WO2015065134A1 - Système de revêtement multicouche utilisant des vides pour système de protection thermique et son procédé de fabrication - Google Patents

Système de revêtement multicouche utilisant des vides pour système de protection thermique et son procédé de fabrication Download PDF

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Publication number
WO2015065134A1
WO2015065134A1 PCT/KR2014/010438 KR2014010438W WO2015065134A1 WO 2015065134 A1 WO2015065134 A1 WO 2015065134A1 KR 2014010438 W KR2014010438 W KR 2014010438W WO 2015065134 A1 WO2015065134 A1 WO 2015065134A1
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layer
spherical
radius
substrate
coating system
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PCT/KR2014/010438
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English (en)
Korean (ko)
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조승래
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조승래
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Priority claimed from US14/146,426 external-priority patent/US9372291B2/en
Application filed by 조승래 filed Critical 조승래
Priority to CN201480060391.4A priority Critical patent/CN105793031B/zh
Priority to US15/033,842 priority patent/US9835929B2/en
Priority to ES14857339T priority patent/ES2818934T3/es
Priority to EP14857339.7A priority patent/EP3067197B1/fr
Publication of WO2015065134A1 publication Critical patent/WO2015065134A1/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
    • F28F13/003—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by using permeable mass, perforated or porous materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • G02B5/0247—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of voids or pores
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2265/00—Safety or protection arrangements; Arrangements for preventing malfunction
    • F28F2265/10—Safety or protection arrangements; Arrangements for preventing malfunction for preventing overheating, e.g. heat shields
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2270/00—Thermal insulation; Thermal decoupling

Definitions

  • the present invention relates to a multi-layered coating system, and more particularly, to a multi-layer coating system for a heat blocking system using voids and a method of manufacturing the same.
  • thermal barrier technology relates to heat resistant paints.
  • glass microspheres or hollow glass extenders are mixed with conventional paint to reduce direct thermal conductivity, which greatly improves insulation against heat loss.
  • glass microspheres with diameters ranging from approximately 50 microns to 150 microns are mixed with conventional paint, while in other embodiments, glass microspheres with diameters of approximately 100 microns Mixed with conventional paints.
  • US Pat. No. 4,463,90 does not discuss any aspect of the multilayer coating structures discussed in the present invention.
  • hollow microspheres selected from glass microspheres, ceramic microspheres and organic polymer microspheres with an average particle size of between 0.5 and 150 microns have a direct thermal conductivity. It is mixed with conventional paint to reduce). Further, US Pat. No. 8287998 incorporates infrared reflecting pigment materials in conventional paint mixtures to reduce thermal conductivity associated with radiative heat transfers. Otherwise, U. S. Patent No. 8287998 does not discuss any aspect of the multilayer coating structures discussed herein.
  • solar reflective roofing granules are disclosed.
  • the sun reflective granules are formed by sintering ceramic particles, which are coated with sun reflecting particles. Otherwise, US Patent 2010/0203336 does not discuss any aspect of the multilayer coating structures covered herein.
  • roofing granule forming particles are coated with a layer of nanoparticles that reflects near infrared radiation.
  • roofing granules are formed of infrared reflective inert mineral core particles with naturally occurring voids (or defects). . Otherwise, US Patent 2013/0108873 and US Patent 2013/0161578 do not discuss any aspect of the multilayer coating structures referred to herein.
  • US 2008/0035021 a method of making aluminum phosphate hollow microspheres is disclosed. This US patent also shows how to use such particulates to improve insulation against heat loss. Otherwise, US 2008/0035021 does not discuss any aspect of the multilayer coating structures covered by the present invention.
  • US 2007/0298242 a lens for filtering optical waves is disclosed, and metal nanoparticles having a thin film layer are formed on the lens surface thereof. Otherwise, US Patent 2007/0298242 does not discuss any aspect of the multilayer coating structures discussed herein.
  • indium tin oxide (ITO) particles are mixed with a film-forming mixture to form a thin film layer that reflects infrared waves. Otherwise, US Patent 2007/0036985 does not discuss any aspect of the multilayer coating structures represented in the present invention.
  • US 2013/0266800 a method of preparing aluminum doped zinc oxide (AZO) nanocrystals is disclosed. Moreover, this patent discloses a thin film structure that reflects infrared light using AZO nano-particulates. Otherwise, US Patent 2013 / 0266800A1 does not describe any aspect of the multilayer coating structures discussed herein.
  • AZO aluminum doped zinc oxide
  • U.S. Patent No. 7760424 and U.S. Patent No. 8009351 disclose multilayer thin film structures using colloidal particles to reflect infrared electromagnetic waves.
  • the fine particles are arranged regularly while maintaining regular lattice spacing such as photonic crystals.
  • the cavities are irregularly distributed in each layer of the multilayer coating system.
  • U.S. Pat. No. 7,758,240 and U.S. Pat.No. 8009351 rely on Bragg's law to describe infrared reflection, whereas in the present invention, Mie scattering theory is used to describe infrared reflection.
  • prior arts relating to quantum dot technologies include US Pat. No. 8362684, US Pat. No. 8395042, US Pat. No. 2013/0003163, and US Pat. No. 2013/0207073.
  • this prior art is not technically relevant to the present invention, there are similarities and distributions of cavities in each layer of the multilayer coating system.
  • the prior art with respect to the subject matter and the quantum dot technology is basically based on different physics and both should not be considered identical.
  • the invention as set forth in claim 1 is a multilayer coating system comprising a plurality of spherical cavities having a radius a 1 irregularly distributed and separated from each other, and a filler material of refractive index n 1 interposed in the space between the spherical cavities.
  • substrate is further provided under the layer 1 of Claim 1, It is characterized by the above-mentioned.
  • substrate is further provided on the said layer located farthest from the layer 1 of Claim 1, It is characterized by the above-mentioned.
  • the substrate according to claim 1 or 3 comprises one selected from the group consisting of a conductive material, a dielectric material, a semiconductor material and a fabric.
  • the layer i according to claim 1 has a thickness different from that of the layer i-1 (where i is an integer greater than 1).
