WO2000009457A2 - Compositions, apparatus and methods for forming coatings of selected color on a substrate and articles produced thereby - Google Patents
Compositions, apparatus and methods for forming coatings of selected color on a substrate and articles produced thereby Download PDFInfo
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- WO2000009457A2 WO2000009457A2 PCT/US1999/018415 US9918415W WO0009457A2 WO 2000009457 A2 WO2000009457 A2 WO 2000009457A2 US 9918415 W US9918415 W US 9918415W WO 0009457 A2 WO0009457 A2 WO 0009457A2
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- WIPO (PCT)
- Prior art keywords
- coating
- substrate
- dispenser
- component
- color
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3694—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer having a composition gradient through its thickness
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/23—Mixtures
Definitions
- the invention relates generally to compositions, apparatus and methods for forming coatings of selected color on a substrate and more particularly varying the components in aqueous suspensions of organometallic compositions and depositing the suspensions onto a glass substrate to pyrolytically produce a stable coating film of selected color or colors on the glass substrate.
- the coating has a graded fade zone on the surface of the substrate, e.g. a float glass ribbon.
- a coating on glass surfaces For example, automotive windshields have coated areas known as “shade bands" or “fade zones". In many passenger vans, the back seat and rear windows are coated with a uniformly thick coating. These coated areas reduce visible, infrared or ultraviolet light transmittance to reduce glare, the visibility of the contents of the vehicle and/or decrease solar energy transmittance to reduce heat gain in the interior of the vehicle.
- the term "fade zone” generally refers to a band adjacent the edge of the transparency e.g. the top edge of an automotive windshield in which the visibility through the transparency changes from a less transparent area to a more transparent area " .
- organometallic salts are dissolved in an organic solution and are sprayed onto a hot glass surface to form a metal oxide film.
- aqueous suspensions of organometallic salts are sprayed onto a hot glass surface to pyrolytically form metal oxide coatings on the surface.
- the presently available coating technology is used to form gray or dark gray coatings, particularly in the automotive industry, so that the coated glass can be used with the widest number of automobile body colors without "clashing" with the automobile body color.
- many of the known coated substrates change color or shade upon subsequent heating during tempering and shaping of the coated substrate. This heat induced color shift makes it difficult to produce coated materials of consistent color stability.
- many of the known coated substrates are not chemically durable e.g. when contacted with solutions having citric acid.
- U.S. Patent No. 2,676,114 discloses the use of a plurality of stationary shields geometrically positioned with respect to a plurality of evaporation coating sources to form a series of adjacent, discrete coating bands of different thicknesses on the substrate.
- a limitation of the technique is the discrete coating bands giving the coated substrate an aesthetically displeasing banded or striped appearance.
- U.S. Patent No. 3,004,875 discloses a plurality of spray guns located above a shield to apply a graded coating to the edge of a substrate.
- the resulting band has a thicker area located remote from the spray guns and a thinner area adjacent the spray guns.
- Limitations of this technology are the device requiring a complex shielded spray arrangement and the resulting band having a mottled appearance due to eddies that evolve beneath the shield near the shield edge during the coating operation.
- U.S. Patent No. 4,138,284 to Postupack discloses applying a dye composition along one edge of a glass substrate.
- the resultant band has a relatively wider area of substantially uniform thickness with a narrow, graded boundary portion located between the coated and uncoated portions of the substrate.
- coating (s) of selected transmitted color onto the surface of a substrate which reduce or eliminate the limitations associated with presently known compositions and methods.
- This invention related to a method for forming a coating, e.g., a copper and manganese containing coating, of a desired color on a substrate, e.g., a glass substrate by applying a copper containing component and a manganese containing component onto the substrate in a selected ratio to form the coating having the selected ratio of copper to manganese. More particularly, when the ratio of copper - containing component and the manganese containing component is one, the coating is blue in transmission. When the ratio of the copper containing component and the manganese containing component is less than about one, the color varies from gray blue to amber in transmission as the ratio decreases. When the ratio of the copper containing component and the manganese containing component is greater than about one, the color varies from gray blue to brown in transmission as the ratio increases .
- the invention further relates to compositions for forming coatings of a selected color on a substrate.
- Copper and manganese containing coatings may be used to form coatings ranging from amber to blue to light brown depending upon the copper to manganese ratio.
- a chromium, copper and manganese system provides a neutral gray colored coating in transmittance.
- Cobalt may be added to this copper and manganese system to increase chemical durability e.g. the citric acid durability of the coating.
- An iron oxide system provides a golden colored coating in transmittance. Copper may be added to this iron oxide system to provide a light grayish-brown colored coating in transmittance. Chromium may be added to the copper iron oxide system to provide a darker grayish-brown colored coating in transmission.
- a manganic oxide (Mn 2 0 3 ) coating provides a mauve/lavender colored coating while a film having an (Mn ++ ) (Mn" ++ ) 2 0 4 phase provides a light amber colored film.
- (Mn ++ ) (Mn +++ ) 2 0 ⁇ will be referred to as "Mn 3 0 4 ".
- the invention still further relates to a method of preventing color shifting of a multi-component or multi-layer coated substrate upon subsequent heat treatment includes the steps of determining the most mobile species in a layer of the coating and placing a concentration gradient layer of an oxide of that mobile species between the substrate, e.g., a glass sheet, and the coating.
- the concentration gradient layer is preferably applied directly on the glass substrate but may also be applied on a coating layer formed on the glass substrate. Upon subsequent heat treatmen-, the mobile species in the concentration gradient layer diffuses into the substrate more readily than the mobile species in the coating, which minimizes depletion of the mobile species from the coating and reduces or eliminates an increase in transmittance .
- This invention further relates to an apparatus for forming a graded coating on a surface of a substrate, for example a piece of glass.
- the apparatus includes a coating station and facilitates for moving the glass piece relative to one another.
- the coating station includes a coating dispenser mounted, preferably pivotally mounted, on a first support.
- An exhaust hood is mounted on one or both sides of the coating dispenser.
- a source of coating material and a source of pressurized fluid are in flow communication with the coating dispenser.
