WO2012018201A2 - A plate comprising an amorphous ceramic coating layer, its use and method of manufacturing the same - Google Patents
A plate comprising an amorphous ceramic coating layer, its use and method of manufacturing the same Download PDFInfo
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- WO2012018201A2 WO2012018201A2 PCT/KR2011/005638 KR2011005638W WO2012018201A2 WO 2012018201 A2 WO2012018201 A2 WO 2012018201A2 KR 2011005638 W KR2011005638 W KR 2011005638W WO 2012018201 A2 WO2012018201 A2 WO 2012018201A2
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- 238000005524 ceramic coating Methods 0.000 title claims abstract description 45
- 239000011247 coating layer Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 60
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000001816 cooling Methods 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 239000000919 ceramic Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 23
- 238000010304 firing Methods 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 27
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052785 arsenic Inorganic materials 0.000 claims description 11
- 229910052733 gallium Inorganic materials 0.000 claims description 11
- 229910052738 indium Inorganic materials 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 6
- 229910017083 AlN Inorganic materials 0.000 claims description 6
- 229910052580 B4C Inorganic materials 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 239000003507 refrigerant Substances 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 239000010410 layer Substances 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 6
- 238000005299 abrasion Methods 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 210000003298 dental enamel Anatomy 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910001651 emery Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
- C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
Abstract
This invention relates to a plate including an amorphous ceramic coating layer, its use and a method of manufacturing the same. More specifically, this invention relates to plate including an amorphous ceramic coating layer obtained by coating a composition including 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.1 to 0.2 parts by weight of an additive, 0.2 to 27 parts by weight of a filling, 0.5 to 5.0 parts by weight of porous ceramic, and 15 to 32 parts by weight of a hardening agent on the plate, followed by firing at 100 to 350℃ and cooling at 10~30℃/sec. The plate including the amorphous ceramic coating layer of this invention has an enhanced durability due to very high improvement of mechanical properties such as abrasion resistance, corrosion resistance, and heat resistance. Also, the plate of this invention has no occurrence of cracks, barely exhibition of brittleness even at an excessive stress, and a hardness increase to the level of twice to three times higher than a conventional ceramic coating layer, which is similar to that of enamel. Furthermore, when multi-layered coating with more than two layers is rapidly cooled or ultra-rapidly cooled, a completed ceramic coating film with a high physical property, no cracksand no peeling shows an electrically semiconductor characteristic due to the amorphous ceramic.
Description
The present invention relates to a plate including an amorphous ceramic coating layer, its use and a method of manufacturing the same.
A ceramic coating agent or an organic-inorganic hybrid composite coating agent, prepared by a sol-gel process, has been increasingly used because it is used at a low temperature, and its final coating film has high physical properties such as abrasion resistance, heat resistance, and corrosion resistance. In use of such a ceramic coating agent, a coating film coated on a to-be-coated substrate with a thickness of less than about 15㎛ has a low opacity, and a low protective capacity on the to-be-coated substrate while a coating film with a thickness of 30㎛ or more shows a high hardness. However, in the coating film, cracks may occur due to the insufficiency of inter-particle bonding of a used raw material during a rapid temperature change such as heating or cooling, and a difference in a thermal expansion coefficient between a to-be-coated substrate and a coated film. This may result in the peeling of the coating film. Also, when fillings are sufficiently mixed or a firing temperature is raised, it is difficult to highly increase the coherence between internal particles, and to achieve a final coating film’s hardness surpassing 9H (pencil hardness). In other words, the film shows a high vulnerability against scratches and brittleness even at a low stress due to its low fracture toughness.
Methods for solving these problems are disclosed in Korean Registered Patent No. 10-0397486, and Korean Publication Patent Nos. 10-2009-0006695, 10-2010-0052824.
Meanwhile, amorphism indicates that a short range order exists but a long range order disappears in the intermolecular bonding, while a new physical property appears. The inventor of the present invention found that rapid cooling does not cause damage to a coating layer and allows the coating layer to have amorphism with only a short range order and no long range order, thereby highly improving mechanical properties such as abrasion resistance, corrosion resistance, heat resistance, and hardness. Then, he completed this invention based on this findings.