  • the layer i according to claim 1 has the same thickness as the layer i-1 (where i is an integer greater than 1).
  • each layer according to claim 1 has a thickness in the range of 0.01 micron to 10,000 microns.
  • the filler material according to claim 1 comprises one selected from the group consisting of a polymeric material, a binder, a resin, a dielectric material and a ceramic material. .
  • the refractive index of the filler material according to claim 1 satisfies n i > n i-1 (where i is an integer greater than 1).
  • the radius of the spherical cavities described in claim 1 satisfies a i > a i-1 (where i is an integer greater than 1).
  • a plurality of spherical cavities of radius b are irregularly distributed and separated from each other in all the layers as set forth in claim 1, and b is b> a 1 and b. > a i (where i is an integer greater than 1).
  • a plurality of spherical particles having a radius c 1 which are irregularly distributed and separated from each other in the filler material constituting the layer 1 according to claim 15, are further included in the filler material constituting the layer i.
  • the spherical particles according to claim 16 include one selected from the group consisting of a conductive material, a dielectric material, a semiconductor material, and a ceramic material.
  • the filler material according to claim 1 further includes a plurality of holes therein.
  • the plurality of holes described in claim 18 are a plurality of spherical holes having a radius of a larger size than the spherical cavities.
  • the spherical cavity according to claim 1 has a cavity radius in the range of 0.002 microns to 500 microns.
  • the spherical cavity according to claim 1 is formed of one selected from the group consisting of a hollow dielectric shell, a hollow conductor shell, and a hollow semiconductor shell.
  • the invention as set forth in claim 23, further comprising the steps of: (1) preparing a first solution in which a plurality of spherical cavities of radius a 1 are mixed into a filler material of refractive index n 1 ; (2) comprising a filler material having a refractive index n 1 is interposed in a space between the by treatment of the substrate to the first solution, to a substrate, the irregularly distributed and separated from each other radially a plurality of the spherical joint and a spherical joint of the first Forming a layer 1; (3) preparing an i solution (where i is an integer greater than 1), wherein a plurality of spherical cavities of radius a i are mixed with a filler material of refractive index n i ; And (4) treating the substrate on which the layer i-1 is formed in the i-th solution, thereby providing a space between the plurality of spherical cavities and the spherical cavities of a radius a
  • the treatment of step (2) according to claim 23 includes a method of dipping the substrate in the first solution, a method of spin coating the first solution on the substrate, and a first And a method of spin casting a solution onto a substrate and a method of spraying the first solution onto a substrate.
  • the process of step (4) according to claim 23 is a method of dipping the substrate on which the layer i-1 is formed in the i-th solution.
  • Spin coating on the substrate spin casting the solution i to the substrate on which layer i-1 is formed, and layer i-1 (where i is an integer greater than 1). It is characterized in that it is one selected from the group consisting of spraying (spraying) to the substrate.
  • the present invention can provide a multilayer coating system for a thermal barrier system using cavities and a method of manufacturing the same.
  • FIG. 1 shows a schematic view of a multilayer coating system according to the invention
  • FIG. 2 shows an embodiment of a multilayer coating system according to the invention, showing a cross section along line AB of FIG. 1;
  • 3 is a square grating for calculating the distance between spherical cavities of a multilayer coating system according to the present invention
  • FIG. 4 shows another embodiment of a multilayer coating system according to the invention, showing a cross-sectional view along line AB of FIG. 1;
  • FIG. 5 shows yet another series of embodiments of a multilayer coating system according to the invention, showing embodiments with a substrate or sealing member;
  • Figure 6 shows another embodiment of a multilayer coating system according to the invention, showing an embodiment with a filler material having a plurality of holes;
  • FIG. 7 shows a modification of a hole formed in the filler material in the embodiment of FIG. 6;
  • FIG. 8 shows another variation of a hole formed in the filler material in the embodiment of FIG. 6;
  • FIG. 9 shows another modification in which the filler material further includes a plurality of spherical particles in the embodiment of FIG. 6;
  • FIG. 10 shows another embodiment of a multilayer coating system according to the invention, showing an embodiment with an electrode as an electromagnetic wavelength filter;
  • FIG. 11 is an illustration of an exemplary action of selectively blocking (or reflecting) electromagnetic radiation at a specific range of wavelengths and transmitting the remainder;
  • 15-17 show a series of embodiments of a method of making a multilayer coating system according to the present invention.
  • the thicknesses, regions, spherical particulates and spherical cavities of layers may be exaggerated for clarity, and like reference numerals refer to like elements throughout the description of the drawings.
  • Exemplary embodiments are described herein with reference to cross-sectional views of ideal embodiments.
  • certain shapes or regions in the exemplary embodiments should not be construed as limited to the specific shapes or regions shown in the exemplary embodiments, and those shapes or regions may not be construed as derivatives due to manufacturing errors. It can be interpreted as being included.
  • the spherical particulates may appear as particles having an ellipsoidal shape that deviates slightly from the ideal sphere in a practical device.
  • An exemplary multilayer coating system 900 includes a first subcoat layer 101, a second subcoat layer 102 located on the first subcoat layer 101, and a third subcoat layer 102 positioned on the second subcoat layer 102. And a fourth subcoat layer 104 positioned on the subcoat layer 103 and the third subcoat layer 103.
  • Exemplary multilayer coating system 900 has four subcoat layers, first subcoat layer 101, second subcoat layer 102, third subcoat layer 103 and fourth subcoat layer 104, for brevity. Although the multilayer coating system according to the present invention does not limit the number of subcoating layers. In an exemplary multilayer coating system 900, it is assumed that electromagnetic radiation is incident from the top to the fourth subcoat layer 104.
  • FIG. 2 shows a first exemplary embodiment 100 as a diagram showing a cross section of an exemplary multilayer coating system 900 along a line AB.
  • the second subcoat layer 102 has a larger thickness than the first subcoat layer 101
  • the third subcoat layer 103 is larger than the second subcoat layer 102.
  • the fourth subcoat layer 104 has a larger thickness than the third subcoat layer 103.