- the coating dispenser is mounted relative to the glass moving facilities such that an imaginary axis through the delivery orifice, e.g., the nozzle or center line of the expected coating spray if more than one nozzle is used, of the coating dispenser intersects the glass moving facilities at a predetermined angle such that the coating spray exiting the delivery end of the coating dispenser provides a graded coating on the glass surface.
- the graded coating is thicker near the delivery end of the coating dispenser and thinner farther from the delivery end of the coating dispenser.
- the coating thickness has a uniform decrease as the distance from the delivery end of the coating dispenser or the edge of the glass piece near the coating dispenser increases .
- the apparatus may include a second coating dispenser pivotally mounted on a second support.
- One or both the coating dispensers may be vertically and horizontally movable.
- the apparatus includes a plurality of spaced apart coating dispensers or nozzles positioned in alignment or off-set from one another over the surface of the substrate to be coated.
- Each coating dispenser dispenses a cone or fan-shaped spray, e.g., an elliptical pattern, of coating material onto a surface portion of the substrate.
- the coated area from one nozzle overlaps a coated area from another nozzle to form a coating having a substantially uniformly thick center region with graded regions located on each side of the center region.
- the invention further relates to a method of forming a fade zone on a surface of the substrate by positioning a coating dispenser adjacent a side of the substrate and angling the coating dispenser toward the opposite side of the substrate such that coating material dispensed from the coating dispenser is deposited onto the substrate as a graded fade zone.
- a coating dispenser adjacent a side of the substrate and angling the coating dispenser toward the opposite side of the substrate such that coating material dispensed from the coating dispenser is deposited onto the substrate as a graded fade zone.
- an organometallic material which pyrolytically forms a coating is used.
- the invention relates to an article of manufacture, e.g. an architectural window or an automotive transparency made using the above methods and apparatus.
- Fig. 1 is an isometric view of a coating station embodying features of the invention
- Fig. 2 is an isometric view of an alternative embodiment of the coating station of the invention
- Fig. 3 is a block diagram of a float glass making apparatus having a coating station of the invention
- Fig. 4 is a side, sectional view of a substrate coated by the coating station of the invention to form a graded fade zone;
- Fig. 5 is a bottom view of a CVD coater incorporating the teachings of the invention.
- Fig. 6 is a perspective view of an additional coating apparatus embodiment of the invention.
- Fig. 7 is a plan view of a coating pattern formed by the apparatus shown in Fig. 6;
- Fig. 8 is an end, sectional view of a substrate coated by the coating apparatus of Fig. 6;
- Figs. 9 and 10 are graphs of the percent reflectance and transmittance across the width of coated glass pieces produced by the coating apparatus of Fig. 6; and
- Fig. 11 is an isometric view of a vehicle having windows formed by glass substrates coated in accordance with the invention.
- Fig. 12 is a plan view of the Samples Al through A14 of Table I.
- embodiments of the invention include coating compositions and methods which can be used to form a coating of a selected transmitted color or colors on a glass substrate. These compositions and methods may be used with conventional coating devices, such as but not limited to, conventional chemical vapor deposition (CVD) , PVD, MSVD or pyrolytic coating devices. Examples of such conventional coating devices are disclosed in U.S. Patent Nos. 2,676,114; 3,004,875 and 4,138,284, the disclosures of which are herein incorporated by reference.
- the coating apparatus 10 includes a coating station 14 for depositing a graded coating on a substrate.
- the graded coating of the invention is represented by spaced lines of decreasing thickness. However, it is to be understood that this representation is symbolic only, and in actuality the coating of the invention has a non-banded, graded appearance.
- a pyrolytic coating is deposited on a heated substrate. Therefore, in the following discussion, a heated chamber, e.g., furnace 12, and a conveyor 16 are utilized with the coating station 14.
- the conveyor 16 extends from the furnace 12 through the coating station 14 and is configured to transport a substrate 18, e.g., a piece of flat glass to be coated, from the furnace 12 through the coating station 14 at a selected speed.
- the conveyor 16 can be of any conventional type, such as a plurality of rotatable metal or ceramic rolls.
- the furnace 12 may be a flat glass forming chamber of the type known in the art where molten glass moves on a metal bath and formed to provide a flat glass ribbon.
- the conveyor 16 may be the conveyor moving the glass ribbon from the forming chamber to an annealing lehr of the type used in the art to anneal the flat glass ribbon.
- the coating station 14 includes a coating dispenser 20, such as a conventional air-atomizing Binks-Sames Model 95 spray nozzle.
- the coating dispenser 20 is configured to spray an atomized liquid material in a fan or cone-shaped pattern toward a surface of the substrate 18 in the coating station 14.
- the coating dispenser 20 is in flow communication with a source 22 of coating material, preferably an aqueous suspension of one or more metal acetylacetonates or other conventional coating materials, by a flexible conduit 24.
- Suitable coating materials are disclosed, for example, in U.S. Patent No. 4,719,127 to Greenberg, which disclosure is herein incorporated by reference.
- the coating dispenser 20 is also in flow communication with a source 28 of compressed fluid, such as air, by a flexible conduit 30.
- the coating dispenser 20 is preferably mounted for pivotal, lateral and vertical movement in any usual manner on a support 34, such as a metal frame.
- the coating dispenser 20 is mounted relative to the glass piece to be coated or the supporting surface of the conveyor 16 such that an angle ⁇ (shown only in Fig. 1) of between about 0-90°, preferably between about 20-40°, is formed between an imaginary axis or line L drawn through the center ' of the spray emitting from the nozzle or discharge end of the coating dispenser 20 and a vertical axis V extending substantially perpendicular to the supporting surface or the surface of the substrate 18 being coated.
- the coating dispenser 20 is also vertically and horizontally movable such that the height of the coating dispenser 20 above the conveyor 16 as well as the position of the dispenser 20 along the conveyor 16 and the lateral position of the coating dispenser 20 with respect to the conveyor 16 can be selectively fixed. While only one coating dispenser 20 is shown in Fig. 1, a plurality of such coating dispensers 20 can be located on the first support 34, for example, beside, over or under the first coating dispenser 20.
