CA2002495A1 - Method and apparatus for manufacturing coated flat glass - Google Patents
Method and apparatus for manufacturing coated flat glassInfo
- Publication number
- CA2002495A1 CA2002495A1 CA 2002495 CA2002495A CA2002495A1 CA 2002495 A1 CA2002495 A1 CA 2002495A1 CA 2002495 CA2002495 CA 2002495 CA 2002495 A CA2002495 A CA 2002495A CA 2002495 A1 CA2002495 A1 CA 2002495A1
- Authority
- CA
- Canada
- Prior art keywords
- glass
- ribbon
- bath
- coating
- controlled atmosphere
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
ABSTRACT
A method of and apparatus for manufacturing coated flat glass which includes delivering glass at a controlled rate to a molten metal bath; advancing the glass along the surface of the bath under thermal conditions assuring that a ribbon of glass having an upwardly facing surface is established on the bath; allowing the coated ribbon of glass to sufficiently cool to permit it to be taken undamaged out of the bath; advancing the coated ribbon through an immediately adjacent controlled atmosphere chamber; and applying at least one coating to the upwardly facing surface of the ribbon of glass within the controlled atmosphere chamber.
A method of and apparatus for manufacturing coated flat glass which includes delivering glass at a controlled rate to a molten metal bath; advancing the glass along the surface of the bath under thermal conditions assuring that a ribbon of glass having an upwardly facing surface is established on the bath; allowing the coated ribbon of glass to sufficiently cool to permit it to be taken undamaged out of the bath; advancing the coated ribbon through an immediately adjacent controlled atmosphere chamber; and applying at least one coating to the upwardly facing surface of the ribbon of glass within the controlled atmosphere chamber.
Description
~ - 200249~
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TITLE .~-~
A METHOD AND APPARATUS FOR ~-MANUFACTURING COATED FLAT GLASS ~ ~
. .:
This invention relates to the manufacture of coated flat .
glass. More particularly, the invention relates to the manufacture of flat glass by the float process, for example, ,;
wherein the glass is coated during the manufacture thereof to ::.
10 produce a resultant coated glass product having improved -energy efficiencies and optical properties. - .;
. . .
DESCRIPTION OF THE PRIOR ART ;~
In the float process for flat glass manufacture, molten glass is delivered at a controlled rate onto one end, the hot end, of a molten metal bath contained in an elongate tank structure. Usually, the molten metal bath is of molten tin or a molten tin alloy in which tin predominates. The final ribbon of glass is discharged from the bath by traction ~-means, usually driven traction rollers, often referred to as lift out rollers, disposed beyond the outlet end of the bath, ;~
which traction means applies a tractive force to advance the ;~
ribbon along the path.
It has been found that certain coatings for glass are 25 designed to control the transmission and emission of energy. ~:
For example, metal oxide coatings can be employed to reduce the emissivity of the resultant glass product in respect of infra-red radiation; and to reduce the total energy transmission in respect of solar radiation. The reduction of infra-red radiation emissivity will result in the ability of the coated glass product to conserve heat energy; and the I
reduction of solar radiation will result in the ability of the coated glass product to reduce solar gain and glare.
Also, it has been found that when the coated glass ~ ;
35 products are utilized as a glazing for building construction ~
purposes, the product must be able to be readily handled -- -without fear of scratching or removing the coat'ing, as well ;~
';' ~ 2002495 : .
as have an inherently uniform optical quality free from an undesirable optical effect which would adversely affect the aesthetic appearance of the glass.
It is known that pyrolytic coating processes are desirable from an abrasion resistance standpoint. For example, it is found that pyrolytic coatlngs applied to glass can be more abrasion resistant than the surface of the glass itself. Most of the energy efficient and optically acceptable coatings are applied to the glass subsequent to the manufacture thereof. Typically, the glass is cut into blanks of desired sizes, and the blanks are then coated by vacuum deposition, sputtering, or similar processes without the requirement of additional heating of the glass; or by a spray or a chemical vapor deposition process requiring 15 reheating of the glass. In the coating processes which are ~
temperature dependent, the coating must be applied in a -temperature controlled environment. Obviously, to allow the glass ribbon to cool following its manufacture in order to cut it into blanks of the desired dimensions, and to then reheat the glass blanks to prepare them for the coating, is not energy efficient. Thus, it is believed that the processes of the prior art have been energy inefficient and, in many instances, too expensive to en~oy commercial success.
Accordingly, it is a main ob~ect of the present 25 invention to provide an on-line process for manufacturing a -~
glass product having an abrasion resistant, color-free, energy-efficient coating thereon. ~`
,;".~''',''', '',':
SUMMARY
The present invention provides a method of and apparatus for manufacturing flat glass having an abrasion-resistant, -colorless, energy-efficient coating formed thereon in an on-line procedure as a ribbon of glass is advanced along and removed from a molten metal bath. ;`'~-It has been found that coaters, as of the chemical vapor deposition type, for example, located within the head space ; ~ `~
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over the molten metal bath, remain clean and deposit free since no outside oxygen is present to dilute the precursor, such as metal oxide (tin oxide). Such dilution results in formation of oxidized flakes at the outlet end of the coater which militate against the deposition of a uniform film on the glass surface.
Amongst the problems encountered in coating the glass surface of the ribbon as it emerges from the float bath is that the surrounding air tends to infiltrate lnto the reaction zones in uncontrolled amounts. The rate of infiltration is dependent, among other factors, upon the ~
speed of the glass ribbon, clearance between the outlet of ~ ;
the coater and the ad~acent surface of the glass ribbon, sealing means ad~acent the glass ribbon, and the exhaust flow ~;
15 rate. Such an environment causes the formation of oxidized -:
flakes at the bottom, outlet end of the coater, causing streaking and a non-uniformity in the deposition of the coating on the glass surface. Also, it has been found that ~ ~
the uppermost surface of the glass ribbon loses heat energy -~ ~-as it emerges from the bath, lowering the surface temperature of the glass, and requiring a reduction in deposition speed or a lower rate of deposition. Further, the presence of outside air may result in ignition of the coating precursors.