An object of the present invention is to provide a plate including an amorphous ceramic coating layer with no damage, and a method of manufacturing the same, in which in the coating layer, a short range order exists but a long range order does not exist. Also, the present invention provides a solar cell or a heating plate for kitchen use, which includes the coating layer.
In one embodiment with an aspect of the present invention, there is provided a plate including an amorphous ceramic coating layer, which is obtained by coating a composition including 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.1 to 0.2 parts by weight of an additive, 0.2 to 27 parts by weight of a filling, 0.5 to 5.0 parts by weight of porous ceramic, and 15 to 32 parts by weight of a hardening agent on the plate, followed by firing at 100 to 350℃ and cooling at 10~30℃/sec. The silica sol provides a plate including an amorphous ceramic coating layer which consists of at least one of afirst silica sol with a particle size of 10 to 50㎚, a second silica sol with a particle size of 100 to 200㎚, and a third silica sol with a particle size of 200 to 300㎚. The silica sol may have a composition ratio of 2:1:1. The alcohol provides a plate including an amorphous ceramic coating layer with aliphatic alcohol. The additive provides a plate including an amorphous ceramic coating layer with K and Na. The hardening agent provides a plate including an amorphous ceramic coating layer with silane. The filling provides a plate including an amorphous ceramic coating layer with mixture including at least one kind selected from the group including Si, Sic, B, Al, In and Ga. The filling provides a plate including a specific amorphous ceramic coating layer with mixture consisting of at least one kind selected from the group including Si, Sb, P and As. The filling provides a plate including a specific amorphous ceramic coating layer with a mixture consisting of at least one kind selected from the group including SiO2, TiO2, ZrO2, Al2O3, CoO, MnO, Fe2O3, AlN, Si3N4, B4C, C and BN. The plate may be used for any one of kitchenuse, architecture, a vehicle, a ship, and an electric product. The plate may be any one selected from the group including metal, ceramic and plastic.
In one embodiment, there is provided a solar cell including an amorphous ceramic coating layer, which is obtained by coating a substrate with a mixture composition including 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.1 to 0.2 parts by weight of an additive, 0.2 to 27 parts by weight of a filling, 0.5 to 5.0 parts by weight of porous ceramic, and 15 to 32 parts by weight of a hardening agent, followed by firing at 100 to 350℃ and cooling at 10~30℃/sec. The silica sol may provide a solar cell including an amorphous ceramic coating layer from mixture consisting of at least one of a first silica sol with a particle size of 10 to 50㎚, asecond silica sol with a particle size of 100 to 200㎚, and athird silica sol with a particle size of 200 to 300㎚. The filling may provide a solar cell including a amorphous ceramic coating layer from mixture consisting of at least one kind selected from the group including Si, Sic, B, Al, In and Ga. The filling is a mixture including at least one kind selected from the group including Si, Sb, P and As.
According to one embodiment, there is provided a method of manufacturing a plate including an amorphous ceramic by the method including the steps of: preparing a coating agent by ball-milling 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.2 to 27 parts by weight of a filling, and 0.5 to 5.0 parts by weight of porous ceramic, and adding 15 to 32 parts by weight of a hardening agent and 0.1 to 0.2 parts by weight of an additive; coating the above coating agent on the plate, followed by firing at 100 to 350℃ and cooling the fired plate at 10~30℃/sec. In the step of cooling the above example of another embodiment, there is provided a specific method with a temperature difference between before-cooling and after-cooling may range from 100℃ to 200℃ The silica sol may provide a method of manufacturing a plate including at least one of a first silica sol with a particle size of 10 to 50㎚, a second silica sol with a particle size of 100 to 200㎚, and a third silica sol with a particle size of 200 to 300㎚. There is provided a method of manufacturing a plate which the silica sol may have a composition ratio of 2:1:1.There is provided a method of manufacturing a plate which the alcohol may include aliphatic alcohol. There is provided a method of manufacturing plate which the additive may include K and Na. There is provided a specific method which the hardening agent may include silane. There is provided a method which the filling may be a mixture including at least one kind selected from the group including Si, Sic, B, Al, In and Ga. There is provided a method of manufacturing a plate which the filling may be a mixture including at least one kind selected from the group including Si, Sb, P and As. There is provided a method of manufacturing a plate which the filling may be a mixture including at least one kind selected from the group including SiO2, TiO2, ZrO2, Al2O3, CoO, MnO, Fe2O3, AlN, Si3N4, B4C, C and BN. There is provided a method of manufacturing a plate which a refrigerant containing Na or K is used in the step of cooling the fired plate in the above example. There is provided a method of manufacturing a plate which t further may include a ceramic coating layer, the coating layer being obtained by additional coating a coating agent on the plate, followed by further coating the above plate with ceramic coating layer which is manufactured by firing at 100 to 350℃ and cooling at 0~30℃ wherein the coating agent is prepared by ball-milling 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.2 to 27 parts by weight of a filling, and 0.5 to 5.0 parts by weight of porous ceramic, and adding 15 to 32 parts by weight of a hardening agent and 0.1 to 0.2 parts by weight of an additive.