- a first exhaust hood 40 is located upstream of the coating dispenser 20 with respect to direction of travel of the conveyor 16 as indicated by arrowed line designated by the numeral 41, and a second exhaust hood 42 is located downstream of the coating dispenser 20 with respect to direction of travel of the conveyor 16.
- a temperature sensor 43 such as a conventional infrared thermometer, may be positioned above the conveyor 16 adjacent to the first exhaust hood 40 to sense the temperature of the substrate 18 for pyrolytic coating.
- Each exhaust hood 40 and 42 is in flow communication with a respective exhaust conduit 44 or 45.
- An auxiliary exhaust hood 49 may be located near the far side of the substrate 18 away from the coating dispenser 20 to provide additional exhaust capability.
- a barrier 51 shown in Fig. 2 may be provided and/or the hood 49 may be used. In this manner, the spray from the coating dispenser 20 is not contacted preventing interference with the spray while any randomly airborne coating material will be prevented from being carried and deposited on the portion of the glass forthwith from the coating dispenser 20.
- the coating apparatus 100 includes a second coating station
- a second coating dispenser 120 pivotally mounted on a second support 134.
- a third exhaust hood 47 is located downstream of the second exhaust hood 42.
- auxiliary exhaust hood 49 as shown in Fig. 1 may also be located in the first and second coating stations 14 and 114 respectively.
- the second support 134 is laterally spaced from the first support 34 so that the second coating dispenser 120 is located between the second and third exhaust hoods 42 and 47.
- additional coating dispensers 121 may be located at the second coating station 114, for example, beside, over or under the second coating dispenser 120. In both the apparatus 10 and 100, no shield or deflector is located between the spray from the coating dispensers and the object being coated.
- the second coating dispenser 120 may be in flow communication with the source 28 of compressed fluid and the source 22 of coating material of the first coating dispenser 20 to spray the same coating material onto the substrate -18.
- the second coating dispenser 120 may be in flow communication with a separate source 128 of compressed fluid by a conduit 130 and a separate source 122 of coating material by a conduit 124 having a metering pump 126 to spray the same or a different coating onto the substrate 18.
- the additional coating dispenser 121 may similarly be in flow communication with the same or different sources of compressed fluid and coating material as the coating dispensers 20 and 120.
- Fig. 3 shows a conventional float glass system 46 embodying features of the invention.
- a conventional float glass system 46 includes a furnace 48 in which molten glass is formed. The molten glass is then transferred onto a molten metal bath contained in a forming chamber 50 to form a glass ribbon on the metal bath surface. The glass ribbon exits the chamber 50 and moves into an annealing lehr 52 by way of a conveyor 54.
- a coating station e.g., coating station 14 of Fig. 1 or the tandem coating station 100 of Fig. 2, can be positioned between the chamber 50 and the annealing lehr 52.
- the heating chamber, or furnace 12 of Fig. 1 may be considered the chamber 50 of Fig. 3 for a continuous piece of glass, e.g., a glass ribbon, or as a conventional furnace for individual glass pieces.
- a continuous substrate, e.g., a glass ribbon, or discrete substrates 18 to be coated, such as pieces of flat glass, are heated to a desired temperature in the chamber 50 or the furnace 12, respectively.
- the conveyor 16 transports the heated substrates 18 into the coating station 14.
- the coating dispenser 20 is selectively positioned at a desired height and lateral position, i.e., distance from the side of the conveyor 16, and at an angle ⁇ such that when the substrate 18 is transported through the coating station 1 ⁇ , the coating dispenser 20 directs the coating material onto the upper surface of the substrate 18.
- This positioning of the coating dispenser 20 can be done either manually or automatically by a conventional automated positioning device attached to the coating dispenser 20.
- coating material is moved from the coating material source 22 to the coating dispenser 20 and mixed with compressed air from the compressed fluid source 28 to exit the nozzle of the coating dispenser 20 as a cone-shaped spray pattern of coating material directed toward the hot substrate 18.
- the first and second exhaust hoods 40 and 42 exhaust excess coating material from the coating station 14 to provide an essentially defect or blemish free uniform coating.
- the auxiliary exhaust hood 49 may also be used to further enhance the exhaust from the coating station 14.
- a barrier 51 shown in Fig. 2 may be used.
- the coating dispenser 20 sprays the coating material onto the top of the hot substrate 18, where the coating material pyrolyzes to form a substantially durable graded pyrolytic coating.
- the size of the spray fan as measured at the glass surface, the speed of the conveyor 16 and the distance between the nozzle of the coating dispenser 20 and the substrate 18 are fixed such that the spray pattern forms a desired coating distribution or grade on top of the substrate 18.
- Coating pressures and volumes through the coating dispenser 20 are selectively controlled to deposit a desired coating gradient and thickness on the surface of the substrate 18.
- the coating dispenser 20 is angled toward the far side of the substrate 18, a thicker layer of the coating material is deposited on the near side of the substrate 18, i.e., the side of the substrate closest to the coating dispenser 20, and the thickness of the coating material deposited on the substrate 18 decreases as the distance from the opposite edge of the substrate (the edge furthermost from the coating dispenser) decreases, with a substantially continuous thickness gradient occurring therebetween, i.e., as the distance from the coating dispenser 20 increases, the coating thickness decreases.
- a smooth, substantially continuously graded coating material 60 is applied across a desired width of the upper surface of the substrate 18.
- the resulting coating forms a smooth, continuous gradient on the substrate 62 without the banding or mottling limitations common with prior art coating devices. Also, by using a pyrolytic coating material rather than the dyes common in the prior art, the resulting coated substrate of the invention can be directly utilized, e.g., as an automotive transparency, without the need for additional protective measures such as protective overcoats or lamination generally required for the dye coated substrates of the prior art.
- the coating system parameters may affect the resulting coating. For example, all else remaining equal, the faster the substrate 18 is moved through the coating station, the thinner will be the overall thickness of the coating. The larger the angle, the thinner will be the coating near the coating dispenser 20 and the thicker will be the coating farther away from the coating dispenser 20. As the distance of the coating dispenser 20 above the substrate 18 increases, the thinner will be the overall coating. The larger the flow rate of coating material through the coating dispenser 20, the thicker will be the overall coating.