In order to overcome the aforesaid problems, amongst ` -others, it is the deslderatum of this invention to provide a controlled atmosphere coating section ad~acent the outlet of the bath to assure that the coater mechanism therewithin is bathed in a substantially oxygen-free atmosphere. The controlled atmosphere prevents the formation of undesirable oxidized material thereon and reduces the amount of heat energy lost by the top surface of the transient glass ribbon, thereby increasing the deposition efficiency and enhancing `
the abrasion-resistant and colorless qualities of the film.
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STATEMENT OF THE INVENTION
In accordance with the present invention there is provided a method of manufacturing coated glass which comprises the steps of: a) delivering molten glass at a controlled rate to a molten metal bath within a tank structure having an enclosed headspace over said molten metal bath; b) advancing the glass along the surface of the bath of molten metal under thermal conditions assuring that a ribbon ---of glass having an upwardly facing surface is established on 10 the bath; c) maintaining a protective atmosphere at a plenum :~
over said ribbon within said enclosed headspace; d) allowing the ribbon of glass to cool sufficiently to be withdrawn ~
undamaged from the bath of molten metal; e) advancing the ~ ::
ribbon from said bath of molten metal on a series of traction ~`~
rolls through an immediately adjacent enclosed controlled atmosphere chamber; and f) applying at least one coating to the upwardly facing surface of the ribbon of glass advancing on said rolls within said adjacent controlled atmosphere chamber Also in accordance with the present invention, there is :. .
provided an apparatus for depositing at least one layer of `~
coating material on the upper surface of a ribbon of float ::~
glass comprising, an elongated tank structure having inlet and outlet ends and containing a bath of molten metal, an 25 enclosure over said tank structure defining a headspace .~:-within which a plenum of protective atmosphere is maintained, :::
means delivering molten glass to the bath at said inlet end -and advancing the glass along the surface of the bath to said - .
outlet end under thermal conditions assuring that a ribbon of ~:
glass having an upwardly facing surface is formed.on the bath, a plurality of traction rolls mounted adjacent said outlet end outside said enclosure for receiving and conveying .
said ribbon from said bath, an enclosed controlled atmosphere :-:
chamber contiguous with said tank structure and enclosure and 35 enveloping said traction rolls, and coating means within said .;.;~
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controlled atmosphere chamber for depositing at least one of said layers on said ribbon on said traction rolls. ;
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
Fig. 1 is a central longitudinal sectional elevation of apparatus embodying the invention, comprising a tank structure for a bath of molten metal and a superimposed roof structure, in which apparatus molten glass delivered to the bath is withdrawn in ribbon form;
Fig. 2 is a top plan view of the tank structure of the apparatus illustrated in Fig. l;
Fig. 3 is a transverse sectional view taken along line 3-3 of Fig. l;
Fig. 4 is a central longitudinal sectional elevational view of a controlled atmosphere chamber ad;acent the outlet ~;
end of the apparatus illustrated in Figs. 1 through 3; and ~-~
Fig. 5 is a schematic vertical sectional view of one of the coaters disposed in the controlled atmosphere chamber.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The drawings illustrate a preferred form of the apparatus according to the invention for use in applying a uniform coating to the upper surface of a ribbon of float glass. Thus, in accordance with the invention one or more coating stations are disposed within a controlled atmosphere chamber contiguous with the outlet end of the bath of molten metal and enclosing the rolls immediately ad~acent the tank structure by which the ribbon is removed from the molten metal.
Referring initially to the construction of the apparatus illustrated in Figs. 1 to 3, inclusive, molten glass 10 is ~;
delivered in a conventional manner from a melting tank (not ~
shown) along a canal 12 which terminates in a spout having -opposite side ~ambs 14 and a spout lip 16. The flow of molten glass to the spout, usually soda-lime-silica glass, is 6 :
controlled by a regulating gate or tweel 18. The spout extends over an inlet end wall 20 of a tank structure including a floor 22, an outlet end wall 24, and associated side walls 26.
The tank structure contains a bath of molten metal 28, usually molten tin or an alloy in which tin predominates.
The molten glass 10 is adapted to flow as illustrated at 30 over the spout lip 16 onto the surface of the molten metal bath 28 at the inlet of the tank structure. The temperature at the inlet is maintained at a desirable level by heaters 32 mounted beneath a roof structure 34 which is supported over -~
the tank structure and defines a head space 36 above the ` ;~
molten metal bath 28. The roof structure 34 has an inlet end wall 38 which depends downwardly close to the surface of the --;-;
molten metal bath 28 to define an inlet 40 of restricted height. An extension 42 of the roof structure 34 extends up to the tweel or gate 18 to provide and define a chamber in which the spout is enclosed.
The roof structure 34 also has a downwardly extending outlet end wall 44. An outlet 46 for a ribbon of glass 48 ~ `
produced on the molten metal bath 28 is defined between the lower face of the out.let end wall 44 of the roof structure 34 and the upper face of the outlet end wall 24 of the bath. '-Driven traction or lift-out rollers 50 are mounted beyond the outlet 46. The rollers 50 are mounted with their supporting `surface slightly above the level of the upper surface of the ,~
bath end wall 24 so that the ribbon of glass 48 is lifted - - ;
gently from the bath surface for traction discharge hori~ontally away from the outlet 46 onto the rollers 50. `~-~
1 A protective atmosphere comprised, for example, ~
primarily of nitrogen with a small amount of hydrogen, is j~ , maintained at a plenum in the head space 36 over the bath, being supplied through ducts 52 extending downwardly through the roof structure 34 and connected to a common header 54.
The protective atmosphere flows outwardly through the inlet , ~" ;~,;, i~
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40 to fill the chamber under the extension 42 enclosing the spout.
A temperature gradient is conventionally maintained down the bath from a temperature of about 1000C. at the inlet of 5 the bath 40 to a temperature on the order of 700C. at the ~ ;
outlet end 46 where the ribbon of glass 48 is removed from the bath. At the outlet 46, the glass is thus sufficiently stiffened to be unharmed by contact with the traction or lift ;
out rollers 50~ but still be lifted from the bath surface as illustrated.