  • the multilayer coating system according to the present invention does not limit the thickness of each subcoating layer.
  • each of the sub-coating layers may have a thickness that is sequentially increased or may have a thickness that is sequentially decreased.
  • each subcoating layer is not limited by how large it should be, as long as it has a thickness sufficient to contain at least a spherical cavity.
  • Each subcoating layer should have at least the same thickness as the diameter of the spherical cavity it contains.
  • each subcoating layer may have a thickness ranging from 0.01 micron to 10,000 micron.
  • each subcoating layer comprises a plurality of spherical cavities arranged to be irregularly distributed.
  • first spherical cavities 11 irregularly distributed in the first subcoat layer 101, and irregularly in the second subcoat layer 102.
  • second spherical cavities 12 there is a plurality of third spherical cavities 13 distributed irregularly in the third subcoat layer 103, and in the fourth subcoat layer 104.
  • fourth spherical cavities 14 distributed irregularly.
  • the spherical cavities of each subcoating layer do not have an orderly patterned arrangement, such as lattice arrangements of crystal structures and photonic crystals.
  • the reason for having an irregularly distributed arrangement is simple.
  • electromagnetic reflections are determined by the lattice constants according to Bragg's law. Will occur.
  • the infrared portion of the electromagnetic spectrum associated with most thermal energy ranges in wavelength from 0.7 microns to approximately 1,000 microns.
  • Such actions are such that spherical cavities are arranged at regular inter-grid distances, such that they are arranged to reflect only selectively in a completely discontinuous series of wavelengths determined by lattice constants according to Bragg's law. Cannot be achieved.
  • the spherical cavities are irregularly distributed, infrared electromagnetic reflections, even if incomplete, occur over a wide range of wavelengths, which is a desirable property for successful thermal barrier action.
  • each subcoating layer comprises a plurality of spherical cavities arranged to be separated from one another.
  • an arrangement in which a plurality of spherical cavities is separated from each other refers to an arrangement in which a plurality of spherical cavities are not in contact with each other.
  • the plurality of spherical cavities in each subcoating layer is preferably sufficiently separated so that any interaction between the two nearest neighboring spherical cavities can be largely ignored.
  • ⁇ represents the wavelength of the electromagnetic wave inside the filler material in which the spherical cavities are arranged
  • n is the wavelength of the filler material in which the spherical cavities are arranged.
  • Refractive index is shown. Based on this, the number and weight of spherical cavities per unit volume of each subcoating layer are calculated.
  • a eff (10 ⁇ + 2a) 2 .
  • V eff (10 ⁇ + 2a) It can be expressed as 3 .
  • the V layer represents the volume for one of the first to fourth subcoat layers 101, 102, 103, 104 of the first exemplary embodiment 100
  • g is the gravity constant
  • ⁇ is the effective mass density of the cavity
  • the total effective mass of the single spherical void defined by ⁇ a 3 or m 4.1888
  • the ideal cavity has no mass because it is hollow.
  • physical cavities can be implemented using structures such as, for example, hollow shells.
  • the radius of the cavity can be called a
  • the closest face-to-face separation distance 10 ⁇ between the closest neighboring spherical cavities shown in FIG. 3 is only an approximation to the distance sufficiently separated such that interactions between the closest neighboring spherical cavities can be ignored. Therefore any separation distances greater than 10 ⁇ are valid analysis here.
  • N p and W p are each in the range of N p ⁇ V layer / (10 ⁇ o / n + 2a) 3 and W p ⁇ 4.1888 ⁇ a 3 gV layer / (10 ⁇ o / n + 2a) 3 , respectively.
  • (N p / V layer ) and (W p / V layer ) are respectively (N p / V layer ) ⁇ 1 / (10 ⁇ o / n + 2a) 3 and (W p / V layer ) ⁇ 4.1888 ⁇ a 3 g / (10 ⁇ o / n + 2a) 3 in the range.
  • the scattering of electromagnetic waves in a mixture of irregularly distributed particulates requires a clear calculation of the scattering solution of a single particulate alignment. And often such scattering solutions are sufficient to account for scattering phenomena in the mixtures.
  • the transmission and reflection of light in a milk bottle or a cloud of cloud can be quantitatively explained by the Mie theory of a single milk particle for a milk bottle or a single raindrop for a cloud of clouds.
  • cases in which irregularly distributed cavities are embedded in a medium such as filler material have been considered.
  • the electromagnetic scattering phenomenon in such systems is related to single particle Mie theory solutions. Details of the physics used in these details can be found in the following references: C. Bohren and D. Huffman, "Absorption and Scattering of Light by Small Particles," John Wiley & Sons, Inc., 1998 ; ISBN 0-471-29340-7
  • the closest face to face separation distance between the nearest neighboring spherical cavities in each subcoating layer of the multilayer coating system of the present invention is not limited to 10 ⁇ , as shown in FIG. 3. If instead another separation distance between the two nearest neighboring cavities, e.g.
  • N p and W p are respectively N p ⁇ V layer / (5 ⁇ o / n + 2a) 3 and W p ⁇ 4.1888 ⁇ a 3 gV layer / (5 ⁇ o / n + 2a) 3 , given by (N p / V layer ) and (W p / V layer ) is given by (N p / V layer ) ⁇ 1 / (5 ⁇ o / n + 2a) 3 and (W p / V layer ) ⁇ 4.1888 ⁇ a 3 g / (5 ⁇ o / n + 2a) 3 , respectively.
  • the separation distance that the two cavities can see as far enough apart to largely ignore any interaction between them depends on the type of cavities involved. For example, if the cavities are charged, a separation distance of 10 ⁇ cannot be sufficient to ignore the interactions between the two cavities. Nevertheless, the choice of 10 ⁇ in FIG. 3 would make most particulate types 'sufficiently separated'.
  • a plurality of cavities of each subcoating layer may be formed in a spherical shape.
  • the plurality of spherical cavities means that the plurality of spherical cavities are spherical.
  • some of the plurality of cavities may be included but not circular, for example, elliptical cavities.
  • the plurality of spherical cavities of each subcoating layer may be formed in various materials.