- Example #1 Pieces or substrates of flat glass (commercially available from PPG Industries, Inc. of Pittsburgh, Pennsylvania, under the registered trademark SOLARBRONZE®) approximately 0.157 inch (4.0 mm) thick, 24 inches (60.1 " cm) wide and 30 inches (76.2 cm) long were coated with the coating station of the invention shown in Fig. 1.
- the substrates were washed with a dilute detergent solution, rinsed with distilled water and then air dried.
- the cleaned glass substrates were heated in an electric horizontal roller hearth furnace with a furnace temperature of about 1150°F (621°C) .
- the heated substrates were transported by the conveyor from the furnace through the coating station at a line speed of about 250 inches (635 cm) per minute.
- the temperature of the substrates entering the coating station was about 1135-1139°F (613- 615°C) , as measured by the infrared thermometer 43 positioned above the conveyor just upstream of the first exhaust hood 40.
- the coating material used was an aqueous suspension of a mixture of finely ground metal acetylacetonates mixed in water at 16.5 wt% and having a specific gravity of 1.025 measured at 72°F (22°C) .
- the metal acetylacetonate mixture consisted of 95 wt% Co(C 5 H 7 0 2 ) 3 hereinafter referred to as "cobaltic acetylacetonate” and 5 wt% Fe (C 5 H 7 0 2 ) 3 hereinafter referred to as “ferric acetylacetonate” .
- the aqueous suspension was placed in a container having an impeller type mixer operated at 352 rpm to maintain the suspension.
- the liquid suspension was delivered to the spray nozzle by a laboratory peristaltic metering pump (Cole-Parmer MasterFlex 07523-20) at a rate of 85 milliliters per minute.
- the spray nozzle was a conventional air-atomizing type (Binks-Sames model 95) and compressed air was utilized at a pressure of 50 lbs. per square inch, gauge (3.5 kg/sq. cm) .
- the spray nozzle was laterally positioned about 7 inches (17.8 cm) from the near side of the substrate and was vertically positioned about 11 inches (27.9 cm) above the surface of the glass substrate to be coated.
- the spray nozzle was angled such that a centerline of the nozzle intersected the top of the substrate at an angle ⁇ of about 25°. This arrangement produced a graduated, substantially bronze colored fade zone on the glass substrate.
- a number of coating stations 14, 114 may be located in series to apply the same or a different coating material onto the substrate 18 at each coating station 14, 114.
- CVD coaters for vapor depositing a coating
- CVD coaters are usually located above a moving substrate.
- the coating block includes delivery slots through which coating material is discharged and one or more exhaust slots positioned transversely to a direction of movement of the substrate.
- a bottom 138 of a CVD type coating block 140 incorporating the principles of the present invention is shown in Fig.
- the CVD coating block 140 may have at least one tapered coating delivery slot 142, tapering from a narrower width at one end to a wider width at the other end, through which a coating material may be directed in conventional manner toward the surface of a substrate moving in the direction of arrow X under the coating block 140.
- Exhaust slots 144 are located on each side of the delivery slot 142.
- the exhaust slots 144 may be of uniform width as shown in Fig. 5 or may be tapered, e.g., in similar manner to the delivery slot 142.
- the delivery slot 142 may be of uniform width and the exhaust slots 144 tapered. A thicker coating will be applied to the substrate surface under the narrower portion of the delivery slot 142 than under the wider portion of the delivery slot 142, with a graded coating thickness being deposited therebetween.
- Fig. 6 shows a further embodiment of a coating station 148 of the invention.
- the coating station 148 has a first exhaust hood 40 spaced from a second exhaust hood 42 with a plurality of staggered, spaced apart coating dispensers 200, e.g., conventional air atomizing spray nozzles, located therebetween.
- three such coating dispensers 200 are shown.
- the coating dispensers 200 are preferably movably or pivotally mounted on a stationary frame above a conveyor 16 used to transport a substrate 18 to be coated into the coating station 148.
- the coating dispensers 200 could alternatively be mounted on a movable frame or gantry to move the coating dispensers 200 relative to the substrate 18.
- the coating dispensers 200 are in flow communication with one or more sources of coating material and/or pressurized fluid.
- the coating dispensers 200 are preferably directed downwardly toward the substrate 18 to form spray patterns, such as elliptical or elongated spray patterns 150, on the substrate 18.
- each elongated pattern 150 has a major axis 152 with a center 154 and an outer periphery or edge 156.
- the coating dispensers 200 are arranged so that the spray pattern from one coating dispenser 200 does not interfere with the spray pattern from another coating dispenser 200.
- the coating dispensers 200 may be arranged in a staggered formation such that the major axes 152 are all substantially parallel and are spaced apart.
- each coating dispenser 200 forms a coated area 158 on the substrate 18 as the substrate 18 moves through the coating station 148.
- the coating dispensers 200 are preferably positioned such that the coated area 158 formed by one coating dispenser 20 does not extend beyond the pattern center 154 of an adjacent coating dispenser 200. Thus, the coated areas 158 overlap to form a coating as shown in Fi-g . 8 having a substantially uniformly thick center region 162 with tapered or graded side regions 164 located at each side of the coating.
- the coated substrate 18 may be cut into two or more pieces. For example, the substrate 18 may be cut in half along a vertical axis Z shown in Fig. 8 to form two separate coated pieces, with each piece having a graded side region 164 or the piece 18 may be cut into three pieces with the center piece having a uniform coating and the outer pieces having the graded region.
- Fig. 9 shows the percent reflectance ("Ri") from the coated surface; percent reflectance ("R 2 ”) from the uncoated surface and percent transmittance for a glass substrate coated in a coating station utilizing the principles of the invention.
- the coating station utilized was similar to the coating station 148 shown in Fig.
- Pieces of flat glass (commercially available from PPG Industries, Inc. of Pittsburgh, Pennsylvania under the registered trademark SOLEXTRA®) approximately 0.157 inch (4.0 mm) thick, 24 inches (60.1 cm) wide and 30 inches (76.2 cm) to 40 inches (101.6 cm) long, were sprayed with an aqueous suspension of a mixture of copper, cobalt and manganese acetylacetonates to pyrolytically deposit a coating onto the glass surface.