The molten glass 10 which flows over the spout lip 16 and onto the bath 28 as at 30, is permitted to flow laterally on the molten metal bath 28 to form a layer 56 of molten glass. The layer 56 is then advanced under thermal and mechanical conditions assuring formation of the ribbon of glass 48 which is cooled and discharged from the bath. The width of the tank structure containing the molten metal bath -~
28 between the side walls 26 is greater than the width of the -ribbon of glass 48. --~
In the embodiment illustrated, there are two coaters or --gas distributor beams 58 and 60 spaced from one another along the path of the ribbon of glass 48 within the tank structure.
The coaters 58 and 60 are employed for supplying coating gases to the surface of the glass ribbon 48 and are located transversely of the path of travel of the ribbon of glass 48 along the bath near the outlet end of the bath as is clearly apparent from an examination of Figs. 1 and 2. A more detailed description of the coaters appears hereinafter.
Mounted outside the discharge end of the tank are the traction or lift out rollers 50. As mentioned hereinbçfore, the rollers are disposed somewhat above the level of the i~
upper surface of the bath end wall 24 and cooperate to apply ~ -a tractive effort to the ribbon of glass 48 moving towards the outlet, which tracti~e effort advances the glass along the bath. The ribbon of glass 48 passes out of the bath into -` - Z002495 and through the controlled atmosphere chamber 70, illustrated in greater detail in Fig. 4, on the rollers 50.
The temperature of the molten metal bath 28 in the tank ` ~
structure is conventionally regulated from the inlet end to ~ `
the discharge end as by providing thermal regulators, not shown, immersed in or extending over the molten metal, and by `~
the heaters 32 mounted in the roof structure 34.
The glass ribbon 48, upon leaving the outlet 46 of the apparatus containing the molten metal bath 28, enters a 10 controlled atmosphere chamber 70 which is defined by an inlet ~ ~;
end wall 72 having an inlet opening 74, a spaced outlet end wall 76 having an outlet opening 78, spaced apart side walls 80, and an sssociated roof 82. Typically, the controlled ;`~
atmosphere chamber 70 also will include a floor member 84, ;~
15 and suitable atmosphere may be provided to the chamber as ~`
deemed appropriate by a duct 85 from a supply (not shown). -All of the above elements cooperate to form the chamber which tends to completely envelope the lift-out or traction rollers 50 and the transient ribbon of glass 48 thereon.
There is provided within the chamber a coater 86, and ' preferably a pair of spaced apart coaters 86 and 86', similar ` -`~
in structure to the coaters 58 and 60 which are disposed within the tank structure containing the molten metal bath 28. Suitable sealing means including seals 90 and 92 are .`~
25 employed to effectively seal the controlled atmosphere ~' chamber 70 by contacting the under surface of the ribbon of ` ``~
glass 48 and the roller 50 ad~acent the outlet opening 78, `~
respectively. The seal members 90 and 92 effectively produce ``~
sufficient sealing means to maintain the desired atmosphere "~
within the chamber 70, and may typically be formed of a graphite material capable of withstanding the temperatures to ;~
which they are exposed. `~
The physical and chemical nature of the reactants used in the chemical vapor deposition processes of the invention dictate that the gases, as well as the surfaces of the coaters 58, 60, 86, and 86', be maintained within a'-.~-,`"'~'..': `
~` 2002495 g . . .
prescribed temperature range or ranges. Such regulation is required because of condensation, premature film deposition, decomposition, and gas phase nucleation (powder formation) which can occur if the environment and the associated temperatures are not correctly maintained. Typically, coaters located within the molten metal bath 28 remain deposit-free since outside oxygen is not present to dilute the precursors used therein. The amount of oxygen used to produce the metal oxide, tin oxide, for example, can be 10 precisely premixed. However, with coaters of the type ;~
described located outside of the molten metal bath 28, it has been found that the surrounding atmosphere air tends to infiltrate the reactor zones in undesirable and uncontrollable quantities, causing deposits to form and the temperature of the upper surface of the emerging ribbon of glass to decrease. The combination results in both non-uniform deposition of the coating and a reduction in the rate of deposit~on of the coating. These problems are obviated by establishment of the controlled atmosphere chamber 70.
In operation, the chamber 70 is preferably maintained at a slightly increased internal pressure compared with the external pressure. Thus, by admitting a suitable atmosphere to the chamber as by the duct 85, the interior atmosphere may -`
comprise a selected composition at a pressure equal to or greater than the external atmosphere so as to preclude infiltration of external atmosphere. Of course, if the atmosphere in the chamber 70 is to be the same as that within the headspace 36, the internal pressure of the chamber 70 may be maintained slightly less than the internal pressure within the,interior of the head space 36 over the molten metal bath 28. The relative pressure conditions will thus result in a flow of the atmosphere from within the head space 36 above -~
the molten metal bath 28 through the outlet 46 to the ~;
controlled atmosphere chamber 70 through inlet opening 74.
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Thus, the atmosphere within the chamber 70 is appropriate to prevent the formation of undesirable oxides and the like on the coaters 86 and 86'. ;~
Also, since the inlet and outlet walls 72 and 76, 5 respectively, the side walls 80, the roof 82, and the floor 84 tend to prevent the dissipation of heat energy, the temperature of the transient ribbon of glass 48 tends to remain within a range suitable for efficient deposition of ~;
the coating material from the coaters 86 and 86'. However, 10 if necessary, additional heat may be provided within the chamber 70 as by heating elements 89.
It will be appreciated that a coating material may be deposited in one or a plurality of layers, or several coating materials may be sequentially deposited in varying ~-combinations, by any or all of the coaters 58, 60, 86 and 86' in accordance with the invention.
By way of example, if it were assumed that it is desired to produce a ribbon of glass containing a colorless, abrasion ` ~-~
resistant, low-E coating in a continuous on-line manner, the .
20 following procedure could be followed. ,~
Initially, the coater 58 positioned over the molten metal bath 28 applies a 250 angstrom thick film of doped tin oxide on ~-the glass ribbon 48, and the coater 60 then applies on the initial -`
coating a supplemental 250 - 280 angstrom thick layer of silica. ~ -~
25 The thus coated glass ribbon 48 exits the molten metal bath 28 and ` =~
enters the controlled atmosphere chamber 70 through the inlet 72, and is caused to travel sequentially under the coaters 86 and 86'.