In one embodiment, there is provided amethod of manufacturing a solar cell, the method including the steps of: coating a coating agent on a substrate, the coating agent being prepared by adding 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.2 to 27 parts by weight of a filling including a mixture with at least one kind selected from the group consisting of Si, Sic, B, Al, In and Ga, 0.5 to 5.0 parts by weight of porous ceramic, 15 to 32 parts by weight of a hardening agent, and 0.1 to 0.2 parts by weight of an additive,; coating a coating agent on the coated substrate, the coating agent being prepared by adding 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.2 to 27 parts by weight of a filling including a mixture at least one kind selected from the group consisting of Si, Sb, P and As,0.5 to 5.0 parts by weight of porous ceramic, 15 to 32 parts by weight of a hardening agent, and 0.1 to 0.2 parts by weight of an additive firing the coated substrate at 100~350℃; cooling the fired substrate at 10~30℃/sec; and coating a transparent conductive material on the cooled substrate. There is provided a method of manufacturing solar cell including the step of re-firing the substrate at 100~350℃ and re-cooling the re-fired substrate at 10~30℃/sec, after the step of cooling the fired substrate at 0~30℃. Also, there is provided a method of manufacturing solar cell including the cooling step which a temperature difference between before-cooling and after-cooling may range from 100℃ to 200℃. There is provided a method of manufacturing solar cell which the transparent conductive material in above example may be any one selected from the group including ITO (Indium Tin Oxide), ZnO, Ag, AlZnO and InZnO. There is provided a method of manufacturing solar cell which the substrate of above example may be any one selected from the group including aluminum, copper, and polyimide.
In one embodiment, there is provided a composition for preparing an amorphous ceramic coating, which includes 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.1 to 0.2 parts by weight of an additive, 0.2 to 27 parts by weight of a filling, 0.5 to 5.0 parts by weight of porous ceramic, and 15 to 32 parts by weight of a hardening agent. There is provided a method of a composition for preparing an amorphous ceramic coating which the silica sol is selected from at least one of first silica sol with a particle size of 10 to 50㎚, second silica sol with a particle size of 100 to 200㎚, and third silica sol with a particle size of 200 to 300㎚. Also, there is provided a method of the composition for preparing an amorphous ceramic coating which the silica sol of above example may have a composition ratio of 2:1:1. Also, there is provided a method of the composition for preparing an amorphous ceramic coating which the alcohol may include aliphatic alcohol. Also, there is provided a method of the composition for preparing an amorphous ceramic coating that the additive of above example may include K and Na. Also, there is provided a method of the composition for preparing an amorphous ceramic coating which the hardening agent may include silane. Also, there is provided a method of the composition for preparing an amorphous ceramic coating that the may be a mixture including at least one kind selected from the group including Si, Sic, B, Al, In and Ga. Also, there is provided a method of the composition for preparing an amorphous ceramic coating that may be a mixture including at least one kind selected from the group including Si, Sb, P and As. Also, there is provided a method of the composition for preparing an amorphous ceramic coating which the filling may be a mixture including at least one kind selected from the group including SiO2, TiO2, ZrO2, Al2O3, CoO, MnO, Fe2O3, AlN, Si3N4, B4C, C and BN.
