US20040107732A1 - Apparatus and method for producing float glass having reduced defect density - Google Patents

Apparatus and method for producing float glass having reduced defect density Download PDF

Info

Publication number
US20040107732A1
US20040107732A1 US10/672,026 US67202603A US2004107732A1 US 20040107732 A1 US20040107732 A1 US 20040107732A1 US 67202603 A US67202603 A US 67202603A US 2004107732 A1 US2004107732 A1 US 2004107732A1
Authority
US
United States
Prior art keywords
glass
section
float
float chamber
threshold temperature
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
Application number
US10/672,026
Inventor
Charlene Smith
George Pecoraro
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PPG Industries Ohio Inc
Original Assignee
PPG Industries Ohio Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to US10/672,026 priority Critical patent/US20040107732A1/en
Priority to AU2003275273A priority patent/AU2003275273A1/en
Priority to PCT/US2003/030576 priority patent/WO2004028987A1/en
Priority to JP2004540235A priority patent/JP5032744B2/en
Priority to CNB038229552A priority patent/CN100339321C/en
Priority to MXPA05003111A priority patent/MXPA05003111A/en
Application filed by PPG Industries Ohio Inc filed Critical PPG Industries Ohio Inc
Priority to CA2499949A priority patent/CA2499949C/en
Priority to EP03759549A priority patent/EP1542935A1/en
Assigned to PPG INDUSTRIES OHIO, INC. reassignment PPG INDUSTRIES OHIO, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PECORARO, GEORGE A., SMITH, CHARLENE S.
Publication of US20040107732A1 publication Critical patent/US20040107732A1/en
Priority to US11/760,194 priority patent/US10280105B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00Shaping glass in contact with the surface of a liquid
    • C03B18/02Forming sheets
    • C03B18/20Composition of the atmosphere above the float bath; Treating or purifying the atmosphere above the float bath
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00Shaping glass in contact with the surface of a liquid
    • C03B18/02Forming sheets
    • C03B18/18Controlling or regulating the temperature of the float bath; Composition or purification of the float bath
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/235Heating the glass
    • C03B5/2353Heating the glass by combustion with pure oxygen or oxygen-enriched air, e.g. using oxy-fuel burners or oxygen lances
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/50Glass production, e.g. reusing waste heat during processing or shaping
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00Technologies relating to the processing of minerals
    • Y02P40/50Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57Improving the yield, e-g- reduction of reject rates