- the deposited coating had a maximum thickness of about 400-600 A with tapered regions on each side of the coated glass piece.
- the percent reflectance Ri and R 2 , and percent transmittance were measured at selected positions across the coated glass from one tapered side or edge of the glass toward the other tapered side.
- the "0" position on the abscissa of Fig. 9 corresponds to one edge of the coated glass sheet, e.g., the left side, with the other abscissa positions indicating the distance from that edge at which percent reflectance Ri and R 2 and transmittance values were measured.
- the coating had higher transmittance regions located at the sides of the substrate, i.e.
- the coating had lower reflective Ri and R 2 at the sides of the substrate and a higher reflectance near the middle of the substrate.
- the R ⁇ values were higher at each measurement than the R 2 values.
- Fig. 10 shows the percent reflectance Ri and R 2 and transmissions values for a coating applied similarly as described above but with the sprays from each of two adjacent coating dispensers 200 deposited in a line normal to the edge of the glass such that the adjacent sprays resulted in interference between the .two spray patterns.
- the interference between the two spray patterns from the coating dispensers 200 formed a coating having a heavily mottled, non-uniformly thick center region.
- the reflectance and transmittance percentages were measured using standard C.I.E. Illuminant C, light 2 degree observer.
- a vehicle 210 is generally shown in Fig. 11.
- the vehicle 210 includes a windshield 212, a rear window 214 and side windows 216, 218, and 220. For purposes of discussion, these will be collectively referred to simply as "windows".
- Side windows 216 and 218 are formed from glass coated in accordance with the invention to form a graded fade zone 222 gradually varying from a thinly coated, substantially transparent first region 224 near the bottom to a more thickly coated, less transparent second region 226 near the top.
- the windows are installed in the vehicle 210 with the fade zones 222 oriented vertically, as shown with respect to side windows 216 and 218.
- the fade zone 222 can be oriented horizontally, if so desired.
- the fade zone 222 could also be oriented with the first region 224 at the top of the window, if so desired.
- the fade zone 222 can be formed such that the first region 224 is of a first color and the second region 226 is of a different, second color by applying different coating materials during formation of the fade zone 222 in adjacent coating stations.
- compositions and methods to achieve coatings of selected transmitted color will now be described. These compositions and methods are generally grouped in accordance with the color produced for ease of discussion. However, the particular groupings should not be considered as limiting to the invention.
- Coatings particularly pyrolytically deposited coatings, formed using a suspension having copper containing and manganese containing components are found to provide excellent coatings ranging in transmitted color from amber or light brown to blue-gray to blue, depending upon the molar ratio of copper to manganese in the applied suspensions.
- aqueous suspensions containing a mixture of manganese containing acetylacetonates e.g., Mn(C 5 H 7 0 2 ) 2 hereinafter referred to as "manganous acetylacetonates” or Mn(C 5 H 7 0 2 ) 3 also referred to as "manganic acetylacetonate”
- copper containing acetylacetonates e.g.
- Cu(C 5 H 7 ⁇ 2 ) 2 also referred to as "cupric acetylacetonate" have been found to produce coatings ranging in transmittea color from a light brown with high copper content or an artber color with high manganese content to a blue color as the copper to manganese molar ratio in the coating is one and to a blue-gray color as the molar ratio is slightly greater or less than 1. Changes in colors as the copper to manganese molar ratio increases or decreases are listed in Table I and shown in Fig. 7 which are discussed below in more detail.
- Coated substrates were formed by hand spraying aqueous suspensions of mixed copper and manganese containing acetylacetonates, such as cupric and manganous acetylacetonates, onto clear float glass substrates cut into 4 inch x 4 inch (10.2 cm x 10.2 cm) squares. The substrates were washed with a dilute detergent solution, rinsed with distilled water and then air dried.
- acetylacetonates such as cupric and manganous acetylacetonates
- An aqueous suspension of cupric acetylacetonate Cu(C 5 H 7 0 2 )2 and manganous acetylacetonate Mn(C 5 H 7 0 2 ) 2 was produced by a conventional wet grinding technique and the copper and manganese containing acetylacetonates were mixed in the desired proportions with deionized water and a chemical wetting agent to disperse, deaerate and suspend the metal acetylacetonate particles.
- the substrates were heated in a conventional bench top muffle furnace to a temperature sufficient to ensure pyrolysis of the applied suspensions, e.g., about 600°C and then hand sprayed with a Binks model 95 spray gun equipped with a gravity feed reservoir.
- the range of transmitted and reflected color of the coated substrates, as a function of composition, are shown in Table I and the color of the Samples shown in Fig. 7.
- the reflected and transmitted colors of the coated substrate are set forth in conventional manner using the standard chromaticity coordinates Y,x,y, for illuminant A, 2° observer established by the Commission Internationale de l'Eclairage (CIE) .
- CIE Commission Internationale de l'Eclairage
- the coated substrates were analyzed using X-ray diffraction. Samples A6 to A8 of Table I were found to contain as a majority phase a cubic Cu ⁇ . 4 Mni.
- substrates were prepared and coated as follows.
- the cleaned glass substrates were sprayed with a 50/50 volume percent solution of two-propanol and distilled water, and wiped dry with a cellulose-polyester cloth to remove dirt, unwanted film, fingerprints and/or debris.
- Aqueous suspensions of cupric acetylacetonate and manganic acetylacetonate were provided by conventional wet grinding techniques.
- films having a higher Cu/Mn mole ratio equal to or greater than about 15.13 produced coated substrates having a brown color in transmittance.
- the Cu/Mn mole ratio as determined by XRF in the film decreased, the transmitted color changed from light brown to grayish blue to deep blue to a lighter blue for Sample Nos. B1-B9 of Table II.
- the deep blue-colored coatings of Sample Nos. B6-B8 of Table II in transmission were determined by XRF analysis to contain a majority of a cubic Cu ⁇ . 4 Mn ⁇ . 6 0 spinel- type phase and generally occurred in the range of 0.8 to 1.2 Cu/Mn molar ratio in the film, as determined by XRF.