In one embodiment, there is provided a method of manufacturing a heating plate for kitchen use, the heating plate including an amorphous ceramic, the method including the steps of: preparing a coating agent by ball-milling 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.2 to 27 parts by weight of a filling, and 0.5 to 5.0 parts by weight of porous ceramic, and adding 15 to 32 parts by weight of a hardening agent and 0.1 to 0.2 parts by weight of an additive; coating the coating agent on the heating plate for kitchen use, followed by firing at 100 to 350℃ and cooling the fired heating plate at 10~30℃/sec.
The plate including the amorphous ceramic coating layer of the present invention has an enhanced durability because the coating layer can greatly improve mechanical properties such as abrasion resistance, corrosion resistance, and heat resistance. Also, in the coating layer, there is no occurrence of cracks, and brittleness is hardly shown even at an excessive stress. And, the coating layer can have a hardness level twice to three times higher thanthat of a conventional ceramic coating layer, which is similar to that of enamel. Furthermore, when two or more multi-layered coating layers are fast cooled or ultra-fast cooled, a completed ceramic coating film with a high physical property of no cracks and no peeling shows an electrically semi-conductive characteristics similiar to the amorphous ceramic.
The foregoing and other objects, features and advantages of the present invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic view showing an NP type cell coated with a coating agent of the present invention and FIG. 2 is a schematic view showing NP type solar cells coated with a coating agent of the present invention, which are connected in parallel.
Example
Example 1: Fabrication of a substrate including aceramic coating layer
1-1. Preparation Example 1
560g (including 400g of water) of silica sol mixture comprising with three particle sizes of 10 to 50nm, 100 to 200nm, and 200 to 300nm at a ratio of 2:1:1, 110g of IPA (Isopropyl Alcohol), 2g of TiO2-based pigment as a filling, and 5g of porous silica were placed in a ball mill, and then were ball-milled at 100RPM for about 4 hours. The resultant liquid was transferred to an agitator. Then 320g of MTMS (methyltrimethoxy silane) as a hardening agent and 1g of formic acid as an acid catalyst were added to the liquid and then the liquid was agitated and cured at 100RPM for about 6 hours. Then, 2g of a mixture of potassium and sodium was added thereto, followed by further agitating and curing for about 30 min, so as to provide 1kg of a coating agent.
An aluminum substrate with a size of 100x100x10mm was cleanly washed through a sanding process of 80# emery, spray-coated with the completed coating agent, and then fired in a firing furnace for about 30min at 250℃ At the outlet, the fired aluminum substrate was immediately immersed in 20℃water, and then rapidly cooled at 10℃/sec so as to provide a substrate coated with an amorphous coating film with a thickness of 30㎛.
1-2. Preparation Example 2
A substrate was fabricated in the same manner as described in Preparation Example 1 except that a mixing ratio in the Preparation example noted in Table 1 below was employed, and Al2O3, ZrO2 and Fe2O3 as fillings were used at a ratio of 1:1:1.
1-3. Preparation Example 3
A substrate was fabricated in the same manner as described in Preparation Example 1 except that a mixing ratio in the Preparation example noted in Table 1 below was employed, and AIN and Si3N4 as fillings were used at a ratio of 1:1.
Coating agents of a control group and Preparation Examples 1, 2 and 3 are noted in below Table 1.
[Corrected under Rule 26 18.08.2011]
Table 1 
Table 1
Example 2: Test on physical properties of the substrate with an amorphous ceramic coating agent
Tests on physical properties of the above prepared ceramic coating agent were carried out. The results are noted in Table 2.
Table 2
| index | Control group | Preparation Example 1 | Preparation Example 2 | Preparation Example 3 | Remark |
| Crack | Slight occurrence of crack | no | no | no | x200 microscope |
| Hardness | 7~8H | 9H or more | 9H or more | 9H or more | Pencil hardness |
| Heat resistance | Occurrence of peeling | No damage | No damage | No | 400℃ |
| Alkali resistance | No damage | No damage | No damage | No damage | 5% Na2CO3 aqueous solution |
| Acid resistance | No damage | No damage | No damage | No damage | Acetic acid 5% aqueous solution |
Example 3: Fabrication of a solar cell with a substrate including an amorphous ceramic coating agent
Two kinds of coating agents were prepared according to the mixing ratio of Preparation Example 4 noted in above Table 1.