  • the plurality of spherical cavities of each subcoating layer may be formed from one selected from the group consisting of a hollow dielectric shell, a hollow conductor shell and a hollow semiconductor shell.
  • the spherical cavity can then have a cavity radius in the range of 0.002 microns to 500 microns.
  • the spherical cavity may also be a hollow shell formed separately from the filler material and mixed into the filler material, but furthermore, the spherical cavity may be a spherical cavity formed in the filler material itself.
  • the spherical cavity may be a hollow shell coated with a material selected from the group consisting of dielectric material, conductor material and semiconductor material on the outer or inner surface of the hollow shell.
  • the list of conductive materials for forming spherical cavities in the form of hollow conductor shells includes aluminum, chromium, cobalt, copper, gold, iridium, lithium, molybdenum, nickel, osmium, Palladium, platinum, rhodium, silver, tantalum, titanium, tungsten, vanadium, alloys thereof (e.g. aluminum-copper and steel) and Mixtures thereof are included, but are not limited to these.
  • Spherical cavities may also be formed from hollow multilayer shells, where the shell of each layer may be formed of a dielectric material, conductor material or semiconductor material. Dielectric materials or semiconductor materials with large refractive indices may also be selected as spherical cavities, but it is desirable to select conductive materials.
  • the plurality of spherical cavities of each subcoating layer has a constant radius a.
  • radius a should be seen as referring to the average radius of a plurality of spherical cavities.
  • a 11 is the average radius size for the plurality of first spherical cavities 11
  • a 12 is the average radius size for the plurality of second spherical cavities 12
  • a 13 is the average radius size for the plurality of third spherical cavities 13
  • a 14 is the average radius size for the plurality of fourth spherical cavities 14.
  • the spherical cavities of each subcoating layer may have a different radius from the spherical cavities of the other subcoating layer.
  • the spherical cavities of the first subcoat layer 101 comprise one type of cavities having a radius a 11
  • the spherical cavities of the second subcoat layer 102 have a radius a comprises a single type of joint with a 12
  • a third spherical joint of the sub-coating layer 103 comprise a single type of joint with a radius a 13
  • a spherical joint of the fourth sub-coating layer 104 are the radius a One type of cavities with 14 .
  • each subcoating layer comprises a filler material of refractive index n interposed in a space between a plurality of spherical cavities.
  • the filler material of each subcoating layer may have a different refractive index from that of the other subcoating layer or may have the same refractive index. Even if the filler materials of the sub-coating layer are identical to each other, the refractive indices may be formed differently, and even if the filler materials are different from each other, the refractive indices may be identical.
  • the first subcoat layer 101 comprises a first filler material 51 of refractive index n 51
  • the second subcoat layer 102 has a second filler of refractive index n 52
  • the third subcoat layer 103 comprises a third filler material 53 of refractive index n 53
  • the fourth subcoat layer 104 comprises a fourth filler material 54 of refractive index n 54. It includes.
  • the filler material included in each sub-coating includes dielectric materials, ceramic materials, composite materials (composite mixtures) and polymers. It may be selected from the group consisting of materials. These lists include paints, clays, glues, cements, asphalts, polymers, gelatins, glasses, resins, binders, oxides, and combinations thereof. But not limited to.
  • the list of composite materials includes paints, clays, adhesives, cements, etc.
  • the list of polymeric materials includes agarose, cellulose, epoxy, hydrogel, polyacrylamide, polyacrylate, poly-diacetylene, Polyepoxide, polyether, polyethylene, polyimidazole, polyimide, polymethylacrylate, polymethylmethacrylate, poly Peptides, polyphenylene-vinylene, polyphosphate, polypyrrole, polysaccharides, polystyrene, polysulfone, polythiophene , Polyurethane, polyvinyl, and the like.
  • Filler materials (51, 52, 53, 54) include agarose, cellulose, epoxy, hydrogel, silica gel, water glass (or sodium silicate) sodium silicate), silica glass, siloxane and the like.
  • Various resins include synthetic resins such as acrylic and vegetable resins such as mastic.
  • the list of oxides based on dielectric materials includes aluminum oxide, beryllium oxide, copper (I) oxide, copper (II) oxide, dysprosium oxide ), Hafnium (IV) oxide, lutetium oxide, magnesium oxide, scandium oxide, silicon monoxide, silicon dioxide, tantalum pentoxide ( tantalum pentoxide, tellurium dioxide, titanium dioxide, yttrium oxide, ytterbium oxide, zinc oxide, zirconium dioxide But not limited to.
  • Each subcoat layer has a structure similar to an aerogel structure. Aerogels are synthetic porous materials.
  • FIG. 4 shows a cross-sectional view along line AB of the multilayer coating system 900 of FIG. 1, showing a second exemplary embodiment 300.
  • the size distribution of the spherical cavities in each subcoating layer is the same as the size distribution of the spherical cavities of the other subcoating layer but the filler of each subcoating layer.
  • the material may have a different refractive index than the filler material of the other subcoating layer.
  • the spherical cavities of each subcoating layer have the same size distribution, but since each filler material of each subcoating layer has a different refractive index, each subcoating layer exhibits different characteristics.
  • the first spherical cavities 15 of one radius size are irregularly distributed across the first to fourth subcoat layers 301, 302, 303, 304,
  • the refractive indices for the first to fourth sub-coating layers 301, 302, 303, and 304 satisfy n 61 ⁇ n 62 ⁇ n 63 ⁇ n 64 , and n 61 , n 62 , n 63 and n 64 are each the first To refractive indexes for the fourth filler material 61, 62, 63, 64.
  • the multilayer coating system based on the second exemplary embodiment 300 suffers internal reflections at the interfaces of the subcoating layers due to different refractive indices for the subcoating layers. Such internal reflections inevitably lead to self-heating of the multilayer coating system.
  • the multilayer coating system according to the present invention may further include a substrate or a sealing member.
  • Substrates may be arranged at various locations, such as below or above the subcoating layer arranged at the bottom of the multilayer coating system.
  • the sealing member may also surround the multilayer coating system to seal the multilayer coating system from the outside.