- ⁇ E (FMCII) percent luminous transmittance
- ⁇ E (FMCII) an increase in transmittance which occurs after heat treatment will be referred to herein as "bleaching".
- ⁇ E (FMCII) in Table II is defined as the difference in color of the coated substrate before and after heating.
- ⁇ E (FMCII) is determined in accordance with the conventional formula established by the Colorimetry Committee of the CIE.
- the blue-colored spinel-type phase of Cu ⁇ . 4 Mn ⁇ . 6 0 4 can be produced by using a Cu ( II ) /Mn (II ) acetylacetonate suspension as in Sample Nos . A6-A8 in Table I .
- the same spinel-type phase is observed for the Cu (II) /Mn (III ) acetylacetonate suspension used for samples B6-B8 in Table II.
- Table I does not show the results after heat treatment of Sample Nos. A6-A8, it is expected that these samples bleach in a similar manner as Sample Nos. B6-B8 in Table II.
- a CuO film was sprayed onto the surface of a first heated quartz substrate.
- the substrates were about 600°C when coated.
- a Mn 3 0 4 film was sprayed onto the surface of a second heated quartz substrate. The two substrates were then coupled face to face with portions of the coated surfaces in contact with one another and the remaining portion of the coated surface spaced from one another, i.e., the portions of the coated surface were out of contact with one another.
- the substrates were heated to 650°C for 16.2 hours.
- a portion of the coated surface of the second substrate in direct contact with the CuO film of the coated surface of the first substrate showed a dark blue color as viewed with the unaided eye. This is believed to be due to Cu ions migrating from the CuO film into the Mn 3 0 film to form a dark blue colored coating of Cu 1 . 4 Mn 1 . 6 O 4 spinel-type phase. The corresponding area of the CuO film was much lighter upon heating, indicating a depletion of Cu ions. The portion of the Mn 3 ⁇ 4 film on the second substrate not in contact with the CuO film converted upon heating from amber to a mauve/lavender colored Mn 2 0 3 film-.
- a CuO film was deposited on a heated quartz substrate and an Mn 3 0 film was deposited on a heated glass substrate.
- the two substrates were then coupled face-to-face with portions of the coated surfaces in contact with one another and the remaining portions out of contact with one another.
- the substrates were heated to 650°C for 30 minutes.
- portion of the coated surface of the second substrate in direct contact with the CuO film of the coated surface of the first substrate showed a dark blue color in transmission as viewed with the unaided eye. This is believed to be due to the migration of copper ions from the copper oxide (CuO) film to the Mn 3 0 film to form the dark blue colored Cu ⁇ . 4 Mn ⁇ . 6 0 4 spinel-type phase.
- the corresponding film area on the quartz substrate was very light, indicating a depletion of Cu ions.
- the remaining areas of the films were little changed, indicating that the Cu ions do not easily diffuse into quartz but preferentially diffuse into the Mn 3 0 4 film deposited on the glass substrate to form the dark blue- colored Cu 1 . 4 Mn 1 . 6 O 4 spinel-type phase. This also indicates that Mn ions do not preferentially diffuse into glass or that they diffuse much more slowly than Cu ions.
- a CuO film was deposited on a heated glass substrate and a Mn 3 0 4 film was deposited on a heated quartz substrate. The two substrates were then coupled face to face and heated to 650 °C for 30 minutes. Upon separation, the surfaces of the amber colored Mn 3 0 4 film on quartz out of contact with the copper oxide film on the glass converted to a lavender colored Mn 2 0 3 film. A small portion of the quartz substrate showed a blue colored area, indicating the presence of the dark blue colored Cu 1 . 4 Mn 1 . 6 O 4 spinel-type phase. However, most of the Cu diffused into the glass rather than towards the Mn 3 0 4 film deposited on quartz. Thus, from these experiments, it was concluded that Cu ions are the more mobile species in the
- CuMnO j . system is the main species that must be prevented from diffusing into the glass substrate.
- a single layer oxide coating represented for example as ABCO x for purposes of discussion where A, B and C are metal ions in the coating layer
- A, B and C are metal ions in the coating layer
- B ions for example, diffusing into the glass substrate in exchange for D ions, for example alkali ions
- a thin film of BO x may be deposited between the glass substrate and the ABCO x coating.
- the invention may be practiced with a single layer oxide coating having two or more metal ions.
- the BO x layer provides a sacrificial or concentration gradient layer to prevent such bleaching.
- B ions from this sacrificial layer diffuse into the glass more readily than the B ions from the ABC0 X coating layer.
- the BO x layer acts as a concentration gradient deterrent layer to prevent or slow down B ions from the top coating layer or the ABCO x coating layer from diffusing into the glass substrate. Consequently, B ions in the top coat ABCO x layer diffuse more slowly into the undercoat BO x layer, if at all, and thus minimize the degradation of the ABCO x layer while B ions from the BO x undercoat layer diffuse mostly into the glass and perhaps slightly into the top coat layer.
- the transmitted color of the coated glass can thus be controlled by the thickness and composition of the BO x layer, as well as the thickness and composition of the top coat layer ABCO x .
- the BO x layer is preferably deposited directly on the glass substrate but may also be deposited on another coating layer deposited on the substrate.
- the BO x layer should be deposited to both minimize a color change in the coated glass and also to minimize the diffusion of B ions away from the top coat layer into the glass.
- the thickness of the CuO layer was varied by varying the spray time for applying the copper acetylacetonate suspension onto the glass substrate, i.e., a two second spray time yields a thinner resultant CuO layer than an eight second spray time.
- the thicknesses of the CuO layers range from about 50A for a two second spray time to about 200A for an eight second spray time.
- the invention is not limited to the thickness of the copper oxide layer and thicknesses in the range of 25 Angstroms (A) - 260 A are acceptable in the practice of the invention.
- the thickness of the Cu ⁇ . 4 Mn ⁇ . 6 ⁇ 4 layers was not varied and had a thickness of about 300A.
- the invention is not limited to the thicknesses of the Cu ⁇ . 4 Mn ⁇ . 6 O ⁇ . 4 films and thicknesses in the range of 100A-700A are acceptable.
- the thicknesses of the films of the Samples were determined by spectroscopic ellipsometry .