Definitions

  • the present invention relates to a float glass chamber used to produce flat glass by the float glass process, and more specifically float glass chambers that can be used to yield glass having reduced defect density.
  • the float glass process is well known for making sheets of glass.
  • batch materials are heated to form molten glass.
  • the molten glass is then poured onto a bath of molten tin.
  • the molten glass is drawn along the bath of molten tin and simultaneously cooled and attenuated to form a dimensionally stable continuous sheet of glass, typically referred to as a glass ribbon.
  • the sheet is then removed from the bath for further processing.
  • an oxy-fuel furnace In an oxy-fuel furnace, oxygen, not air, supports combustion. As a result, an oxy-fuel furnace provides a much more efficient melt than an air-fuel furnace because energy is no longer being wasted heated up nitrogen in the air and oxy-fuel flames have a higher flame temperature which radiates more efficiently. The increased melting efficiency allows more tonnage to be processed through an oxy-fuel furnace than through a similarly sized, air-fuel furnace.
  • Both air-fuel and oxy-fuel furnaces have water in their atmospheres.
  • the head space (the area of the furnace above the molten glass) in an oxy-fuel furnace has a higher concentration of water than in an air-fuel furnace because the oxy-fuel atmosphere lacks the nitrogen provided in an air-fired furnace that dilutes the total water formed by combustion.
  • the water typically constitutes about 66% by volume of the head space in an oxy-fuel furnace versus 18% in an air-fired furnace. Since the amount of water in the glass melt is proportional to the square root of the concentration of water in the head space, glass melted in an oxy-fuel furnace has a 1.7 to 2 times higher water concentration than glass melted in a conventional air-fuel furnace. Typically, glass melted in an oxy-fuel furnace contains more than 0.045 weight percent water based on the total weight of the composition.
  • the molten tin temperature in the float bath ranges from 1800° F. to 1900° F. (981° C. to 1037° C.).
  • 1800° F. at the glass-tin interface, water that diffuses out of the molten glass dissociates into hydrogen and oxygen. Because hydrogen isn't very soluble in tin at 1800° F., much of the hydrogen does not dissolve in the tin but remains in the atmosphere of the bath.
  • open bottom bubbles Some of the hydrogen from the disassociation of water gets trapped at the interface between the molten glass and tin and ultimately impinges on the bottom surface of the glass ribbon and form defects along the ribbon surface typically referred to as open bottom bubbles.
  • the open-bottom bubbles can be described as voids in glass that generally have an inverted-U shape cross-section. The presence of open bottom bubbles increases the overall defect density of the glass.
  • the present invention provides a novel apparatus and method that yields float glass having a lower total defect density as a result of reduced open bottom bubble defects.
  • the present invention is float glass chamber comprising:
  • a hot section having an atmosphere in at least the lower plenum comprises less than 3 percent hydrogen based on volume
  • a cold section wherein the boundary line between the hot section and the cold section is where the temperature of the glass falls below a threshold temperature.
  • the present invention is method for making float glass with reduced defect density comprising:
  • the hot section has an atmosphere in at least the lower plenum comprises less than 3 percent hydrogen based on volume
  • FIG. 1. is a sectional view of a float chamber according to the present invention, with portions removed for clarity.
  • a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 5.5 to 10 or 3.2 to 7.8.
  • a glass batch composition is heated to a molten state and poured into the float chamber.
  • the float chamber has a refractory roof 3 that divides the chamber into an upper plenum 1 and a lower plenum 2 .
  • the lower plenum contains the glass 4 and the tin 5 .
  • the upper plenum contains all of the overhead electrical heating elements to provide controlled heating of the liquid metal float bath and the formed glass ribbon.
  • a controlled atmosphere is maintained in the chamber via gas inlets 6 and gas outlet(s) 7 .
  • the novel float glass chamber of the present invention comprises at least two sections—a hot section and a cold section.
  • the boundary line between the hot section and the cold section is where the temperature of the glass falls below a predetermined temperature, hereinafter referred to as the “threshold temperature,” required for glass in the hot section.
  • the threshold temperature a predetermined temperature
  • the threshold temperature is 2100° F. In another non-limiting embodiment of the invention, the threshold temperature is 1800° F. In another non-limiting embodiment of the invention, the threshold temperature is 1600° F. The lower the threshold temperature for the hot section, the larger the hot section and the smaller the cold section and visa versa.
  • the hot section of the chamber is approximately 90 to 100 feet from the point where the molten glass is poured onto the tin.
  • the cold section of the chamber is the next approximately 70 to 140 feet of chamber behind the hot section, depending on the size of the bath.
  • numerous gas inlets and outlets are present in the upper plenum and lower plenum of the float chamber.
  • Various gaseous mixtures can be pumped into the chamber through the gas inlets or out of the chamber through the gas outlets to control the atmosphere within the chamber.
  • the gas inlets to at least the lower plenum over the hot section of the chamber deliver in a gas comprising less than 1 weight percent hydrogen based on volume.
  • the remainder of the gas can be an inert gas, such as but not limited to nitrogen.
  • the atmosphere of the lower plenum over the hot section of the chamber can comprise 3 percent hydrogen based on volume.
  • the atmosphere of the lower plenum over the hot section of the chamber can comprise 1 percent hydrogen based on volume.
  • Various mixtures of hydrogen and nitrogen or argon or ammonia in placed of mixed gases can be pumped into the atmosphere of at least the lower plenum over the cold section of the chamber.
  • the gaseous mixture can comprise up to 10 percent of the hydrogen based on volume.
  • the rest of the gas can be nitrogen.
  • the gas outlets in the float chamber can be used to remove gas from the chamber.
  • up to 40 volume percent based on volume of the total flow of the gas pumped into the chamber as discussed above can be removed from the hot section.
  • the present invention also encompasses a method for producing glass.
  • glass can be produced via the following steps: adding glass batch materials to a furnace; melting the batch materials; pouring molten glass from the furnace into the float chamber; and removing the float glass from the float chamber.
  • the first step of the present invention comprises adding glass batch materials to a furnace.
  • the furnace can be an air-fuel furnace or an oxy-fuel furnace.
  • the glass batch materials can be of any conventional type including, but not limited to, conventional soda-lime-silica glass batch materials.
  • a conventional glass composition can be characterized as follows:
  • the third step of the present invention involves pouring molten glass from the furnace into the float chamber.
  • the molten glass flows onto the top of the molten tin and moves along the top of the tin from the hot section of the chamber to the cold section of the chamber.
  • the temperature of the glass in the hot section and the cold section of the chamber are as discussed above.
  • the environments above the glass in the hot section and the cold section of the chamber are as discussed above.
  • the glass melt coming into the tin bath can contain water.
  • the glass melt can have a water content equal to or greater than 0.045 weight percent based on the total weight percent of the composition.
  • the next step of the invention involves removing the float glass from the bath as is well known in the art.
  • the glass can also be coated.
  • the glass is coated.
  • the coating can include one or more coating layers and/or coating films.
  • the coating can be of any desired type.
  • the coating can be an electroconductive coating, a heatable coating, an antenna coating, or a solar control coating, such as a low emissivity coating.
  • Non-limiting examples of solar control and antenna coatings are disclosed in U.S. Pat. Nos.
  • Glass made by a float process typically ranges from a sheet thickness of 2 millimeter to 20 millimeters. Glass having the aforementioned thickness can be prepared on a conventional float line having a line speed ranging from 100 to 800 inches per minute. The required thickness of the glass is determined by the end use of the glass.
  • Glass produced according to the present invention can meet the various commercial standards for defect density.
  • car manufactures set standards for defect density for automotive windshields.
  • One automobile manufacture requires-automotive windshield glass production to have less than 1 total defect per 100 square feet.
  • the glass produced according to the present invention can be used as automotive transparencies, in colored glasses, laminated products, etc. as is well known in the art.
  • a laminated product can comprise at least one piece of glass produced according to the present invention.
  • Such a laminated product can be a windshield.
  • the apparatus and method of the present invention allows float glass to be produced which has substantially reduced open-bottom bubble defects as compared to conventional float glass.