The coater 86 applies a 1500 angstrom thick layer of tin oxide, ` i `
and the coater 86' applies a 1500 angstrom thick layer of doped --30 tin oxide. Upon completion of the coating process, the coated glass ribbon 48 exits the chamber 70 through the outlet opening 78 and is conveyed into and through an associated temperature controlled lehr (not shown).
The coaters described above are similar in operation to the 35 coater illustrated and described in United States Patent No.
4,504,526 to Hofer et al., entitled APPARATUS AND METHOD FOR
.:, ~ 02495 PRODUCING A LANINAR FLOW OF CONSTANT VELOCITY FLUID ALONG A
SUBSTRATE.
More specifically, the coaters 86 and 86' include, as schematically illustrated in Fig. 5, a vacuum source 91 which ls operative to effectively remove the atmosphere immediately over the ribbon 48 in the direction of the inlet zone of the chamber 70, and an associated down stream source of precursor 93 having an elongated outlet nozzle 94 for producing a laminar flow of precursor of constant velocity over the width of the transient glass ribbon 48. The coaters also include a vacuum source 96 which is operative to remove the atmosphere immediately over the glass ribbon 48 downstream from the precursor source 93. The -source of precursor 93 and associated elongate outlet nozzle 94 thus produce a constant velocity laminar flow of precursor fluid over the width of the transient glass ribbon 48 both upstream and downstream of the precursor source. ; :
It will be appreciated that the selected precursor fluid emitted from the outlet nozzles 94 of the sequentially arranged coaters 86 and 86' will deposit the desired film or films 20 sequentially on the upper surface of the previously formed films, -;
if any, on the glass ribbon 48. Due to the disposition of the 1,, ~ . . ' -respective vacuum sources 91 and 96 of the coaters, the precursor ~ ~-emitted from the outlet nozzle 94 is deposited on the moving -ribbon of glass, and any of the precursor which does not deposit ~ -25 on the ribbon is caused to flow either upstream of the glass -ribbon 48 and be removed from the surface thereof by the vacuum source 91, or downstream with the glass ribbon 48 and be removed therefrom by the vacuum source 96. In the manner explained, a zone of precursor fluid is maintained over the glass ribbon 48 ~
30 under both of the sources of precursor fluid 86 and 86'. By -;
controlling the speed of the glass ribbon 48, the temperature within the chamber 70, the quantity of precursor emitted from the coaters 86 and 86', and/or the associated vacuum sources 91 and -96, the thickness of the deposited layers of the precursors may be 35 controlled. ~.
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It will be appreciated that the process and apparatus herein described are useful in the manufacture of coated glass for various purposes. Of particular importance are coatings designed to reduce the emissivity of coated glass in respect of infrared radiation and those designed to reduce total energy transmissivity of coated glass in respect of solar radiation. .
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TITLE .~-~
A METHOD AND APPARATUS FOR ~-MANUFACTURING COATED FLAT GLASS ~ ~
. .:
This invention relates to the manufacture of coated flat .
glass. More particularly, the invention relates to the manufacture of flat glass by the float process, for example, ,;
wherein the glass is coated during the manufacture thereof to ::.
10 produce a resultant coated glass product having improved -energy efficiencies and optical properties. - .;
. . .
DESCRIPTION OF THE PRIOR ART ;~
In the float process for flat glass manufacture, molten glass is delivered at a controlled rate onto one end, the hot end, of a molten metal bath contained in an elongate tank structure. Usually, the molten metal bath is of molten tin or a molten tin alloy in which tin predominates. The final ribbon of glass is discharged from the bath by traction ~-means, usually driven traction rollers, often referred to as lift out rollers, disposed beyond the outlet end of the bath, ;~
which traction means applies a tractive force to advance the ;~
ribbon along the path.
It has been found that certain coatings for glass are 25 designed to control the transmission and emission of energy. ~:
For example, metal oxide coatings can be employed to reduce the emissivity of the resultant glass product in respect of infra-red radiation; and to reduce the total energy transmission in respect of solar radiation. The reduction of infra-red radiation emissivity will result in the ability of the coated glass product to conserve heat energy; and the I
reduction of solar radiation will result in the ability of the coated glass product to reduce solar gain and glare.
Also, it has been found that when the coated glass ~ ;
35 products are utilized as a glazing for building construction ~
purposes, the product must be able to be readily handled -- -without fear of scratching or removing the coat'ing, as well ;~
';' ~ 2002495 : .
as have an inherently uniform optical quality free from an undesirable optical effect which would adversely affect the aesthetic appearance of the glass.
It is known that pyrolytic coating processes are desirable from an abrasion resistance standpoint. For example, it is found that pyrolytic coatlngs applied to glass can be more abrasion resistant than the surface of the glass itself. Most of the energy efficient and optically acceptable coatings are applied to the glass subsequent to the manufacture thereof. Typically, the glass is cut into blanks of desired sizes, and the blanks are then coated by vacuum deposition, sputtering, or similar processes without the requirement of additional heating of the glass; or by a spray or a chemical vapor deposition process requiring 15 reheating of the glass. In the coating processes which are ~
temperature dependent, the coating must be applied in a -temperature controlled environment. Obviously, to allow the glass ribbon to cool following its manufacture in order to cut it into blanks of the desired dimensions, and to then reheat the glass blanks to prepare them for the coating, is not energy efficient. Thus, it is believed that the processes of the prior art have been energy inefficient and, in many instances, too expensive to en~oy commercial success.
Accordingly, it is a main ob~ect of the present 25 invention to provide an on-line process for manufacturing a -~
glass product having an abrasion resistant, color-free, energy-efficient coating thereon. ~`
,;".~''',''', '',':
SUMMARY
The present invention provides a method of and apparatus for manufacturing flat glass having an abrasion-resistant, -colorless, energy-efficient coating formed thereon in an on-line procedure as a ribbon of glass is advanced along and removed from a molten metal bath. ;`'~-It has been found that coaters, as of the chemical vapor deposition type, for example, located within the head space ; ~ `~
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.--................................................................. :, .
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over the molten metal bath, remain clean and deposit free since no outside oxygen is present to dilute the precursor, such as metal oxide (tin oxide). Such dilution results in formation of oxidized flakes at the outlet end of the coater which militate against the deposition of a uniform film on the glass surface.