- the bleaching effect is clearly noted for coatings deposited on glass, e.g. glass made by the float process; however, for coatings deposited on quartz, the bleaching effect is not as pronounced as for glass substrates because there is little to no ion exchange between the quartz substrate and coating because the quartz substrate has ions present in the parts per million thereby reducing ion exchange .
- the two layer system did not give the typical blue color associated with a Cu ⁇ . 4 Mn ⁇ . 6 0 spinel-type phase due to the presence of the light brown colored CuO bottom layer.
- the two layer system was heat treated for 10 minutes at 650°C and compared with a single layer as-deposited and unheated sample having a Cu ⁇ . 4 Mn ⁇ . 6 0 4 spinel-type phase coating. Results of varying the Cu/Mn molar ratio from 0.82 to 1.49 in the top coat with the same CuO bottom layer (the layer close to the glass) and comparing the as-deposited two layer system with the same heat treated two layer systems are shown on Table IV.
- the transmitted color was again blue due to the diffusion of Cu ions from the concentration gradient deterrent CuO layer in the glass, leaving behind a desired Cu ⁇ . 4 n ⁇ . 6 0 4 blue colored spinel-type top layer.
- the change in transmittance (bleaching) ⁇ Y, before and after heat treatment with a two layer system was reduced from 11% to 0.75% for a Cu/Mn ratio of 0.82 and from 6.4% to 0.26% for a Cu/Mn ratio of 1.00 and from 3.4% to -0.32% (darkened after heat treatment) for a Cu/Mn ratio of 1.49.
- the ⁇ E (FMCII) (the color change in Mac Adam Units for the above- mentioned three samples) decreased from 18.1 to 3.4, 17.8 to 3.7 and 15.1 to 4.9 respectively as a result of the presence of the CuO layer on the supported surface of the glass.
- MnCuCr oxide films tend to be neutral gray.
- a suspension of a copper containing material such as cupric acetylacetonate
- a copper containing material such as cupric acetylacetonate
- a manganese containing material such as manganous or manganic acetylacetonate
- Manganous or manganic acetylacetonate may be first sprayed onto the substrate, followed by a separate coating of cupric acetylacetonate.
- the desired color is achieved.
- the temperature of the substrate during coating is not limited to the invention and any temperature at which pyrolysis coating occurs is acceptable, e.g. 400°C and 900°C.
- a binary or tertiary metal acetylacetonate may also be used to deposit the films e.g. A x B y (C 5 H 7 0 2 ) i where A or B are any metal ions e.g. copper or manganese and x,y and 1 are the number of moles to balance the equation for the desired binary acetylacetonate compound.
- compositions of the starting mixture and the resulting films were analyzed by D.C. plasma analysis.
- the films which were blue-gray color in transmittance were found to have a Cu/Mn molar ratio in the range of about one.
- the other compositions were amber in appearance.
- the right column of Table V gives the results of the coating tested in accordance with a conventional ASTM 282- 67 test (STANDARD TEST METHOD FOR ACID RESISTANCE OF ENAMEL, CITRIC ACID SPOT TEST) .
- a "yes" indicates acceptable durability.
- Iron oxide coatings pyrolytically formed on glass generally yield a bronze or gold colored film in transmission and enhance the solar performance of the glass by among other ways absorbing part of the solar spectrum in the visible region reducing the heat load through the glass.
- the iron oxide can be applied to hot glass by spray pyrolysis or by chemical vapor deposition.
- the preferred method is to spray an iron containing material, -such as an aqueous suspension of ferric acetylacetonate, onto the glass to form the iron oxide coating.
- the color of the iron containing chromophore can be changed by adding additional metal ions to form a binary or ternary metal oxide thin film.
- a binary Cu-Fe oxide coating tends to have a light grayish-amber color in transmission when formed on a clear glass substrate.
- a ternary oxide compound formed from materials e.g. acetylacetonates, of Cu, Cr and Fe produces a dark grayish- amber absorbing film on a clear glass substrate.
- compounds having acetylacetonates of cobalt, manganese, aluminum, cerium, calcium, titanium, yttrium, zinc, zirconium and tin may be used to vary the color of the deposited film.
- a problem with typical iron oxide coatings is that they tend to darken upon further heat treatment, such as tempering or bending. This darkening is believed to be caused by an increase in crystallization and grain size produced at the temperatures required for tempering or bending.- ' While, it may be possible to add a barrier layer between the iron oxide and the glass to help prevent such darkening, this darkening can be diminished by adding a selected second component to the iron oxide system, such as, but not limiting to the invention, Ca, Cu, Al, Ce, Mg, Mn, Ti, Y, Zn, Zr.
- a selected second component such as, but not limiting to the invention, Ca, Cu, Al, Ce, Mg, Mn, Ti, Y, Zn, Zr.
- a calcium acetylacetonate suspension was combined with an iron acetylacetonate suspension of different mole ratios and pyrolytically sprayed onto a heated glass substrate to form an iron calcium oxide thin film.
- the substrate was cleaned as previously discussed.
- Two pieces of clear glass 4 inches (10.2 cm) square were sprayed for the time listed in Table VI with the same molar solution listed in Table VI.
- One piece was heat treated.
- the film thicknesses were not measured.
- Sample F2 had a luminous transmittance LT A measured as previously discussed of 66.94%. After heat treatment, LT A was 66.85%, giving a change in LT A of less than 1%.
- Sample FI which is an FeO x film deposited onto the glass piece and subsequently heat treated (650°C, 10 minutes) resulting in the coating darkening with a change in LT A of -7.65% (63.32% transmission before heating and 55.67% transmission after heating) .
- Similar results are shown for Fe-Mg oxide and Fe-Zr oxide (Samples F4-F6) where the binary metal oxide changes much less in luminous transmittance than does the single metal oxide FeO x (FI) .
- Mauve/lavender colored films in transmission can be produced by Mn 2 0 3 oxide films formed on a clear glass substrate.
- An Mn 3 0 oxide film formed on a clear glass or quartz substrate produces a light amber color in transmission.
- This amber colored film can be transformed into a mauve/lavender colored film by heating, such as by heating the coated substrate to 650°C for 8-30 minutes.