Abstract

A float glass chamber and related methods comprising a hot section having an atmosphere in at least the lower plenum comprises less than 3 percent hydrogen based on volume and a cold section, wherein the boundary line between the hot section and the cold section is where the temperature of the glass falls below a threshold temperature

Description

    RELATED APPLICATION
  • This application claims the benefits of U.S. Provisional Application Serial No. 60/414,516 filed Sep. 27, 2002, which application is herein incorporated by reference in its entirety.[0001]
  • FIELD OF THE INVENTION
  • The present invention relates to a float glass chamber used to produce flat glass by the float glass process, and more specifically float glass chambers that can be used to yield glass having reduced defect density. [0002]
  • BACKGROUND
  • The float glass process is well known for making sheets of glass. In a typical float glass process, batch materials are heated to form molten glass. The molten glass is then poured onto a bath of molten tin. The molten glass is drawn along the bath of molten tin and simultaneously cooled and attenuated to form a dimensionally stable continuous sheet of glass, typically referred to as a glass ribbon. The sheet is then removed from the bath for further processing. [0003]
  • Two types of furnaces are used in the float glass process—an air-fuel furnace and an oxy-fuel furnace. In an air-fuel furnace, fuel is mixed with warm air and combusted to provide heat to melt the glass batch materials. [0004]
  • In an oxy-fuel furnace, oxygen, not air, supports combustion. As a result, an oxy-fuel furnace provides a much more efficient melt than an air-fuel furnace because energy is no longer being wasted heated up nitrogen in the air and oxy-fuel flames have a higher flame temperature which radiates more efficiently. The increased melting efficiency allows more tonnage to be processed through an oxy-fuel furnace than through a similarly sized, air-fuel furnace. [0005]
  • Both air-fuel and oxy-fuel furnaces have water in their atmospheres. The head space (the area of the furnace above the molten glass) in an oxy-fuel furnace has a higher concentration of water than in an air-fuel furnace because the oxy-fuel atmosphere lacks the nitrogen provided in an air-fired furnace that dilutes the total water formed by combustion. Stoichiometrically, the water typically constitutes about 66% by volume of the head space in an oxy-fuel furnace versus 18% in an air-fired furnace. Since the amount of water in the glass melt is proportional to the square root of the concentration of water in the head space, glass melted in an oxy-fuel furnace has a 1.7 to 2 times higher water concentration than glass melted in a conventional air-fuel furnace. Typically, glass melted in an oxy-fuel furnace contains more than 0.045 weight percent water based on the total weight of the composition. [0006]
  • At the stage of the float glass process where molten glass is poured onto molten tin, the molten tin temperature in the float bath ranges from 1800° F. to 1900° F. (981° C. to 1037° C.). At 1800° F., at the glass-tin interface, water that diffuses out of the molten glass dissociates into hydrogen and oxygen. Because hydrogen isn't very soluble in tin at 1800° F., much of the hydrogen does not dissolve in the tin but remains in the atmosphere of the bath. Some of the hydrogen from the disassociation of water gets trapped at the interface between the molten glass and tin and ultimately impinges on the bottom surface of the glass ribbon and form defects along the ribbon surface typically referred to as open bottom bubbles. The open-bottom bubbles can be described as voids in glass that generally have an inverted-U shape cross-section. The presence of open bottom bubbles increases the overall defect density of the glass. [0007]
  • Customers set requirements for the defect density of glass for certain applications. The standards are very difficult to meet with conventional float glass processes due to the presence of open bottom bubbles. [0008]
  • The present invention provides a novel apparatus and method that yields float glass having a lower total defect density as a result of reduced open bottom bubble defects. [0009]
  • SUMMARY OF THE INVENTION
  • In one embodiment, the present invention is float glass chamber comprising: [0010]
  • a hot section having an atmosphere in at least the lower plenum comprises less than 3 percent hydrogen based on volume; and [0011]
  • a cold section, wherein the boundary line between the hot section and the cold section is where the temperature of the glass falls below a threshold temperature. [0012]
  • In another embodiment, the present invention is method for making float glass with reduced defect density comprising: [0013]
  • a. melting a glass composition to form a glass melt; and [0014]
  • b. pouring the glass melt in a float chamber having a hot section and an cold section, the boundary line between the hot section and the cold section is where the temperature of the glass falls below a threshold temperature, [0015]
  • wherein the hot section has an atmosphere in at least the lower plenum comprises less than 3 percent hydrogen based on volume[0016]
  • DRAWINGS
  • FIG. 1. is a sectional view of a float chamber according to the present invention, with portions removed for clarity.[0017]
  • DESCRIPTION OF THE INVENTION
  • As used herein, spatial or directional terms, such as “left”, “right”, “inner”, “outer”, “above”, “below”, “top”, “bottom”, and the like, relate to the invention as it is shown in the drawing figures. However, it is to be understood that the invention may assume various alternative orientations and, accordingly, such terms are not to be considered as limiting. [0018]
  • Unless otherwise indicated, all numbers expressing dimensions, physical characteristics, quantities of ingredients, reaction conditions and so forth, used in the specification and claims are to be understood as being modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical values set forth in the following specification and claims can vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Moreover, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 5.5 to 10 or 3.2 to 7.8. [0019]
  • Conventional float glass processes are typically carried out using a float chamber as shown in FIG. 1. Non-limiting examples of float glass processes are disclosed in U.S. Pat. No. 3,083,551, U.S. Pat. No. 3,961,930, and U.S. Pat. No. 4,091,156, which are all hereby incorporated by reference. [0020]
  • In a conventional float glass process, a glass batch composition is heated to a molten state and poured into the float chamber. Typically, the float chamber has a [0021] refractory roof 3 that divides the chamber into an upper plenum 1 and a lower plenum 2. The lower plenum contains the glass 4 and the tin 5. The upper plenum contains all of the overhead electrical heating elements to provide controlled heating of the liquid metal float bath and the formed glass ribbon. A controlled atmosphere is maintained in the chamber via gas inlets 6 and gas outlet(s) 7.
  • The novel float glass chamber of the present invention comprises at least two sections—a hot section and a cold section. The boundary line between the hot section and the cold section is where the temperature of the glass falls below a predetermined temperature, hereinafter referred to as the “threshold temperature,” required for glass in the hot section. In a non-limiting embodiment of the present invention, there is no physical barrier between the hot section and the cold section. [0022]
  • In one non-limiting embodiment of the invention, the threshold temperature is 2100° F. In another non-limiting embodiment of the invention, the threshold temperature is 1800° F. In another non-limiting embodiment of the invention, the threshold temperature is 1600° F. The lower the threshold temperature for the hot section, the larger the hot section and the smaller the cold section and visa versa. [0023]
  • In a non-limiting embodiment of the present invention, the hot section of the chamber is approximately 90 to 100 feet from the point where the molten glass is poured onto the tin. The cold section of the chamber is the next approximately 70 to 140 feet of chamber behind the hot section, depending on the size of the bath. [0024]