Type A Al, Ga and Inas fillings were used at a ratio of 2:1:1 (used as a P-type semiconductor).
Type B - P, Sb and As as fillings were used at a ratio of 2:1:1 (used as a N-type semiconductor).
An aluminum substrate with a size of 200x200x2mm was prepared, cleanly washed through a sanding process of 100# emery, and then base-coated with the type A coating agent of a coating film thickness of about 20㎛ (P-type semiconductor). On the film, the type B coating agent was spray-coated with a coating film thickness of about 15㎛ (N-type semiconductor), and heated/fired for about 30min at a firing temperature of 150℃ and then, was immediately rapidly cooled at 10℃/sec or more for less than 5 min with cool air having a temperature less than 15℃. The coating film which had become amorphous by rapid cooling was thinly coated with a high light transmittable ITO conductive coating film made of In and Sn with a thickness of about 5 to 7㎛, followed by heating/firing at 100℃ for 20 min, so as to provide a substrate. The completed substrate was grounded as shown in FIG. 2, and exposed to sun light for about 10 min. Then, electricity generation was checked.
As described in Preparation Examples 1, 2 and 3, the inventive amorphous ceramic coating film, which was prepared by coating with a coating agent obtained by a metallic oxide or a non-oxide as fillings, followed by heating and firing, and rapid cooling, shows very high excellent mechanical properties such as abrasion resistance, corrosion resistance, heat resistance, and hardness. Also, by selecting a filling as described in Example 4, the above coating film may be utilized as P-type, and N-type semiconductors for a solar cell capable of converting sunlight into electricity
The amorphous ceramic coating fabricated according to the present invention can be used across overall industries such as solar cells, vehicles, architectures, ships, or kitchen utensils.
[Description of codes]
100: ITO Transparent conductive layer
200: Type N Semiconductor layer (layer for generator)
300: Type P Semiconductor layer (layer for generator)
400: A1 Substrate
500: Wire
Claims (42)
- A plate comprising an amorphous ceramic coating layer, which is obtained by coating with a composition comprising 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.1 to 0.2 parts by weight of an additive, 0.2 to 27 parts by weight of a filling, 0.5 to 5.0 parts by weight of porous ceramic, and 15 to 32 parts by weight of a hardening agent on the plate, followed by firing at 100 to 350℃ and cooling at 10~30℃/sec.
- The plate as claimed in claim 1, wherein the silica sol employs at least one of a first silica sol with a particle size of 10 to 50㎚, a second silica sol with a particle size of 100 to 200㎚, and a third silica sol with a particle size of 200 to 300㎚.
- The plate as claimed in claim 2, wherein the silica sol has a composition ratio of 2:1:1.
- The plate as claimed in claim 1, wherein the alcohol comprises aliphatic alcohol.
- The plate as claimed in claim 1, wherein the additive comprises K and Na.
- The plate as claimed in claim 1, wherein the hardening agent comprises silane.
- The plate as claimed in claim 1, wherein the filling is a mixture comprising at least one kind selected from the group including Si, Sic, B, Al, In and Ga.
- The plate as claimed in claim 1, wherein the filling is a mixture comprising at least one kind selected from the group including Si, Sb, P and As.
- The plate as claimed in claim 1, wherein the filling is a mixture comprising at least one kind selected from the group including SiO2, TiO2, ZrO2, Al2O3, CoO, MnO, Fe2O3, AlN, Si3N4, B4C, C and BN.
- The plate as claimed in claim 1, which is used for any one of kitchen use, architecture, a vehicle, a ship, and an electric product.
- The plate as claimed in claim 1, wherein the plate is any one selected from the group including metal, ceramic and plastic.
- A solar cell comprising an amorphous ceramic coating layer, which is obtained by coating with a mixture composition comprising 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.1 to 0.2 parts by weight of an additive, 0.2 to 27 parts by weight of a filling, 0.5 to 5.0 parts by weight of porous ceramic, and 15 to 32 parts by weight of a hardening agent on a substrate, followed by firing at 100 to 350℃ and cooling at 10~30℃/sec.
- The solar cell as claimed in claim 12, wherein the silica sol employs at least one of a first silica sol with a particle size of 10 to 50㎚, a second silica sol with a particle size of 100 to 200㎚, and a third silica sol with a particle size of 200 to 300㎚.