  • the substrate 10 is arranged under the first subcoat layer 401.
  • Substrate 10 may also be arranged over a layer that is furthest from first subcoat layer 401, such as fourth subcoat layer 404, although not explicitly shown in FIG. 5.
  • fourth subcoat layer 404 although not explicitly shown in FIG. 5.
  • the substrate 10 is arranged both below the first subcoat layer 401 and above the fourth subcoat layer 404.
  • the multilayer coating system including the substrate 10 is surrounded by the sealing member 80.
  • This sealing member 80 is arranged to surround the multilayer coating system to seal the multilayer coating system from the outside.
  • the inside of the sealing member 80 may be discharged to the outside to maintain the vacuum in the absence of air.
  • the first to fourth subcoat layers 401, 402, 403, and 404 are provided with the first to fourth filler materials 61, 62, 63, and 64, respectively. Spherical cavities 15 of one size are irregularly distributed and separated from each other across the first to fourth filler materials 61, 62, 63, 64.
  • the multilayer coating system of the present invention can be applied directly to any surfaces. These include surfaces found in houses, household appliances, windows, cars, fabrics, clothing, papers, electronics, ceramic products, and the like.
  • the substrate 10 represents a wall
  • the fourth exemplary embodiment of FIG. 5B is a fabric
  • Substrate 10 represents a fabric
  • the substrate 10 may Indicates.
  • the materials for the substrate 10 may be selected from the group consisting of conductive materials, dielectric materials, ceramic materials, composite materials, semiconductor materials, polymeric materials and fabrics.
  • ceramic materials, composite materials, polymeric materials and fabrics are mentioned as if they are other materials than conductive materials, dielectric materials or semiconductor materials.
  • all materials can be classified into three materials: conductive materials, dielectric materials and semiconductor materials.
  • each of the ceramic materials, composite materials, polymeric materials and fabrics can be classified as conductive materials, dielectric materials or semiconductor materials.
  • the term 'dielectric material' or 'dielectric' is referred to in the description before or after this text, the term is referred to as ceramic materials, composite materials, polymeric materials or fabrics classified as dielectric materials. It will be understood to include all materials having the properties of a dielectric, including these.
  • the term 'conductive material' or 'conductor' is mentioned in the description, the term is a conductor, including ceramic materials, composite materials, polymeric materials or fabrics, which are classified as conductive materials. It will be understood to include all materials.
  • the term 'semiconductor material' or 'semiconductor' is any semiconductor material, including ceramic materials, composite materials, polymeric materials or fabrics classified as semiconductor materials. It will be understood to include them.
  • the list of conductive materials that can be used to form the substrate 10 includes aluminum, chromium, cobalt, copper, gold, iridium, lithium, molybdenum, nickel, osmium, palladium, platinum, rhodium, silver, tantalum, titanium, tungsten, Vanadium, alloys thereof (eg, aluminum-copper and steel) and mixtures thereof, including but not limited to.
  • the list of composite materials that can be used to form the substrate 10 includes concrete, asphalt-concrete, fiber-reinforced polymers, carbon-fibre reinforced plastics, glass-reinforced plastics, reinforced rubbers. Laminated woods, plywood, paper, fiber glass, bricks, and various composite glasses.
  • the list of polymeric materials that can be used to form the substrate 10 includes polyacrylamide, polyacrylate, poly-diacetylene, polyepoxide, polyether ( polyether, polyethylene, polyimidazole, polyimide, polymethylacrylate, polymethylmethacrylate, polypeptide, polyphenylene-vinylene (polyphenylene-vinylene), polyphosphate, polypyrrole, polysaccharide, polystyrene, polysulfone, polythiophene, polyurethane, polyvinyl ) And the like, but are not limited thereto.
  • Substrate 10 also includes other polymeric materials such as agarose, cellulose, epoxy, hydrogel, silica gel, silica glass, siloxane, and the like. Can be formed from them.
  • the list of fabrics that can be used to form the substrate 10 includes animal textiles, plant textiles, mineral textiles, synthetic textiles and combinations thereof. Included.
  • a plurality of holes irregularly distributed in the filler material of the sub-coating layer and separated from each other may be further included.
  • a plurality of holes contained in such a filler material may be provided in every subcoat layer or some subcoat layers forming a multilayer coating system. These plurality of holes may be smaller or larger than the plurality of spherical cavities of the subcoating layer. Furthermore, the plurality of holes may be spherical holes or like amorphous holes like the plurality of spherical cavities.
  • the plurality of holes provided in the filler material may improve the scattering efficiency of the radiation incident on the multilayer coating system or improve the thermal conductivity reduction rate.
  • the sixth embodiment 100 ′ exemplarily shown in FIG. 6 is a modification of the first exemplary embodiment 100, and in the sixth exemplary embodiment 100 ′, the first to fourth subs.
  • the plurality of holes 25 ′ are formed to be smaller in size than the first to fourth spherical cavities 11, 12, 13, 14.
  • the plurality of holes 25 ' may be chemically or naturally generated bubbles when forming the first to fourth filler materials 51', 52 ', 53', 54 '.
  • the first to fourth filler materials 51 ', 52', 53 ', and 54' are formed of polyurethane foam, chemically generated bubbles are present.
  • FIG. 7 shows a variation of the holes 25 ′ within the fourth filler material 54 ′ included in the fourth subcoat layer 104 ′ of the sixth exemplary embodiment 100 ′.
  • a variant is shown in which the plurality of holes 25 ′ in the filler material are larger in size than the fourth spherical cavity 14.
  • the filler material may have a shape such as Swiss cheese.
  • FIG. 8 shows a plurality of holes 25 ′ in the fourth filler material 54 ′ included in the fourth sub-coating layer 104 ′ of the sixth exemplary embodiment 100 ′ and other variations thereof. Is shown.
  • the plurality of holes 25 ′′ inside the fourth filler material 54 ′ have spherical shapes of radius b having a larger size than the fourth spherical cavity 14.
  • Such a large plurality of spherical holes 25 ′′ may be realized, for example, by embedding large hollow spherical shells into the filler material or forming large spherical cavities in the filler material itself.