Amongst the problems encountered in coating the glass surface of the ribbon as it emerges from the float bath is that the surrounding air tends to infiltrate lnto the reaction zones in uncontrolled amounts. The rate of infiltration is dependent, among other factors, upon the ~
speed of the glass ribbon, clearance between the outlet of ~ ;
the coater and the ad~acent surface of the glass ribbon, sealing means ad~acent the glass ribbon, and the exhaust flow ~;
15 rate. Such an environment causes the formation of oxidized -:
flakes at the bottom, outlet end of the coater, causing streaking and a non-uniformity in the deposition of the coating on the glass surface. Also, it has been found that ~ ~
the uppermost surface of the glass ribbon loses heat energy -~ ~-as it emerges from the bath, lowering the surface temperature of the glass, and requiring a reduction in deposition speed or a lower rate of deposition. Further, the presence of outside air may result in ignition of the coating precursors.
In order to overcome the aforesaid problems, amongst ` -others, it is the deslderatum of this invention to provide a controlled atmosphere coating section ad~acent the outlet of the bath to assure that the coater mechanism therewithin is bathed in a substantially oxygen-free atmosphere. The controlled atmosphere prevents the formation of undesirable oxidized material thereon and reduces the amount of heat energy lost by the top surface of the transient glass ribbon, thereby increasing the deposition efficiency and enhancing `
the abrasion-resistant and colorless qualities of the film.
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STATEMENT OF THE INVENTION
In accordance with the present invention there is provided a method of manufacturing coated glass which comprises the steps of: a) delivering molten glass at a controlled rate to a molten metal bath within a tank structure having an enclosed headspace over said molten metal bath; b) advancing the glass along the surface of the bath of molten metal under thermal conditions assuring that a ribbon ---of glass having an upwardly facing surface is established on 10 the bath; c) maintaining a protective atmosphere at a plenum :~
over said ribbon within said enclosed headspace; d) allowing the ribbon of glass to cool sufficiently to be withdrawn ~
undamaged from the bath of molten metal; e) advancing the ~ ::
ribbon from said bath of molten metal on a series of traction ~`~
rolls through an immediately adjacent enclosed controlled atmosphere chamber; and f) applying at least one coating to the upwardly facing surface of the ribbon of glass advancing on said rolls within said adjacent controlled atmosphere chamber Also in accordance with the present invention, there is :. .
provided an apparatus for depositing at least one layer of `~
coating material on the upper surface of a ribbon of float ::~
glass comprising, an elongated tank structure having inlet and outlet ends and containing a bath of molten metal, an 25 enclosure over said tank structure defining a headspace .~:-within which a plenum of protective atmosphere is maintained, :::
means delivering molten glass to the bath at said inlet end -and advancing the glass along the surface of the bath to said - .
outlet end under thermal conditions assuring that a ribbon of ~:
glass having an upwardly facing surface is formed.on the bath, a plurality of traction rolls mounted adjacent said outlet end outside said enclosure for receiving and conveying .
said ribbon from said bath, an enclosed controlled atmosphere :-:
chamber contiguous with said tank structure and enclosure and 35 enveloping said traction rolls, and coating means within said .;.;~
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controlled atmosphere chamber for depositing at least one of said layers on said ribbon on said traction rolls. ;
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
Fig. 1 is a central longitudinal sectional elevation of apparatus embodying the invention, comprising a tank structure for a bath of molten metal and a superimposed roof structure, in which apparatus molten glass delivered to the bath is withdrawn in ribbon form;
Fig. 2 is a top plan view of the tank structure of the apparatus illustrated in Fig. l;
Fig. 3 is a transverse sectional view taken along line 3-3 of Fig. l;
Fig. 4 is a central longitudinal sectional elevational view of a controlled atmosphere chamber ad;acent the outlet ~;
end of the apparatus illustrated in Figs. 1 through 3; and ~-~
Fig. 5 is a schematic vertical sectional view of one of the coaters disposed in the controlled atmosphere chamber.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The drawings illustrate a preferred form of the apparatus according to the invention for use in applying a uniform coating to the upper surface of a ribbon of float glass. Thus, in accordance with the invention one or more coating stations are disposed within a controlled atmosphere chamber contiguous with the outlet end of the bath of molten metal and enclosing the rolls immediately ad~acent the tank structure by which the ribbon is removed from the molten metal.
Referring initially to the construction of the apparatus illustrated in Figs. 1 to 3, inclusive, molten glass 10 is ~;
delivered in a conventional manner from a melting tank (not ~
shown) along a canal 12 which terminates in a spout having -opposite side ~ambs 14 and a spout lip 16. The flow of molten glass to the spout, usually soda-lime-silica glass, is 6 :
controlled by a regulating gate or tweel 18. The spout extends over an inlet end wall 20 of a tank structure including a floor 22, an outlet end wall 24, and associated side walls 26.
The tank structure contains a bath of molten metal 28, usually molten tin or an alloy in which tin predominates.
The molten glass 10 is adapted to flow as illustrated at 30 over the spout lip 16 onto the surface of the molten metal bath 28 at the inlet of the tank structure. The temperature at the inlet is maintained at a desirable level by heaters 32 mounted beneath a roof structure 34 which is supported over -~
the tank structure and defines a head space 36 above the ` ;~
molten metal bath 28. The roof structure 34 has an inlet end wall 38 which depends downwardly close to the surface of the --;-;
molten metal bath 28 to define an inlet 40 of restricted height. An extension 42 of the roof structure 34 extends up to the tweel or gate 18 to provide and define a chamber in which the spout is enclosed.
The roof structure 34 also has a downwardly extending outlet end wall 44. An outlet 46 for a ribbon of glass 48 ~ `
produced on the molten metal bath 28 is defined between the lower face of the out.let end wall 44 of the roof structure 34 and the upper face of the outlet end wall 24 of the bath. '-Driven traction or lift-out rollers 50 are mounted beyond the outlet 46. The rollers 50 are mounted with their supporting `surface slightly above the level of the upper surface of the ,~
bath end wall 24 so that the ribbon of glass 48 is lifted - - ;
gently from the bath surface for traction discharge hori~ontally away from the outlet 46 onto the rollers 50. `~-~
1 A protective atmosphere comprised, for example, ~
primarily of nitrogen with a small amount of hydrogen, is j~ , maintained at a plenum in the head space 36 over the bath, being supplied through ducts 52 extending downwardly through the roof structure 34 and connected to a common header 54.