- The solar cell as claimed in claim 12 or 13, wherein the filling is a mixture comprising at least one kind selected from the group including Si, Sic, B, Al, In and Ga.
- The solar cell as claimed in claim 12 or 13, wherein the filling is a mixture comprising at least one kind selected from the group including Si, Sb, P and As.
- A method of manufacturing a plate comprising an amorphous ceramic, the method comprising the steps of:preparing a coating agent by ball-milling 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.2 to 27 parts by weight of a filling, and 0.5 to 5.0 parts by weight of porous ceramic, and adding 15 to 32 parts by weight of a hardening agent and 0.1 to 0.2 parts by weight of an additive,coating the coating agent on the plate, followed by firing at 100 to 350℃ andcooling the fired plate at 10~30℃/sec.
- The method of manufacturing plate as claimed in claim 16, wherein in the step of cooling the fired plate, a temperature difference between before-cooling and after-cooling ranges from 100℃ to 200℃
- The method as claimed in claim 16, wherein the silica sol employs at least one of first a silica sol with a particle size of 10 to 50㎚, asecond silica sol with a particle size of 100 to 200㎚, and athird silica sol with a particle size of 200 to 300㎚.
- The method as claimed in claim 16, wherein the silica sol has a composition ratio of 2:1:1.
- The method as claimed in claim 16, wherein the alcohol comprises aliphatic alcohol.
- The method as claimed in claim 16, wherein the additive comprises K and Na.
- The method as claimed in claim 16, wherein the hardening agent comprises silane.
- The method as claimed in claim 16, wherein the filling is a mixture comprising at least one kind selected from the group including Si, Sic, B, Al, In and Ga.
- The method as claimed in claim 16, wherein the filling is a mixture comprising at least one kind selected from the group including Si, Sb, P and As.
- The method as claimed in claim 16, wherein the filling is a mixture comprising at least one kind selected from the group including SiO2, TiO2, ZrO2, Al2O3, CoO, MnO, Fe2O3, AlN, Si3N4, B4C, C and BN.
- The method as claimed in claim 16, wherein in the step of cooling the fired plate, a refrigerant containing Na or K is used.
- The method as claimed in any one of claims 16 to 26, wherein the plate further comprises a ceramic coating layer, the coating layer being obtained by further coating a coating agent on the plate, followed by firing at 100 to 350℃ and cooling at 0~30℃ wherein the coating agent is prepared by ball-milling 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.2 to 27 parts by weight of a filling , and 0.5 to 5.0 parts by weight of porous ceramic, and adding 15 to 32 parts by weight of a hardening agent and 0.1 to 0.2 parts by weight of an additive.
- A method of manufacturing a solar cell, the method comprising the steps of:coating a coating agent on a substrate, the coating agent being prepared by adding 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.2 to 27 parts by weight of a filling comprising a mixture at least one kind selected from the group including Si, Sic, B, Al, In and Ga, 0.5 to 5.0 parts by weight of porous ceramic, 15 to 32 parts by weight of a hardening agent, and 0.1 to 0.2 parts by weight of an additive,coating a coating agent on the coated substrate, the coating agent being prepared by adding 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.2 to 27 parts by weight of a filling with at least one mixture selected from group consisting of Si,Sb,P and As, 0.5 to 5.0 parts by weight of porous ceramic, 15 to 32 parts by weight of a hardening agent, and 0.1 to 0.2 parts by weight of an additive,firing the coated substrate at 100~350℃cooling the fired substrate at 10~30℃/sec; andcoating a transparent conductive material on the cooled substrate.
- The method as claimed in claim 28, comprisingthe step of re-firing the substrate at 100~350℃ and re-cooling the re-fired substrate at 10~30℃/sec, after the step of cooling the fired substrate at 0~30℃.
- The method as claimed in claim 28, wherein in the step of cooling the fired substrate, a temperature difference between before-cooling and after-cooling ranges from 100℃ to 200℃.
- The method as claimed in claim 28, wherein the transparent conductive material is any one selected from the group including ITO (Indium Tin Oxide), ZnO, Ag, AlZnO and InZnO.
- The method as claimed in claim 28, wherein the substrate is any one selected from the group including aluminum, copper, andpolyimide.