  • In a non-limiting embodiment of the present invention, numerous gas inlets and outlets are present in the upper plenum and lower plenum of the float chamber. Various gaseous mixtures can be pumped into the chamber through the gas inlets or out of the chamber through the gas outlets to control the atmosphere within the chamber. [0025]
  • In a non-limiting embodiment of the invention, the gas inlets to at least the lower plenum over the hot section of the chamber deliver in a gas comprising less than 1 weight percent hydrogen based on volume. The remainder of the gas can be an inert gas, such as but not limited to nitrogen. Under normal operating conditions, in one non-limiting embodiment of the present invention, the atmosphere of the lower plenum over the hot section of the chamber can comprise 3 percent hydrogen based on volume. In another non-limiting embodiment of the present invention, the atmosphere of the lower plenum over the hot section of the chamber can comprise 1 percent hydrogen based on volume. [0026]
  • Various mixtures of hydrogen and nitrogen or argon or ammonia in placed of mixed gases can be pumped into the atmosphere of at least the lower plenum over the cold section of the chamber. In a non-limiting embodiment of the invention, the gaseous mixture can comprise up to 10 percent of the hydrogen based on volume. The rest of the gas can be nitrogen. [0027]
  • The gas outlets in the float chamber can be used to remove gas from the chamber. In one non-limiting embodiment of the invention, up to 40 volume percent based on volume of the total flow of the gas pumped into the chamber as discussed above can be removed from the hot section. In this embodiment, it may be necessary to adjust the level of nitrogen in the atmosphere to prevent hydrogen from flowing upstream into the hot section of the chamber. [0028]
  • By reducing the hydrogen in the hot section of the float chamber, the present invention reduces the level of saturation of molten tin, specifically with respect to hydrogen, at the hot section of the float chamber. The molten tin is able to dissolve more hydrogen from the disassociation of water so open-bottom bubble defects in the glass are reduced. [0029]
  • The present invention also encompasses a method for producing glass. According to the present invention, glass can be produced via the following steps: adding glass batch materials to a furnace; melting the batch materials; pouring molten glass from the furnace into the float chamber; and removing the float glass from the float chamber. [0030]
  • The first step of the present invention comprises adding glass batch materials to a furnace. The furnace can be an air-fuel furnace or an oxy-fuel furnace. The glass batch materials can be of any conventional type including, but not limited to, conventional soda-lime-silica glass batch materials. A conventional glass composition can be characterized as follows: [0031]
  • from 65 to 75 weight percent SiO[0032] 2;
  • from 10 to 20 weight percent Na[0033] 2O;
  • from 5 to 15 weight percent CaO; [0034]
  • from 0 to 5 weight percent MgO; [0035]
  • from 0 to 5 weight percent Al[0036] 2O3;
  • from 0 to 5 weight percent K[0037] 2O; and
  • from 0 to 2 weight percent Fe[0038] 2O3.
  • All values are in weight percent based on the total weight of the glass composition. [0039]
  • The second step of the present invention comprises melting the batch materials in the furnace. The melting processes can be accomplished using techniques that are well known in the art. For example, in an oxy-fuel furnace, the batch materials can be melted by supplying oxygen and fuel to melt the batch materials. [0040]
  • The third step of the present invention involves pouring molten glass from the furnace into the float chamber. As is well known in the art, the molten glass flows onto the top of the molten tin and moves along the top of the tin from the hot section of the chamber to the cold section of the chamber. The temperature of the glass in the hot section and the cold section of the chamber are as discussed above. Also, the environments above the glass in the hot section and the cold section of the chamber are as discussed above. [0041]
  • The glass melt coming into the tin bath can contain water. The glass melt can have a water content equal to or greater than 0.045 weight percent based on the total weight percent of the composition. [0042]
  • The next step of the invention involves removing the float glass from the bath as is well known in the art. [0043]
  • After the float glass is removed from the float chamber, the glass is controllably cooled and cut into glass sheets. The sheet can be further processed, e.g. cut to shape and heat processed, to form a desired glass article. [0044]
  • The glass can also be coated. In a non-limiting embodiment of the invention, the glass is coated. The coating can include one or more coating layers and/or coating films. The coating can be of any desired type. For example, but not to be considered as limiting, the coating can be an electroconductive coating, a heatable coating, an antenna coating, or a solar control coating, such as a low emissivity coating. Non-limiting examples of solar control and antenna coatings are disclosed in U.S. Pat. Nos. 4,898,789; 5,821,001; 4,716,086; 4,610,771; 4,902,580; 4,716,086; 4,806,220; 4,898,790; 4,834,857; 4,948,677; 5,059,295; and 5,028,579, which patents are herein incorporated by reference. Non-limiting examples of electroconductive coatings are disclosed in U.S. Pat. Nos. 5,653,903 and 5,028,759, which are herein incorporated by reference. [0045]
  • Glass made by a float process typically ranges from a sheet thickness of 2 millimeter to 20 millimeters. Glass having the aforementioned thickness can be prepared on a conventional float line having a line speed ranging from 100 to 800 inches per minute. The required thickness of the glass is determined by the end use of the glass. [0046]
  • The present invention provides glass having reduced defect density; specifically open-bottom bubbles. Such defects in glass can be measured using on-line and off-line methods. An Automatic Inspection System manufactured by Inspection Technologies Inc. can be used to measure defects on-line. Defects can be measured off-line by visual inspection. The defect density of glass is measured as number of defects per 100 square feet. The standards for measuring defects in glass are well known in the art. For example, defects can be measured in categories from <0.06″ to >0.25″. [0047]
  • Glass produced according to the present invention can meet the various commercial standards for defect density. For example, car manufactures set standards for defect density for automotive windshields. One automobile manufacture requires-automotive windshield glass production to have less than 1 total defect per 100 square feet. [0048]
  • The glass produced according to the present invention can be used as automotive transparencies, in colored glasses, laminated products, etc. as is well known in the art. A laminated product can comprise at least one piece of glass produced according to the present invention. Such a laminated product can be a windshield. [0049]
  • EXAMPLES
  • The invention is illustrated by the following non-limiting examples. The following is an example of a control run where hydrogen was in the lower plenum of the hot end and a run according to the present invention. [0050]
    Control Example of the Invention
    H2 in total chamber 1900 scfh 600 scfh
    H2 in at least lower 1300 scfh 0 scfh
    plenum of hot end
    Open Bottom Bubble 1.36 per 100 sq. ft. 0.07 per 100 sq. ft.
    defects
    Thickness of glass 3 mm 3 mm
    Tonnage 599 Tons per day 604 TPD
    Threshold Temperature 1769° F. 1761° F.
    H2O in glass 0.049% 0.049%
  • CONCLUSION
  • The apparatus and method of the present invention allows float glass to be produced which has substantially reduced open-bottom bubble defects as compared to conventional float glass. [0051]
  • The above examples are offered only to illustrate the present invention. The scope of the present invention is defined by the following claims. [0052]