  • FIG. 9 illustrates another variation of the plurality of holes 25 ′ within the fourth filler material 54 ′ included in the fourth subcoat layer 104 ′ of the sixth exemplary embodiment 100 ′. Is shown.
  • a plurality of holes 25 ′′ of radius b having a larger size than the plurality of fourth spherical cavities 14 of radius a 14 are formed in the fourth filler material 54 ′.
  • the radius c 24 of the fourth spherical particle 24 is smaller than the radius b of the spherical hole and the radius a 14 of the fourth spherical cavity 14. That is, it satisfies b> a 14 > c 24 .
  • the plurality of first spherical cavities having a radius a 11 in the first filler material 51 ' A plurality of holes 25 ′′ of radius b having a larger size than (11) as well as a plurality of first spherical particles 21 of radius c 21 are irregularly distributed and separated from each other, and the second filler material
  • the third filler material (53 ') a plurality of radius b with a larger size than the plurality of third rectangular cavity 13 of the radius 13 to a Holes 25 ′′ are of course irregularly distributed and separated from the plurality of third spherical particles 23 having a radius c 23 .
  • each radius of the first to third spherical particles 21, 22, 23 is the same as the radius of the fourth spherical particle 24, b> a 11 > c 21 , b> a 12 > c 22 and b> satisfies a 13 > c 23 Further, each radius of the first to fourth spherical particles 21, 22, 23, 24 satisfies c 21 ⁇ c 22 ⁇ c 23 ⁇ c 24 with each other.
  • the plurality of holes 25 ′ are shown to be spherical in the first to fourth filler materials 51 ′, 52 ′, 53 ′, and 54 ′. It is not limited to this.
  • the seventh embodiment 500 is a modification of the first exemplary embodiment 100 and shows that the electrodes constituting the activated electromagnetic wavelength filter are provided.
  • the starting point of the reflection area here can be changed by an applied electric field.
  • a second electrode 6 positioned between the 101 and the substrate 10 is provided, and a first voltage is applied to the first electrode 5 and a second voltage is applied to the second electrode 6.
  • the first electrode 5 or the second electrode 6 is limited to the surface located farthest from the first sub-coating layer 101 of the two surfaces of the fourth sub-coating layer 104 or the first electrode 5 and the first electrode 5.
  • the first sub-coating layer 101 and the substrate 10 are not limited to each other and may be arranged at various positions as necessary.
  • the electric field between the first and second electrodes 5, 6 is generated by applying a bias voltage to these electrodes.
  • Semiconductor materials react like dielectric materials in the absence of an electric field. However, when exposed to electric fields, semiconductor materials react like conductive materials. Such a property can be used to effectively control the wavelength at which electromagnetic waves begin to reflect. For example, the value of ⁇ 4 in reference numeral 504 of FIG. 11 to be described later may be changed by adjusting the strength of an electric field exposed to the sub-coating layer corresponding to 504.
  • the first and second electrodes 5, 6 of the seventh exemplary embodiment 500 may be formed of planar conductors that are transparent to the wavelengths of interest.
  • the first electrode 5 should be transparent to the infrared electromagnetic waves of interest.
  • the multilayer coating system shown in the seventh exemplary embodiment 500 is optically transparent, the infrared waves of interest as well as the first and second electrodes 5, 6 are both optically transparent as well. It must pass through.
  • the first electrode 5 or the second electrode 6 or both may be arranged such as a grid or grating structures or an array of holes or squares or the like. It can be patterned into more complex patterns. When the electrodes are patterned into such structures, the infrared wavelengths and visible light of interest can be transmitted through the openings of the patterned electrodes. If the electrodes are patterned with openings, the conductive materials for the electrodes are not limited to optically transparent conductors that transmit infrared wavelengths of interest, but any conductive materials may be used.
  • FIG. 11 is a schematic diagram illustrating the action of transmission and reflection in a physical (real) multilayer coating system 100 and other ideal multilayer coating systems 100.
  • the transmission and reflection actions shown in FIG. 11 are too ideal for a physical multilayer coating system, it provides a concise description of how wavelengths are selectively filtered in a multilayer coating system. It will be shown later that the physical multilayer coating system also exhibits equivalent properties as shown in FIG. 11. With this in mind, the following describes the effects of transmission and reflection in an ideal multilayer coating system.
  • An ideal multilayer coating system has ideal subcoating layers.
  • the ideal multilayer coating system 100 has ideal first to fourth subcoat layers 101, 102, 103, 104.
  • the actions of transmission and reflection in the ideal multilayer coating system 100 are shown in FIG. 11, and reference numeral 501 illustrates the action of transmission and reflection associated with the ideal first subcoat layer 101 and reference numeral 504. Describes similar operations for the ideal fourth subcoat layer 104.
  • the description of the other two actions, although not explicitly indicated in FIG. 11, may be easily associated with the ideal second and third subcoat layers 102, 103.
  • incident electromagnetic waves of wavelength ⁇ are completely transmitted for ⁇ ⁇ 4 , fully reflected for ⁇ 4 ⁇ ⁇ ⁇ ⁇ c , and partially transmitted and partially for ⁇ > ⁇ c. Is reflected.
  • Sub-coating layers with such wavelength filter characteristics are usefully applied to window panes where it is very necessary to reflect thermal or infrared electromagnetic waves and transmit electromagnetic waves of the visible spectrum and wavelengths used in the broadcast communications industry.
  • the width of the reflective area in the subcoat layer is limited.
  • the physical subcoat layer has a very narrow width ⁇ with respect to the reflective region. For this reason, a single subcoating layer is often not enough to block all unwanted wavelengths of the infrared spectrum in thermal barrier applications.
  • the reflective area of the subcoating layer can be varied within the wavelength range by adjusting the diameters of the spherical cavities provided in the subcoating layer. To illustrate this, reference is made to reference numeral 501 in FIG. 11 that illustrates the effects of transmission and reflection in the ideal first subcoat layer 101.