The protective atmosphere flows outwardly through the inlet , ~" ;~,;, i~
~- ~oo~
40 to fill the chamber under the extension 42 enclosing the spout.
A temperature gradient is conventionally maintained down the bath from a temperature of about 1000C. at the inlet of 5 the bath 40 to a temperature on the order of 700C. at the ~ ;
outlet end 46 where the ribbon of glass 48 is removed from the bath. At the outlet 46, the glass is thus sufficiently stiffened to be unharmed by contact with the traction or lift ;
out rollers 50~ but still be lifted from the bath surface as illustrated.
The molten glass 10 which flows over the spout lip 16 and onto the bath 28 as at 30, is permitted to flow laterally on the molten metal bath 28 to form a layer 56 of molten glass. The layer 56 is then advanced under thermal and mechanical conditions assuring formation of the ribbon of glass 48 which is cooled and discharged from the bath. The width of the tank structure containing the molten metal bath -~
28 between the side walls 26 is greater than the width of the -ribbon of glass 48. --~
In the embodiment illustrated, there are two coaters or --gas distributor beams 58 and 60 spaced from one another along the path of the ribbon of glass 48 within the tank structure.
The coaters 58 and 60 are employed for supplying coating gases to the surface of the glass ribbon 48 and are located transversely of the path of travel of the ribbon of glass 48 along the bath near the outlet end of the bath as is clearly apparent from an examination of Figs. 1 and 2. A more detailed description of the coaters appears hereinafter.
Mounted outside the discharge end of the tank are the traction or lift out rollers 50. As mentioned hereinbçfore, the rollers are disposed somewhat above the level of the i~
upper surface of the bath end wall 24 and cooperate to apply ~ -a tractive effort to the ribbon of glass 48 moving towards the outlet, which tracti~e effort advances the glass along the bath. The ribbon of glass 48 passes out of the bath into -` - Z002495 and through the controlled atmosphere chamber 70, illustrated in greater detail in Fig. 4, on the rollers 50.
The temperature of the molten metal bath 28 in the tank ` ~
structure is conventionally regulated from the inlet end to ~ `
the discharge end as by providing thermal regulators, not shown, immersed in or extending over the molten metal, and by `~
the heaters 32 mounted in the roof structure 34.
The glass ribbon 48, upon leaving the outlet 46 of the apparatus containing the molten metal bath 28, enters a 10 controlled atmosphere chamber 70 which is defined by an inlet ~ ~;
end wall 72 having an inlet opening 74, a spaced outlet end wall 76 having an outlet opening 78, spaced apart side walls 80, and an sssociated roof 82. Typically, the controlled ;`~
atmosphere chamber 70 also will include a floor member 84, ;~
15 and suitable atmosphere may be provided to the chamber as ~`
deemed appropriate by a duct 85 from a supply (not shown). -All of the above elements cooperate to form the chamber which tends to completely envelope the lift-out or traction rollers 50 and the transient ribbon of glass 48 thereon.
There is provided within the chamber a coater 86, and ' preferably a pair of spaced apart coaters 86 and 86', similar ` -`~
in structure to the coaters 58 and 60 which are disposed within the tank structure containing the molten metal bath 28. Suitable sealing means including seals 90 and 92 are .`~
25 employed to effectively seal the controlled atmosphere ~' chamber 70 by contacting the under surface of the ribbon of ` ``~
glass 48 and the roller 50 ad~acent the outlet opening 78, `~
respectively. The seal members 90 and 92 effectively produce ``~
sufficient sealing means to maintain the desired atmosphere "~
within the chamber 70, and may typically be formed of a graphite material capable of withstanding the temperatures to ;~
which they are exposed. `~
The physical and chemical nature of the reactants used in the chemical vapor deposition processes of the invention dictate that the gases, as well as the surfaces of the coaters 58, 60, 86, and 86', be maintained within a'-.~-,`"'~'..': `
~` 2002495 g . . .
prescribed temperature range or ranges. Such regulation is required because of condensation, premature film deposition, decomposition, and gas phase nucleation (powder formation) which can occur if the environment and the associated temperatures are not correctly maintained. Typically, coaters located within the molten metal bath 28 remain deposit-free since outside oxygen is not present to dilute the precursors used therein. The amount of oxygen used to produce the metal oxide, tin oxide, for example, can be 10 precisely premixed. However, with coaters of the type ;~
described located outside of the molten metal bath 28, it has been found that the surrounding atmosphere air tends to infiltrate the reactor zones in undesirable and uncontrollable quantities, causing deposits to form and the temperature of the upper surface of the emerging ribbon of glass to decrease. The combination results in both non-uniform deposition of the coating and a reduction in the rate of deposit~on of the coating. These problems are obviated by establishment of the controlled atmosphere chamber 70.
In operation, the chamber 70 is preferably maintained at a slightly increased internal pressure compared with the external pressure. Thus, by admitting a suitable atmosphere to the chamber as by the duct 85, the interior atmosphere may -`
comprise a selected composition at a pressure equal to or greater than the external atmosphere so as to preclude infiltration of external atmosphere. Of course, if the atmosphere in the chamber 70 is to be the same as that within the headspace 36, the internal pressure of the chamber 70 may be maintained slightly less than the internal pressure within the,interior of the head space 36 over the molten metal bath 28. The relative pressure conditions will thus result in a flow of the atmosphere from within the head space 36 above -~
the molten metal bath 28 through the outlet 46 to the ~;
controlled atmosphere chamber 70 through inlet opening 74.
:'~
,, :.;, ~' ': ~' " 200z4g~
Thus, the atmosphere within the chamber 70 is appropriate to prevent the formation of undesirable oxides and the like on the coaters 86 and 86'. ;~
Also, since the inlet and outlet walls 72 and 76, 5 respectively, the side walls 80, the roof 82, and the floor 84 tend to prevent the dissipation of heat energy, the temperature of the transient ribbon of glass 48 tends to remain within a range suitable for efficient deposition of ~;
the coating material from the coaters 86 and 86'. However, 10 if necessary, additional heat may be provided within the chamber 70 as by heating elements 89.