- a silicon containing barrier layer can be used to form a more uniform color.
- a silicon oxide layer may first be deposited onto the clear float glass substrate before spraying the manganese containing acetylacetonate suspension onto the clear float glass.
- the silicon containing layer can be as thin as 20 nanometers.
- This mauve/lavender colored coating in transmittance has been found to contain mostly Mn 2 0 3 by X-ray diffraction.
- the mauve/lavender coating was tested for citric acid resistant per the above mentioned ASTM 282-67 test and found to be citric acid durable.
- Co-Mn Oxide systems Co (II), Co (III), Mn(II), Mn(III), combinations in suspension)may be used in the practice of the invention.
- Two systems used were a Co (II) /Mn (II) system and a Co (III ) /Mn (II ) system. These systems have been found to produce coatings having transmitted colors ranging from brown to gray brown to light green to light yellow-green when viewed in transmittance by the unaided eye under fluorescent lighting conditions as the Co to Mn molar ratio in suspension is varied from 9.0 - 0.1 (See Table VII) .
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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EP99941109A EP1119525A2 (en) | 1998-08-13 | 1999-08-11 | Compositions, apparatus and methods for forming coatings of selected color on a substrate and articles produced thereby |
CA002340044A CA2340044A1 (en) | 1998-08-13 | 1999-08-11 | Compositions, apparatus and methods for forming coatings of selected color on a substrate and articles produced thereby |
AU54826/99A AU748247B2 (en) | 1998-08-13 | 1999-08-11 | Compositions, apparatus and methods for forming coatings of selected color on a substrate and articles produced thereby |
BR9914310-0A BR9914310A (en) | 1998-08-13 | 1999-08-11 | Compositions, apparatus and methods for forming coatings of selected color on a substrate and articles thus produced |
KR1020017001895A KR20010079644A (en) | 1998-08-13 | 1999-08-11 | Compositions, apparatus and methods for forming coatings of selected color on a sustrate and articles produced thereby |
JP2000564912A JP2002522347A (en) | 1998-08-13 | 1999-08-11 | Compositions, apparatus, methods, and articles made thereby for forming a selected color coating on a substrate |
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US09/270,702 US6649214B2 (en) | 1997-12-18 | 1999-03-17 | Compositions and methods for forming coatings of selected color on a substrate and articles produced thereby |
US09/270,702 | 1999-03-17 |
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US6805960B1 (en) * | 1999-06-08 | 2004-10-19 | Turkiye Sise Ve Cam Fabrikalari | Thermostable glazing |
EP2733127A4 (en) * | 2011-07-12 | 2015-09-09 | Asahi Glass Co Ltd | Method for manufacturing layered-film-bearing glass substrate |
JP2014185036A (en) * | 2011-07-12 | 2014-10-02 | Asahi Glass Co Ltd | Method for manufacturing glass substrate |
DE102012018525A1 (en) * | 2012-09-19 | 2014-03-20 | Fresenius Medical Care Deutschland Gmbh | Device for producing a tack-free gas barrier film with a ceramic barrier layer |
JP6376438B2 (en) * | 2013-05-31 | 2018-08-22 | 日立金属株式会社 | Cu-Mn alloy sputtering target material and method for producing the same |
KR101485980B1 (en) * | 2014-03-03 | 2015-01-27 | 주식회사 기가레인 | Coating Apparatus |
JP2017510397A (en) | 2014-03-06 | 2017-04-13 | ザ プロクター アンド ギャンブル カンパニー | 3D substrate |
WO2017034796A1 (en) | 2015-08-26 | 2017-03-02 | The Procter & Gamble Company | Absorbent articles having three-dimensional substrates and indicia |
WO2018000410A1 (en) | 2016-07-01 | 2018-01-04 | The Procter & Gamble Company | Absorbent articles with improved topsheet dryness |
DE102016014943A1 (en) | 2016-12-14 | 2018-06-14 | Dürr Systems Ag | Printhead with tempering device |
DE102016014944A1 (en) | 2016-12-14 | 2018-06-14 | Dürr Systems Ag | Coating method and corresponding coating device |
DE102016014919A1 (en) * | 2016-12-14 | 2018-06-14 | Dürr Systems Ag | Application device and method for applying a coating agent |
DE102016014952A1 (en) | 2016-12-14 | 2018-06-14 | Dürr Systems Ag | Coating device for coating components |
DE102016014956A1 (en) | 2016-12-14 | 2018-06-14 | Dürr Systems Ag | Coating device and associated operating method |
DE102016014951A1 (en) | 2016-12-14 | 2018-06-14 | Dürr Systems Ag | Coating device and associated operating method |
DE102016014955A1 (en) | 2016-12-14 | 2018-06-14 | Dürr Systems Ag | Coating device and corresponding coating method |
DE102016014948A1 (en) | 2016-12-14 | 2018-06-14 | Dürr Systems Ag | Printhead and related operating procedures |
DE102016014947A1 (en) | 2016-12-14 | 2018-06-14 | Dürr Systems Ag | Printhead for applying a coating agent |
DE102016014946A1 (en) | 2016-12-14 | 2018-06-14 | Dürr Systems Ag | Printhead for applying a coating agent to a component |
DE102019104260A1 (en) * | 2019-02-20 | 2020-08-20 | Stefan Böttger | Method and device for determining a layer thickness of a layer applied to a substrate |
CN117361894B (en) * | 2023-10-23 | 2024-03-26 | 中国耀华玻璃集团有限公司 | Glass rapid coloring and color changing equipment and process method |
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- 1999-08-11 BR BR9914310-0A patent/BR9914310A/en not_active IP Right Cessation
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ID28206A (en) | 2001-05-10 |
AU5482699A (en) | 2000-03-06 |
AU748247B2 (en) | 2002-05-30 |
CN1272270C (en) | 2006-08-30 |
TW200427642A (en) | 2004-12-16 |
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KR20010079644A (en) | 2001-08-22 |
CA2340044A1 (en) | 2000-02-24 |
EP1119525A2 (en) | 2001-08-01 |
WO2000009457A3 (en) | 2000-08-31 |
CN1331661A (en) | 2002-01-16 |
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