  • the change in the initial point of the reflective region at 501 is a result of the smaller first spherical cavity 11 distributed irregularly inside the first subcoat layer 101.
  • the radii of the first to fourth spherical cavities 11, 12, 13, 14 of the first to fourth subcoat layers 101, 102, 103, 104 are a 11. ⁇ a 12 ⁇ a 13 ⁇ a 14 , and such an arrangement of spherical cavities of an ideal multilayer coating system 100 exhibits the transmissive and reflective actions shown in FIG. 11.
  • the single subcoat layer is not sufficient to reflect all of the unwanted wavelengths due to the ⁇ of the finite width for its reflection area.
  • the first through fourth subcoat layers 101, 102, 103, 104 can be stacked together to form a multilayer coating system having a larger effective width ( ⁇ ) eff for the reflective region.
  • ⁇ effective width
  • any electromagnetic waves of undesired wavelengths that are not reflected by the fourth subcoat layer 104 are followed by the first to third subcoat layers 101, 102, 103. Eventually it will be reflected.
  • 11 reflected waves in the wavelength range ⁇ 1 ⁇ ⁇ ⁇ ⁇ ⁇ 4 are not confined inside the multilayer coating system 100 because there are no reflective regions on the travel path for these electromagnetic waves.
  • electromagnetic waves in the wavelength range ⁇ 1 ⁇ ⁇ ⁇ ⁇ 2 are reflected by the first subcoat layer 101.
  • Such reflected electromagnetic waves travel across the second to fourth subcoat layers 102, 103, 104 without internal reflection and finally exit the multilayer coating system 100. Since there is no reflection area on the travel path, internal reflection does not occur. Also for that reason any reflected electromagnetic waves in the wavelength range ⁇ 1 ⁇ ⁇ ⁇ ⁇ 2 will not cause magnetic heating in the multilayer coating system.
  • electromagnetic waves in the wavelength range ⁇ > ⁇ c travel across the subsequent subcoat layers, some are transmitted and some are reflected. Such electromagnetic waves are internally reflected at the interfaces between the subcoats. As a result, these electromagnetic waves cause self heating of the multilayer coating system 100. Fortunately, electromagnetic waves in the wavelength range ⁇ > ⁇ c are not as active as those in the wavelength range ⁇ ⁇ ⁇ 4 . It is negligible that electromagnetic waves in the wavelength range ⁇ > ⁇ c cause heating of the multilayer coating system.
  • the multilayer coating system has been irradiated on top.
  • the topmost portion is the fourth subcoat layer 104 and the bottommost portion is the first subcoat layer 101.
  • the multilayer coating system 100 may also be irradiated at the bottom and many of the transmission and reflection actions of the basic electromagnetic waves in this regard can still be described as shown in FIG. 11. For example, incident electromagnetic waves with wavelengths satisfying 0 ⁇ ⁇ 1 are transmitted completely across the sub-coating layers, while incident electromagnetic waves with wavelengths satisfying ⁇ > ⁇ c are partially transmitted and partially reflected. However, major modifications in the transmission and reflection actions occur when the direction of the incident electromagnetic wave is reversed in FIG. 2.
  • the physical first subcoat layer 104 does not have transmissive and reflective regions so clearly outlined as shown at 504 as opposed to the ideal first subcoat layer 104. However, when the physical subcoating layers are stacked together to form a multilayer coating system, the resulting transmissive and reflective actions exhibit most of the properties described with reference to FIG. 11 for an ideal coating system.
  • ⁇ Q Q bac -Q ext is a difference function
  • Q bac is a backward scattering efficiency factor or back-scattering efficiency factor
  • Q ext is an extinction efficiency factor.
  • Mie theory was used to calculate Q bac and Q ext . 12, it can be easily seen that each ⁇ Q graph has two distinct regions.
  • the first region I exhibits the characteristic that ⁇ Q has a negative value ( ⁇ Q ⁇ 0), while the second region II exhibits the characteristic of ⁇ Q having a positive value ( ⁇ Q> 0).
  • ⁇ Q has a negative value
  • ⁇ Q> 0 the characteristic of ⁇ Q having a positive value
  • the spherical cavity is centered and irradiated from the left.
  • the results in FIGS. 13 and 14 show that the wavelengths of the first region I are strongly scattered (ie transmitted) while the wavelengths of the second region II are scattered forward (ie, transmitted). As well as being scattered back (ie, reflected).
  • the first region I of FIG. 12 may be associated with a wavelength range 0 ⁇ ⁇ 4 at 504, and the second region II of FIG. 12 is a wavelength range at 504. ⁇ 4 ⁇ ⁇ ⁇ c .
  • the ratio of scattered wave intensity I s and incident wave intensity I o approaches 1 for sufficiently large wavelengths.
  • the waves in this region correspond to waves with wavelengths satisfying ⁇ > ⁇ c at 504 in FIG. 10, which are partially transmitted and partially reflected at the same scales.
  • the 15 illustrates an exemplary method of making a multilayer coating system.
  • Small spherical cavities of constant size are mixed in the first container containing the first solution.
  • the second container containing the second solution is mixed with large spherical cavities of constant size larger than the small spherical cavities of the first solution. If the spherical cavities are mixed in a conventional paint, the first solution of the first container and the second solution of the second container may be formed of the conventional paint.
  • the first subcoat layer on the substrate can be formed by dipping an uncoated substrate into a first solution of a first container. Subsequently, the substrate to which the first subcoat layer is applied may be dried or cured before dipping into the second solution of the second container.
  • the second subcoat layer is applied onto the first subcoat layer by dipping the substrate on which the first subcoat layer is formed into the second solution of the second container.
  • a multilayer coating system in which two subcoating layers are sequentially formed on the substrate can be manufactured. This dipping method can form a multilayer coating system on both surfaces of a substrate.
  • the multilayer coating system may be applied by applying a mixture of spherical cavities onto one surface of the substrate by repeating spin coating. Can be formed.
  • a mixture of spherical cavities can be applied to the cylindrical medial side by repeated spin casting to form a multilayer coating system.
  • the first and second solutions as a mixture for each subcoating layer are formed by mixing conventional paint with spherical cavities, but not limited thereto. Does not.