It will be appreciated that a coating material may be deposited in one or a plurality of layers, or several coating materials may be sequentially deposited in varying ~-combinations, by any or all of the coaters 58, 60, 86 and 86' in accordance with the invention.
By way of example, if it were assumed that it is desired to produce a ribbon of glass containing a colorless, abrasion ` ~-~
resistant, low-E coating in a continuous on-line manner, the .
20 following procedure could be followed. ,~
Initially, the coater 58 positioned over the molten metal bath 28 applies a 250 angstrom thick film of doped tin oxide on ~-the glass ribbon 48, and the coater 60 then applies on the initial -`
coating a supplemental 250 - 280 angstrom thick layer of silica. ~ -~
25 The thus coated glass ribbon 48 exits the molten metal bath 28 and ` =~
enters the controlled atmosphere chamber 70 through the inlet 72, and is caused to travel sequentially under the coaters 86 and 86'.
The coater 86 applies a 1500 angstrom thick layer of tin oxide, ` i `
and the coater 86' applies a 1500 angstrom thick layer of doped --30 tin oxide. Upon completion of the coating process, the coated glass ribbon 48 exits the chamber 70 through the outlet opening 78 and is conveyed into and through an associated temperature controlled lehr (not shown).
The coaters described above are similar in operation to the 35 coater illustrated and described in United States Patent No.
4,504,526 to Hofer et al., entitled APPARATUS AND METHOD FOR
.:, ~ 02495 PRODUCING A LANINAR FLOW OF CONSTANT VELOCITY FLUID ALONG A
SUBSTRATE.
More specifically, the coaters 86 and 86' include, as schematically illustrated in Fig. 5, a vacuum source 91 which ls operative to effectively remove the atmosphere immediately over the ribbon 48 in the direction of the inlet zone of the chamber 70, and an associated down stream source of precursor 93 having an elongated outlet nozzle 94 for producing a laminar flow of precursor of constant velocity over the width of the transient glass ribbon 48. The coaters also include a vacuum source 96 which is operative to remove the atmosphere immediately over the glass ribbon 48 downstream from the precursor source 93. The -source of precursor 93 and associated elongate outlet nozzle 94 thus produce a constant velocity laminar flow of precursor fluid over the width of the transient glass ribbon 48 both upstream and downstream of the precursor source. ; :
It will be appreciated that the selected precursor fluid emitted from the outlet nozzles 94 of the sequentially arranged coaters 86 and 86' will deposit the desired film or films 20 sequentially on the upper surface of the previously formed films, -;
if any, on the glass ribbon 48. Due to the disposition of the 1,, ~ . . ' -respective vacuum sources 91 and 96 of the coaters, the precursor ~ ~-emitted from the outlet nozzle 94 is deposited on the moving -ribbon of glass, and any of the precursor which does not deposit ~ -25 on the ribbon is caused to flow either upstream of the glass -ribbon 48 and be removed from the surface thereof by the vacuum source 91, or downstream with the glass ribbon 48 and be removed therefrom by the vacuum source 96. In the manner explained, a zone of precursor fluid is maintained over the glass ribbon 48 ~
30 under both of the sources of precursor fluid 86 and 86'. By -;
controlling the speed of the glass ribbon 48, the temperature within the chamber 70, the quantity of precursor emitted from the coaters 86 and 86', and/or the associated vacuum sources 91 and -96, the thickness of the deposited layers of the precursors may be 35 controlled. ~.
'', :::
Z002495i ~ ~
12 ::
It will be appreciated that the process and apparatus herein described are useful in the manufacture of coated glass for various purposes. Of particular importance are coatings designed to reduce the emissivity of coated glass in respect of infrared radiation and those designed to reduce total energy transmissivity of coated glass in respect of solar radiation. .
.,~ . ., 1 0 . . :, ';```' ;"'~
.. . ~ ,~. .~, .~,, ,-. ,, `;~
., ~. -.
`.~ ~: ,:, .. .
.~; ..',, `.. ,'-. -~,. ,,., ..:-~
~
., .~
,`~;:'. ,.:
, ~ ,.. , .~.
: . . .
.,~
..:,.~,,:, .-:
'''''-~'.'',"'.-,, :, .:::: ,:
,, ' , .:, . . ...
'':~-,' '
Claims (17)
1. A method of manufacturing coated glass which comprises the steps of:
a) delivering molten glass at a controlled rate to a molten metal bath within a tank structure having an enclosed headspace over said molten metal bath;
b) advancing the glass along the surface of the bath of molten metal under thermal conditions assuring that a ribbon of glass having an upwardly facing surface is established on the bath;
c) maintaining a protective atmosphere at a plenum over said ribbon within said enclosed headspace;
d) allowing the ribbon of glass to cool sufficiently to be withdrawn undamaged from the bath of molten metal;
e) advancing the ribbon from said bath of molten metal on a series of traction rolls through an immediately adjacent enclosed controlled atmosphere chamber; and f) applying at least one coating to the upwardly facing surface of the ribbon of glass advancing on said rolls within said adjacent controlled atmosphere chamber.
a) delivering molten glass at a controlled rate to a molten metal bath within a tank structure having an enclosed headspace over said molten metal bath;
b) advancing the glass along the surface of the bath of molten metal under thermal conditions assuring that a ribbon of glass having an upwardly facing surface is established on the bath;
c) maintaining a protective atmosphere at a plenum over said ribbon within said enclosed headspace;
d) allowing the ribbon of glass to cool sufficiently to be withdrawn undamaged from the bath of molten metal;
e) advancing the ribbon from said bath of molten metal on a series of traction rolls through an immediately adjacent enclosed controlled atmosphere chamber; and f) applying at least one coating to the upwardly facing surface of the ribbon of glass advancing on said rolls within said adjacent controlled atmosphere chamber.
2. The method defined in claim 1, including the step of applying a coating to the upwardly facing surface of the ribbon of glass on said molten metal bath.
3. The method defined in claim 1, wherein said enclosed controlled atmosphere chamber is in communication with and receives said protective atmosphere from said enclosed headspace.
4. The method defined in claim 3, including maintaining said adjacent controlled atmosphere chamber substantially free from atmosphere other than said protective atmosphere at a plenum within said enclosed headspace.
