a pore channel of various shapes ranging from sub-micron to nano-sized uniform diameters and cylinders of appropriate depth to circular shapes.
  • an aluminum plate having nanoseeds was immersed in 0.01 M phosphoric acid solution for a second anodization for 1 hour.
  • the phosphoric acid solution concentration was increased from 0.01M to 0.1M for 2 minutes, and then maintained at 0.1M until the end of anodization.
  • the anodized plate was immersed in 0.1 M phosphoric acid solution for 1 hour and then anodized for 30 minutes. Then, this was again immersed in phosphoric acid solution in the same manner and anodized for 1 hour, followed by etching for 30 minutes.
  • the diameter of the conical pores was approximately 350nm at the top, the distance between the pores was 500nm.
  • the long cone-shaped diamond embossed pillar with the long cone-shaped intaglio pores with one end of the alumina mold turned into a hexagonal diamond embossed pillar with a depth of about 10 ⁇ m and a 350 nm diameter bottom.
  • a plate-shaped embossed mold was prepared. Subsequently, using a plate-shaped diamond embossed mold, a hole was formed in the titanium thin plate having a thickness of 5 ⁇ m by a method of drilling as shown in FIG. 8, and the titanium metal of FIG. 8 (b) having an air gap distance of 500 nm and a pore diameter of about 350 nm. (Separation) A membrane was prepared.
  • anodizing and etching are performed on the surface of the aluminum sheet. That is, the following process is performed to manufacture a negative mold having a porous alumina surface having a pore channel of various angles ranging from a sub-micron to a nano-sized uniform diameter and a cylinder having a proper depth to a conical shape.
  • the 99.999% pure aluminum sheet is cleaned using alcohol, acetone, aqueous solution, and then mechanically polished with sand paper and alumina powder. Then, using a mixed solution of hypochlorous acid and alcohol in a 1: 4 weight ratio as an electrolyte, electrolytic polishing by applying 20V at -2 ° C for 10 minutes, drying for 1 hour to make the surface roughness less than 5nm. Anodized by applying a voltage of 195V for 20 hours while maintaining a temperature of ⁇ 1 ° C. using a 0.1 M phosphoric acid solution, and then removing the 30 micron thick layer using a mixture of chromic acid and phosphoric acid. An aluminum plate surface having nanoseeds was prepared.
  • the aluminum plate having the nanoseed was immersed in 0.01 M phosphoric acid solution according to FIG.
  • the phosphoric acid solution concentration was increased from 0.01M to 0.1M for 2 minutes, and then maintained at 0.1M until the end of anodization.
  • the anodized plate was immersed in 0.1 M phosphoric acid solution and etched for 30 minutes.
  • the solution was immersed in a phosphoric acid solution and anodized for 1 hour, and then etched for 30 minutes was repeated 10 times.
  • Anodized intaglio mold having a long cone-shaped straight pore with one end of ⁇ m was prepared.
  • the pore channel had a length of 624 nm and a width of 500 mm.
  • the diameter of the lower portion of the cylindrical pores was approximately 350 nm and the distance between the pores was 500 nm.
  • Ni-Cr alloy is deposited on the surface and pores of the alumina engraved mold by electro-deposition, and then demolded or the alumina mold is removed.
  • a flat plate-shaped embossed mold was prepared. Then, using a plate-shaped Ni-Cr embossed mold, wound around an aluminum alloy cylinder having a diameter of 200 mm and a width of 500 mm, as shown in FIG. 9 (c), and a polypropylene having a thickness of 10 ⁇ m by a roll-to-roll type punching process as shown in FIG. PP) was punched into a film to prepare a large volume of 500 mm wide PP polymer (separation) membranes with pores with a 500 nm pore distance and a pore diameter of about 350 nm.
  • the present invention can be used in the manufacturing method of an embossed mold, (separation) membranes manufactured using the embossed mold, and the manufacturing method thereof.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un procédé de production d'un moule en relief, une membrane produite en utilisant le moule en relief et un procédé de production associé, et la présente invention comprend : une étape de formation d'une première couche d'oxyde d'anode en soumettant une surface en métal destinée à un moule en creux à une oxydation anodique ; une étape de formation d'une nanofeuille immergée dans la surface en métal pour le moule en creux, en retirant la première couche d'oxyde d'anode ; une étape de formation d'une seconde couche d'oxyde d'anode par l'intermédiaire de l'oxyde d'anode sur la nanofeuille ; une étape de formation d'un nanomotif de diamètre et profondeur accrus par rapport à la nanofeuille, par attaque chimique de la seconde couche d'oxyde d'anode dans la région de nanofeuille ; et une étape d'obtention d'un moule d'anode par dépôt à la vapeur et démoulage d'un matériau de moule d'anode sur un métal pour moulage en creux sur lequel est formé le nanomotif.
PCT/KR2015/008430 2014-08-14 2015-08-12 Procédé de production d'un moule en relief, membrane produite en utilisant le moule en relief et procédé de production associé WO2016024803A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR20140106315 2014-08-14
KR10-2014-0106315 2014-08-14
KR20140116483 2014-09-02
KR10-2014-0116483 2014-09-02
KR1020150113243A KR20160021047A (ko) 2014-08-14 2015-08-11 양각 몰드 제조방법, 양각 몰드를 이용하여 제조한 막 및 그 제조방법
KR10-2015-0113243 2015-08-11

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007247070A (ja) * 2007-06-22 2007-09-27 Kanagawa Acad Of Sci & Technol 陽極酸化ポーラスアルミナ複合体の製造方法
KR20080038385A (ko) * 2005-08-26 2008-05-06 카나가와 아카데미 오브 사이언스 앤드 테크놀로지 다공성 고분자막 및 그 제조 방법, 및 그 제조에 이용하는스탬퍼의 제조 방법
KR20100011463A (ko) * 2008-07-25 2010-02-03 창원대학교 산학협력단 수직 이방성을 가지는 나노기둥 자성박막 제조방법
KR100973522B1 (ko) * 2007-08-06 2010-08-02 포항공과대학교 산학협력단 양극 산화 알루미늄과 원자층 증착 공정을 이용한 루테늄 나노 구조물의 제조방법
KR20110007724A (ko) * 2009-07-17 2011-01-25 한국전자통신연구원 반사방지 나노구조물 및 그의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080038385A (ko) * 2005-08-26 2008-05-06 카나가와 아카데미 오브 사이언스 앤드 테크놀로지 다공성 고분자막 및 그 제조 방법, 및 그 제조에 이용하는스탬퍼의 제조 방법
JP2007247070A (ja) * 2007-06-22 2007-09-27 Kanagawa Acad Of Sci & Technol 陽極酸化ポーラスアルミナ複合体の製造方法
KR100973522B1 (ko) * 2007-08-06 2010-08-02 포항공과대학교 산학협력단 양극 산화 알루미늄과 원자층 증착 공정을 이용한 루테늄 나노 구조물의 제조방법
KR20100011463A (ko) * 2008-07-25 2010-02-03 창원대학교 산학협력단 수직 이방성을 가지는 나노기둥 자성박막 제조방법
KR20110007724A (ko) * 2009-07-17 2011-01-25 한국전자통신연구원 반사방지 나노구조물 및 그의 제조 방법

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