- A composition for preparing an amorphous ceramic coating, which comprises 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.1 to 0.2 parts by weight of an additive, 0.2 to 27 parts by weight of a filling, 0.5 to 5.0 parts by weight of porous ceramic, and 15 to 32 parts by weight of a hardening agent.
- The composition as claimed in claim 33, wherein the silica sol employs at least one of a first silica sol with a particle size of 10 to 50㎚, a second silica sol with a particle size of 100 to 200㎚, and a third silica sol with a particle size of 200 to 300㎚.
- The composition as claimed in claim 34, wherein the silica sol has a composition ratio of 2:1:1.
- The composition as claimed in claim 33, wherein the alcohol comprises aliphatic alcohol.
- The composition as claimed in claim 33, wherein the additive comprises K and Na.
- The composition as claimed in claim 33, wherein the hardening agent comprises silane.
- The composition as claimed in claim 33, wherein the filling is a mixture comprising at least one kind selected from the group including Si, Sic, B, Al, In and Ga.
- The composition as claimed in claim 33, wherein the filling is a mixture comprising at least one kind selected from the group including Si, Sb, P and As.
- The composition as claimed in claim 33, wherein the filling is a mixture comprising at least one kind selected from the group including SiO2, TiO2, ZrO2, Al2O3, CoO, MnO, Fe2O3, AlN, Si3N4, B4C, C and BN.
- A method of manufacturing a heating plate for kitchen use, the heating plate comprising an amorphous ceramic, the method comprising the steps of:preparing a coating agent by ball-milling 24 to 56 parts by weight of silica sol, 11 to 30 parts by weight of alcohol, 0.2 to 27 parts by weight of a filling, and 0.5 to 5.0 parts by weight of porous ceramic, and adding 15 to 32 parts by weight of a hardening agent and 0.1 to 0.2 parts by weight of an additive; coating the coating agent on the heating plate for kitchen use, followed by firing at 100 to 350℃ and cooling the fired heating plate at 10~30℃/sec.
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| CN201180038812XA CN103025682A (en) | 2010-08-06 | 2011-08-01 | A plate comprising an amorphous ceramic coating layer, its use and method of manufacturing the same |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020100075972A KR101030150B1 (en) | 2010-08-06 | 2010-08-06 | A plate comprising amorphous ceramic coating layer, its use and method of manufacturing the same |
| KR10-2010-0075972 | 2010-08-06 |
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| KR (1) | KR101030150B1 (en) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015069050A1 (en) * | 2013-11-07 | 2015-05-14 | Hanpoong Fine Ceramics Co., Ltd. | Reversible color changeable coating composition and preparation method thereof |
| CN115074034A (en) * | 2022-06-24 | 2022-09-20 | 华中科技大学 | Adhesive for additive manufacturing of ceramic parts and adhesive method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102542012B1 (en) * | 2020-08-28 | 2023-06-12 | 한국과학기술연구원 | Method for forming high heat resistant coating film using liquid ceramic composition and high heat resistant coating film prepared thereby |
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| KR20070002112A (en) * | 2005-06-30 | 2007-01-05 | 대영케미칼(주) | Marble coating method |
| KR20100037153A (en) * | 2005-08-26 | 2010-04-08 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Coating compositions exhibiting corrosion resistance properties, related coated substrates, and methods |
| KR20090006695A (en) * | 2007-07-12 | 2009-01-15 | 김준형 | The ceramic coating agent for metal face and ceramic coating method of metal face using it |
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| WO2015069050A1 (en) * | 2013-11-07 | 2015-05-14 | Hanpoong Fine Ceramics Co., Ltd. | Reversible color changeable coating composition and preparation method thereof |
| US20160264790A1 (en) * | 2013-11-07 | 2016-09-15 | Seb S.A. | Reversible Color Changeable Coating Composition and Preparation Method Thereof |
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| CN115074034A (en) * | 2022-06-24 | 2022-09-20 | 华中科技大学 | Adhesive for additive manufacturing of ceramic parts and adhesive method |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012018201A3 (en) | 2012-05-03 |
| KR101030150B1 (en) | 2011-04-18 |
| CN103025682A (en) | 2013-04-03 |
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