  • Mixtures for each subcoating layer of the multilayer coating system can be prepared by mixing the spherical cavities together in any solutions.
  • These solutions include solvent base coatings, composite mixtures (such as adhesives, clays, etc.), polyurethanes, elastomers, plastics, gelatin, epoxy but also not limited to polymeric materials such as epoxy, acrylic, polymethylmethacrylate (PMMA), as well as some listed resins and binders such as cement. Does not.
  • spherical cavities of one size may be mixed in a liquefied PMMA (polymethylmethacrylate) solution.
  • the second solution in FIG. 15 may also be represented by liquefied PMMA, but spherical cavities of larger diameter sizes are mixed than those mixed in the first solution.
  • the multilayer coating system can be formed on the substrate according to the dipping procedures already described.
  • the mixtures for each subcoating layer of a multilayer coating system may be prepared by mixing spherical cavities into a solution formed of a polymeric material such as polyurethane.
  • the first solution and the second solution of FIG. 15 may be represented as polyurethane solutions, where each solution contains spherical cavities of appropriate diameter sizes.
  • FIG. 16 illustrates another method of manufacturing a multilayer coating system, by way of example.
  • a multilayer coating system can be formed thereon by soaking (or dipping) a fabric net into a first solution and a second solution according to the processes described previously.
  • First prepare a fabric network as shown in FIG. 16A.
  • a woven net is a kind of net made of thread or wire.
  • FIG. 16B one subcoating layer is formed by dipping and coating the fabric net into a first container containing a first solution in which spherical cavities are mixed.
  • the fabric network serves as a skeleton, the sub-coating layer is not easily broken or broken, as well as the structure is flexible. In this way a plurality of sub-coating layers are formed.
  • the plurality of sub-coating layers thus formed may be stacked to form a multilayer coating system.
  • the sub-coating layers may be bonded with a material such as an adhesive or sewn with a thread.
  • a material such as an adhesive or sewn with a thread.
  • a multilayer coating system can be formed on strands of textile fibers. That is, the fabric fiber strands may be formed thereon by soaking (or dipping) the fabric fiber strands into the first and second solutions according to the processes described previously. Threads of such fiber strands coated with a multilayer coating system can be used to make heat resistant clothes. Such multilayer coating systems may also be utilized as insulation in shoes.
  • FIG. 17 illustrates another method of manufacturing a multilayer coating system by way of example.
  • the first solution refers to a material in which a solution and a small cavity are mixed.
  • This first solution can be poured into a mold and then cured to make each subcoating layer of the multilayer coating system.
  • the first solution in the first container may be poured into a mold and dried to form a first subcoat layer.
  • the second solution in the second container can be poured into another mold and dried to form a second subcoating layer.
  • the first subcoating layer and the second subcoating layer thus formed may be pasted with an adhesive to form a multilayer coating system.
  • the first and second solutions of FIG. 17 may be made by mixing variously, and one of them is a method of mixing spherical cavities in an aqueous polyurethane or water based polyurethane.
  • the water-soluble polyurethane has a structure in which a solid polyurethane polymer is emulsified in water, and there is a difference in specific gravity between water and a solid polyurethane polymer depending on the product.
  • the co-particles can contain at least twice the mass of the solid polyurethane polymer. The higher the specific gravity of the cavity, the higher the viscosity of the solution.
  • the solid polyurethane polymer mass can be up to 40 grams and the K1 glass bubble mass can be up to 20 grams.
  • 3M's S60HS glass bubble can be used to weigh 40 grams of solid polyurethane polymer and up to 88 grams of S60HS glass bubble mass. As the amount of glass bubble is added, the viscosity of the solution becomes too high to reach the state of no flow. In order to increase the thermal insulation, glass bubbles should be added as much as possible, but it is necessary to compromise the viscosity of the working solution.
  • the present invention can be used in the field to which the heat shield system and its manufacturing method are applied.

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Abstract

La présente invention concerne un système de revêtement multicouche et son procédé de fabrication, le système de revêtement multicouche comprenant : une couche 1 qui comprend une pluralité de vides sphériques, qui sont répartis de façon irrégulière, bien séparés et ont un rayon de a1, et un matériau de remplissage ayant un indice de réfraction de n1 qui est intercalé entre les vides sphériques ; et des couches suivantes représentées par l'équation à mots suivante, "couche i qui est positionnée sur la couche i-1 et comprend une pluralité de vides sphériques, qui sont répartis de façon irrégulière, bien séparés et ont un rayon de ai, et un matériau de remplissage ayant un indice de réfraction de ni qui est intercalé entre les vides sphériques (i étant un entier supérieur à 1)."
PCT/KR2014/010438 2013-11-04 2014-11-03 Système de revêtement multicouche utilisant des vides pour système de protection thermique et son procédé de fabrication WO2015065134A1 (fr)

Priority Applications (4)

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CN201480060391.4A CN105793031B (zh) 2013-11-04 2014-11-03 用于热阻隔系统的多层涂覆系统及其制造方法
US15/033,842 US9835929B2 (en) 2013-11-04 2014-11-03 Multi-layer coating system using voids for heat blocking system and method for manufacturing same
ES14857339T ES2818934T3 (es) 2013-11-04 2014-11-03 Sistema de recubrimiento multicapa que utiliza huecos para un sistema de blindaje térmico y procedimiento de fabricación del mismo
EP14857339.7A EP3067197B1 (fr) 2013-11-04 2014-11-03 Système de revêtement multicouche utilisant des vides pour système de protection thermique et son procédé de fabrication

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US201361899832P 2013-11-04 2013-11-04
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US201361908608P 2013-11-25 2013-11-25
US61/908,608 2013-11-25
US14/146,426 US9372291B2 (en) 2013-11-04 2014-01-02 Heat blocking system utilizing particulates
US14/146,426 2014-01-02
KR1020140052953A KR101596453B1 (ko) 2013-11-04 2014-04-30 공동들을 이용한 열 차단 시스템용 다중층 코팅 시스템 및 그 제조방법
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