Claims (19)

What is claimed is:
1. A float glass chamber comprising:
a hot section having an atmosphere in at least the lower plenum comprises less than 3 percent hydrogen based on volume; and
a cold section, wherein the boundary line between the hot section and the cold section is where the temperature of the glass falls below a threshold temperature.
2. A float chamber according to claim 1 wherein the threshold temperature of the chamber is 1600° F.
3. A float chamber according to claim 1 wherein the threshold temperature of the float chamber is 1800° F.
4. A float chamber according to claim 1 wherein the threshold temperature of the float chamber is 2100° F.
5. A float chamber according to claim 1 wherein the atmosphere in at least the lower plenum of the cold section comprises up to 10 percent of hydrogen based on volume.
6. A float chamber comprising:
a hot section having an atmosphere in at least the lower plenum comprises less than 3 percent hydrogen based on volume; and
a cold section, wherein the boundary line between the hot section and the cold section is where the temperature of the glass falls below a threshold temperature of greater than 1600° F.
7. A float chamber according to claim 6 wherein the atmosphere in at least the lower plenum of the cold section comprises up to 10 percent of hydrogen based on volume.
8. A method for making float glass with reduced defect density comprising:
a. melting a glass composition to form a glass melt; and
b. pouring the glass melt in a float chamber having a hot section and an cold section, the boundary line between the hot section and the cold section is where the temperature of the glass falls below a threshold temperature, wherein the hot section has an atmosphere in at least the lower plenum comprises less than 3 percent hydrogen based on volume
9. A method according to claim 8 wherein the threshold temperature of the float chamber is 1600° F.
10. A method according to claim 8 wherein the threshold temperature of the float chamber is 1800° F.
11. A method according to claim 8 wherein the threshold temperature of the float chamber is 2100° F.
12. A method according to claim 8 wherein the atmosphere in at least the lower plenum of the cold section comprises up to 10 percent of hydrogen based on volume
13. A method according to claim 8 wherein the glass melt has a water content equal to or greater than 0.035 weight percent based on the total weight percent of the composition.
14. A method according to claim 8 wherein the float glass produced comprises at least one piece of glass in a laminated product.
15. A method according to claim 14 wherein the laminated product is a windshield.
16. A method for making float glass with reduced defect density comprising:
a. melting a glass composition to form a glass melt; and
b. pouring the glass melt into a float chamber having a hot section and an cold section, the boundary line between the hot section and the cold section is where the temperature of the glass falls below a threshold temperature;
c. pumping a gas mixture comprising less than 3% hydrogen based on volume into at least the lower plenum of the hot section.
17. A method according to claim 16 wherein the pumping comprises pumping a gas mixture comprising less than 1% hydrogen based on volume into at least the lower plenum of the hot section.
18. A method according to claim 16 wherein the glass composition comprises:
from 65 to 75 weight percent SiO2;
from 10 to 20 weight percent Na2O;
from 5 to 15 weight percent CaO;
from 0 to 5 weight percent MgO;
from 0 to 5 weight percent Al2O3;
from 0 to 5 weight percent K2O; and
from 0 to 2 weight percent Fe2O3,
with weight percents being based on the total weight of the glass composition.
19. A method according to claim 16 wherein the melting occurs in an oxy-fuel furnace.
US10/672,026 2002-09-27 2003-09-26 Apparatus and method for producing float glass having reduced defect density Abandoned US20040107732A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
AU2003275273A AU2003275273A1 (en) 2002-09-27 2003-09-26 Apparatus and method for producing float glass having reduced defect density
PCT/US2003/030576 WO2004028987A1 (en) 2002-09-27 2003-09-26 Apparatus and method for producing float glass having reduced defect density
JP2004540235A JP5032744B2 (en) 2002-09-27 2003-09-26 Apparatus and method for producing float glass with reduced defect density
CNB038229552A CN100339321C (en) 2002-09-27 2003-09-26 Apparatus and method for producing float glass having reduced defect density
MXPA05003111A MXPA05003111A (en) 2002-09-27 2003-09-26 Apparatus and method for producing float glass having reduced defect density.
US10/672,026 US20040107732A1 (en) 2002-09-27 2003-09-26 Apparatus and method for producing float glass having reduced defect density
CA2499949A CA2499949C (en) 2002-09-27 2003-09-26 Method for producing float glass having reduced defect density
EP03759549A EP1542935A1 (en) 2002-09-27 2003-09-26 Apparatus and method for producing float glass having reduced defect density
US11/760,194 US10280105B2 (en) 2002-09-27 2007-06-08 Apparatus and methods for producing float glass having reduced defect density