5. The method defined in claim 1, wherein said at least one coating is applied by a coater mechanism capable of applying a supply of precursor to the surface of the ribbon of glass and simultaneously evacuating the zones immediately upstream and downstream from the application zone.
6. The method defined in claim 1, wherein additional heat energy is selectively applied within said adjacent controlled atmosphere chamber.
7. The method defined in claim 4, including maintaining the internal pressure within said controlled atmosphere chamber at a level above the external ambient pressure and below the plenum pressure within said enclosed headspace.
8. A method of pyrolytically coating float glass during the manufacture thereof including the steps of:
a) advancing a ribbon of glass along the surface of a molten metal bath within an enclosed headspace, said bath having an inlet end and an outlet end;
b) maintaining a protective atmosphere at a plenum within said headspace;
c) maintaining an enclosed controlled atmosphere chamber immediately adjacent the outlet end of the molten metal bath and enclosed headspace;
d) advancing the coated ribbon of glass through the controlled atmosphere chamber; and e) applying at least one coating to the upwardly facing surface of the ribbon of glass within the controlled atmosphere chamber.
a) advancing a ribbon of glass along the surface of a molten metal bath within an enclosed headspace, said bath having an inlet end and an outlet end;
b) maintaining a protective atmosphere at a plenum within said headspace;
c) maintaining an enclosed controlled atmosphere chamber immediately adjacent the outlet end of the molten metal bath and enclosed headspace;
d) advancing the coated ribbon of glass through the controlled atmosphere chamber; and e) applying at least one coating to the upwardly facing surface of the ribbon of glass within the controlled atmosphere chamber.
9. The method defined in claim 8, wherein at least one coating is applied to an upwardly facing surface of the ribbon of glass as said ribbon is advanced between the inlet and the outlet ends of said bath.
10. Apparatus for depositing at least one layer of coating material on the upper surface of a ribbon of float glass comprising, an elongated tank structure having inlet and outlet ends and containing a bath of molten metal, an enclosure over said tank structure defining a headspace within which a plenum of protective atmosphere is maintained, means delivering molten glass to the bath at said inlet end and advancing the glass along the surface of the bath to said outlet end under thermal conditions assuring that a ribbon of glass having an upwardly facing surface is formed on the bath, a plurality of traction rolls mounted adjacent said outlet end outside said enclosure for receiving and conveying said ribbon from said bath, an enclosed controlled atmosphere chamber contiguous with said tank structure and enclosure and enveloping said traction rolls, and coating means within said controlled atmosphere chamber for depositing at least one of said layers on said ribbon on said traction rolls.
11. Apparatus as claimed in claim 10 for sequentially depositing a plurality of layers of coating materials, including coating means within said enclosure for depositing at least one of said layers.
12. Apparatus for depositing said at least one layer as claimed in claim 10, including an inlet opening in said enclosed chamber over said ribbon providing communication with said headspace for admitting said protective atmosphere from said headspace to said enclosed chamber.
13. Apparatus for depositing said at least one layer as claimed in claim 10, in which said coating means within said enclosure sequentially deposits two of said layers.
14. Apparatus for sequentially depositing a plurality of layers as claimed in claim 11, wherein said coating means within said controlled atmosphere chamber sequentially deposits two of said layers.
15. Apparatus for depositing said at least one layer as claimed in claim 12, wherein said tank structure and said enclosure include outlet end walls defining an opening through which said ribbon advances onto said traction rolls, whereby said opening through which said ribbon advances comprises said inlet opening in communication with said headspace.
16. Apparatus for depositing said at least one layer as claimed in claim 15, wherein said coating means includes a pair of spaced apart coaters disposed above and extending transversely of said ribbon within said controlled atmosphere chamber.
17. Apparatus for sequentially depositing a plurality of layers as claimed in claim 15, wherein said controlled atmosphere chamber enveloping said rolls comprises inlet and outlet end walls, opposite side walls, a roof and a floor, said inlet end wall of said chamber being common with said outlet end wall of said tank structure and enclosure.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US36574489A | 1989-06-13 | 1989-06-13 | |
| US365,744 | 1989-06-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2002495A1 true CA2002495A1 (en) | 1990-12-13 |
Family
ID=23440162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2002495 Abandoned CA2002495A1 (en) | 1989-06-13 | 1989-11-08 | Method and apparatus for manufacturing coated flat glass |
Country Status (5)
| Country | Link |
|---|---|
| CN (1) | CN1048021A (en) |
| AU (1) | AU4742390A (en) |
| CA (1) | CA2002495A1 (en) |
| ES (1) | ES2019767A6 (en) |
| WO (1) | WO1990015783A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110108373A (en) * | 2009-01-26 | 2011-10-05 | 아사히 가라스 가부시키가이샤 | Method for producing electronic device substrate, method for manufacturing electronic device, electronic device substrate, and electronic device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1283432A (en) * | 1970-03-24 | 1972-07-26 | Pilkington Brothers Ltd | Improvements in or relating to the coating of glass |
| CA1083881A (en) * | 1977-08-25 | 1980-08-19 | General Foods, Lmited | Separation and recovery of coffee aroma constituents from roasted coffee |
| JPS5637251A (en) * | 1979-08-31 | 1981-04-10 | Nippon Sheet Glass Co Ltd | Manufacture of covered glass |
| US4661381A (en) * | 1985-10-07 | 1987-04-28 | Libbey-Owens-Ford Co. | Continuous vapor deposition method for producing a coated glass article |
| US4761171A (en) * | 1987-02-09 | 1988-08-02 | Libbey-Owens-Ford Co. | Apparatus for coating glass |
-
1989
- 1989-11-08 CA CA 2002495 patent/CA2002495A1/en not_active Abandoned
- 1989-11-22 WO PCT/US1989/005312 patent/WO1990015783A1/en unknown
- 1989-11-22 AU AU47423/90A patent/AU4742390A/en not_active Abandoned
- 1989-12-21 ES ES8904314A patent/ES2019767A6/en not_active Expired - Lifetime
-
1990
- 1990-02-06 CN CN 90100637 patent/CN1048021A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO1990015783A1 (en) | 1990-12-27 |
| AU4742390A (en) | 1991-01-08 |
| ES2019767A6 (en) | 1991-07-01 |
| CN1048021A (en) | 1990-12-26 |
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