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41451602P 2002-09-27 2002-09-27
US10/672,026 US20040107732A1 (en) 2002-09-27 2003-09-26 Apparatus and method for producing float glass having reduced defect density

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/760,194 Continuation US10280105B2 (en) 2002-09-27 2007-06-08 Apparatus and methods for producing float glass having reduced defect density

Publications (1)

Publication Number Publication Date
US20040107732A1 true US20040107732A1 (en) 2004-06-10

Family

ID=32045292

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/672,026 Abandoned US20040107732A1 (en) 2002-09-27 2003-09-26 Apparatus and method for producing float glass having reduced defect density
US11/760,194 Active 2025-10-03 US10280105B2 (en) 2002-09-27 2007-06-08 Apparatus and methods for producing float glass having reduced defect density

Family Applications After (1)

Application Number Title Priority Date Filing Date
US11/760,194 Active 2025-10-03 US10280105B2 (en) 2002-09-27 2007-06-08 Apparatus and methods for producing float glass having reduced defect density

Country Status (8)

Country Link
US (2) US20040107732A1 (en)
EP (1) EP1542935A1 (en)
JP (1) JP5032744B2 (en)
CN (1) CN100339321C (en)
AU (1) AU2003275273A1 (en)
CA (1) CA2499949C (en)
MX (1) MXPA05003111A (en)
WO (1) WO2004028987A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070022780A1 (en) * 2005-07-28 2007-02-01 House Keith L Method of increasing the effectiveness of a fining agent in a glass melt
US20070175241A1 (en) * 2005-07-28 2007-08-02 Delamielleure Megan A Method of reducing gaseous inclusions in a glass making process
DE102008041661A1 (en) 2008-08-28 2010-03-04 Schott Ag Method for the production of flat glass in a float bath apparatus, comprises melting glass in a melting end, pouring the glass melt on a fluid metal bath and then forming to a glass strip, where the apparatus comprises a float bath base
DE102009000348A1 (en) 2008-08-28 2010-03-04 Schott Ag Production of flat glass used in the manufacture of e.g. plasma screens comprises introducing a hydrogen-containing protective gas into a float bath housing
US20100199721A1 (en) * 2008-11-12 2010-08-12 Keisha Chantelle Ann Antoine Apparatus and method for reducing gaseous inclusions in a glass
US9512026B2 (en) 2012-03-14 2016-12-06 Asahi Glass Company, Limited Float glass plate and method of manufacturing thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7475568B2 (en) * 2005-04-27 2009-01-13 Corning Incorporated Method of fining glass
BR112013023880A2 (en) * 2011-03-23 2016-12-13 Asahi Glass Co Ltd flat glass and process to produce the same
EP3617158A1 (en) * 2018-08-28 2020-03-04 Linde Aktiengesellschaft Method for manufacturing float glass
WO2020191275A1 (en) * 2019-03-20 2020-09-24 Air Products And Chemicals, Inc. Method for tin bath monitoring and control

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3333936A (en) * 1965-10-15 1967-08-01 Libbey Owens Ford Glass Co Cooler compensating heater for temperature control in glass making
US3337322A (en) * 1962-10-17 1967-08-22 Pilkington Brothers Ltd Method of manufacture of flat glass with reducing atmosphere
US3356476A (en) * 1965-02-08 1967-12-05 Pittsburgh Plate Glass Co Method of removing contaminates from the protective atmosphere of a glass sheet float bath
US3594143A (en) * 1967-06-30 1971-07-20 Pilkington Brothers Ltd Process of floating glass on molten metal with a particular atmosphere
US3615316A (en) * 1967-06-17 1971-10-26 Nippon Sheet Glass Co Ltd Float glass method and apparatus with gas extraction means
US3865680A (en) * 1972-03-29 1975-02-11 Ppg Industries Inc Automobile windshield and its method of fabrication
US3970442A (en) * 1975-07-16 1976-07-20 Ppg Industries, Inc. Method of introducing protective atmosphere gases into a glass forming chamber
US4610771A (en) * 1984-10-29 1986-09-09 Ppg Industries, Inc. Sputtered films of metal alloy oxides and method of preparation thereof
US4716086A (en) * 1984-12-19 1987-12-29 Ppg Industries, Inc. Protective overcoat for low emissivity coated article
US4806220A (en) * 1986-12-29 1989-02-21 Ppg Industries, Inc. Method of making low emissivity film for high temperature processing
US4834857A (en) * 1988-04-01 1989-05-30 Ppg Industries, Inc. Neutral sputtered films of metal alloy oxides
US4898789A (en) * 1988-04-04 1990-02-06 Ppg Industries, Inc. Low emissivity film for automotive heat load reduction
US4898790A (en) * 1986-12-29 1990-02-06 Ppg Industries, Inc. Low emissivity film for high temperature processing
US4902580A (en) * 1988-04-01 1990-02-20 Ppg Industries, Inc. Neutral reflecting coated articles with sputtered multilayer films of metal oxides
US4948677A (en) * 1984-01-31 1990-08-14 Ppg Industries, Inc. High transmittance, low emissivity article and method of preparation
US5028759A (en) * 1988-04-01 1991-07-02 Ppg Industries, Inc. Low emissivity film for a heated windshield
US5028579A (en) * 1988-07-08 1991-07-02 Canon Kabushiki Kaisha Image forming method
US5059295A (en) * 1986-12-29 1991-10-22 Ppg Industries, Inc. Method of making low emissivity window
US5653903A (en) * 1995-06-27 1997-08-05 Ppg Industries, Inc. L-shaped heating element with radiused end for a windshield
US5821001A (en) * 1996-04-25 1998-10-13 Ppg Industries, Inc. Coated articles
US20020059811A1 (en) * 2000-09-15 2002-05-23 Landa Ksenia A. Photochromic float glasses and methods of making the same
US6532771B1 (en) * 2001-08-21 2003-03-18 Praxair Technology, Inc. Method for controlling glass furnace atmosphere

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3615315A (en) * 1962-04-19 1971-10-26 Ppg Industries Inc Method and apparatus having sealing means and gaseous takeoff for float glass
NL134932C (en) * 1962-10-17
US3337319A (en) * 1962-10-17 1967-08-22 Pilkington Brothers Ltd Method and apparatus for purifying the molten bath of a glass sheet forming operation
DE1596419B1 (en) * 1967-04-01 1970-10-15 Floatglas Gmbh Process for the continuous production of a ribbon of flat glass on a bath of molten tin
US3584475A (en) * 1967-04-14 1971-06-15 Ppg Industries Inc Float glass tank with a particulate bottom covering
US3607203A (en) * 1967-07-07 1971-09-21 Nippon Sheet Glass Co Ltd Float glass apparatus with longitudinal dams and metal flow control means
GB1248910A (en) * 1967-12-29 1971-10-06 Pilkington Brothers Ltd Improvements in or relating to the manufacture of flat glass
US3462253A (en) * 1968-03-20 1969-08-19 Ppg Industries Inc Manufacture of float glass using enclosed bath zones
GB1264958A (en) * 1968-07-15 1972-02-23
LU56578A1 (en) * 1968-07-24 1970-01-26
GB1314537A (en) * 1970-09-23 1973-04-26 Pilkington Brothers Ltd Manufacture of flat glass by the float process
US3881905A (en) * 1974-02-21 1975-05-06 Ppg Industries Inc Method of manufacture of metal oxide-containing colored glass
US4015966A (en) * 1976-06-01 1977-04-05 Owens-Illinois, Inc. Manufacture of X-ray absorbing glass composition by a float glass process
CN1031636C (en) * 1992-05-04 1996-04-24 化学工业部上海化工研究院 Ammonia decomposition method for prodn. of highly pure hydrogen and nitrogen gas for use in float glass industry
US5364435A (en) * 1992-11-20 1994-11-15 Libbey-Owens-Ford Co. Method of introducing protective atmosphere gases into a glass forming chamber
EP0812809A3 (en) * 1996-06-12 1998-11-25 Praxair Technology, Inc. Method to reduce toxic emissions from glass melting furnaces by water enhanced fining process
US5925158A (en) * 1997-12-19 1999-07-20 Praxair Technology, Inc. Gas recycle for float glass system
US5888265A (en) * 1997-12-22 1999-03-30 Praxair Technology, Inc. Air separation float glass system
JP3846026B2 (en) * 1998-04-27 2006-11-15 旭硝子株式会社 Sheet glass manufacturing method and apparatus used for the method
US6997018B2 (en) * 2003-06-02 2006-02-14 Ferro Corporation Method of micro and nano texturing glass
KR100998457B1 (en) * 2004-04-07 2010-12-06 아사히 가라스 가부시키가이샤 Apparatus and method for manufacturing plate glass

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3337322A (en) * 1962-10-17 1967-08-22 Pilkington Brothers Ltd Method of manufacture of flat glass with reducing atmosphere
US3356476A (en) * 1965-02-08 1967-12-05 Pittsburgh Plate Glass Co Method of removing contaminates from the protective atmosphere of a glass sheet float bath
US3333936A (en) * 1965-10-15 1967-08-01 Libbey Owens Ford Glass Co Cooler compensating heater for temperature control in glass making
US3615316A (en) * 1967-06-17 1971-10-26 Nippon Sheet Glass Co Ltd Float glass method and apparatus with gas extraction means
US3594143A (en) * 1967-06-30 1971-07-20 Pilkington Brothers Ltd Process of floating glass on molten metal with a particular atmosphere
US3865680A (en) * 1972-03-29 1975-02-11 Ppg Industries Inc Automobile windshield and its method of fabrication
US3970442A (en) * 1975-07-16 1976-07-20 Ppg Industries, Inc. Method of introducing protective atmosphere gases into a glass forming chamber
US4948677A (en) * 1984-01-31 1990-08-14 Ppg Industries, Inc. High transmittance, low emissivity article and method of preparation
US4610771A (en) * 1984-10-29 1986-09-09 Ppg Industries, Inc. Sputtered films of metal alloy oxides and method of preparation thereof
US4716086A (en) * 1984-12-19 1987-12-29 Ppg Industries, Inc. Protective overcoat for low emissivity coated article
US4806220A (en) * 1986-12-29 1989-02-21 Ppg Industries, Inc. Method of making low emissivity film for high temperature processing
US5059295A (en) * 1986-12-29 1991-10-22 Ppg Industries, Inc. Method of making low emissivity window
US4898790A (en) * 1986-12-29 1990-02-06 Ppg Industries, Inc. Low emissivity film for high temperature processing
US4834857A (en) * 1988-04-01 1989-05-30 Ppg Industries, Inc. Neutral sputtered films of metal alloy oxides
US4902580A (en) * 1988-04-01 1990-02-20 Ppg Industries, Inc. Neutral reflecting coated articles with sputtered multilayer films of metal oxides
US5028759A (en) * 1988-04-01 1991-07-02 Ppg Industries, Inc. Low emissivity film for a heated windshield
US4898789A (en) * 1988-04-04 1990-02-06 Ppg Industries, Inc. Low emissivity film for automotive heat load reduction
US5028579A (en) * 1988-07-08 1991-07-02 Canon Kabushiki Kaisha Image forming method
US5653903A (en) * 1995-06-27 1997-08-05 Ppg Industries, Inc. L-shaped heating element with radiused end for a windshield
US5821001A (en) * 1996-04-25 1998-10-13 Ppg Industries, Inc. Coated articles
US20020059811A1 (en) * 2000-09-15 2002-05-23 Landa Ksenia A. Photochromic float glasses and methods of making the same
US6532771B1 (en) * 2001-08-21 2003-03-18 Praxair Technology, Inc. Method for controlling glass furnace atmosphere

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070022780A1 (en) * 2005-07-28 2007-02-01 House Keith L Method of increasing the effectiveness of a fining agent in a glass melt
US20070175241A1 (en) * 2005-07-28 2007-08-02 Delamielleure Megan A Method of reducing gaseous inclusions in a glass making process
US7584632B2 (en) 2005-07-28 2009-09-08 Corning Incorporated Method of increasing the effectiveness of a fining agent in a glass melt
US7854144B2 (en) 2005-07-28 2010-12-21 Corning Incorporated Method of reducing gaseous inclusions in a glass making process
DE102008041661A1 (en) 2008-08-28 2010-03-04 Schott Ag Method for the production of flat glass in a float bath apparatus, comprises melting glass in a melting end, pouring the glass melt on a fluid metal bath and then forming to a glass strip, where the apparatus comprises a float bath base
DE102009000348A1 (en) 2008-08-28 2010-03-04 Schott Ag Production of flat glass used in the manufacture of e.g. plasma screens comprises introducing a hydrogen-containing protective gas into a float bath housing
DE102009000348B4 (en) * 2008-08-28 2011-09-01 Schott Ag Process for the production of flat glass
DE102008041661B4 (en) * 2008-08-28 2011-12-08 Schott Ag Process for the production of flat glass and float bath apparatus
US20100199721A1 (en) * 2008-11-12 2010-08-12 Keisha Chantelle Ann Antoine Apparatus and method for reducing gaseous inclusions in a glass
US9512026B2 (en) 2012-03-14 2016-12-06 Asahi Glass Company, Limited Float glass plate and method of manufacturing thereof

Also Published As

Publication number Publication date
WO2004028987A1 (en) 2004-04-08
JP2006513118A (en) 2006-04-20
AU2003275273A1 (en) 2004-04-19
EP1542935A1 (en) 2005-06-22
MXPA05003111A (en) 2005-06-22
JP5032744B2 (en) 2012-09-26
CA2499949C (en) 2012-02-07
US20070227190A1 (en) 2007-10-04
CN100339321C (en) 2007-09-26
US10280105B2 (en) 2019-05-07
CN1684914A (en) 2005-10-19
CA2499949A1 (en) 2004-04-08

Similar Documents

Publication Publication Date Title
US10280105B2 (en) Apparatus and methods for producing float glass having reduced defect density
AU2004218197B2 (en) Method for the production of glass from a mixture of various metals
US20240002276A1 (en) Low Iron, High Redox Ratio, and High Iron, High Redox Ratio, Soda-Lime-Silica Glasses and Methods of Making Same
EP1477464B1 (en) Transparent glass having blue edge color
US20110302962A1 (en) Method for producing clear glass or clear drawn glass by utilizing a special refining process
US11780764B2 (en) Low iron, high redox ratio, and high iron, high redox ratio, soda-lime-silica glasses and methods of making same
EP4103522B1 (en) Feed material for producing colorless glass using submerged combustion melting
TWI552972B (en) A molten glass manufacturing apparatus, a method for producing a molten glass, and a method for manufacturing the same
EP2043962B1 (en) Method of making glass including surface treatment with aluminum chloride at or just prior to annealing lehr
CN109336380A (en) A kind of ultra-clear glasses and its production method and special equipment
CN104876424A (en) Float Process For Producing A Float Glass Pane And Float Glass Pane
JP2006513118A5 (en)
TW201111312A (en) Molten glass manufacturing device, molten glass manufacturing method, and sheet glass manufacturing method using the device and the method
IE42326B1 (en) Manufacture of glass
CN114634307A (en) Glass suitable for one-kiln two-line production and production method thereof
CN110656266A (en) Aluminum plate alloy suitable for aluminum-plastic composite plate and preparation method thereof
CN111470754B (en) Method for calendering and coloring microcrystalline glass and product processing technology thereof
WO2023189559A1 (en) Method for producing glass article
KR20170107903A (en) Low iron, high redox ratio, and high iron, high redox ratio, soda-lime-silica glasses and methods of making same
Rajab The Process of Making Glass Bottles
RU2166482C2 (en) Method of manufacturing sheet glass

Legal Events

Date Code Title Description
AS Assignment

Owner name: PPG INDUSTRIES OHIO, INC., OHIO

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SMITH, CHARLENE S.;PECORARO, GEORGE A.;REEL/FRAME:014930/0708;SIGNING DATES FROM 20040107 TO 20040113

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION