(19)
(11)EP 0 912 452 B2

(12)NEW EUROPEAN PATENT SPECIFICATION
After opposition procedure

(45)Date of publication and mention of the opposition decision:
27.03.2013 Bulletin 2013/13

(45)Mention of the grant of the patent:
22.10.2003 Bulletin 2003/43

(21)Application number: 97932585.9

(22)Date of filing:  14.07.1997
(51)Int. Cl.: 
C03C 1/00  (2006.01)
C03B 17/06  (2006.01)
C03B 5/167  (2006.01)
C03B 17/00  (2006.01)
C03B 5/08  (2006.01)
C03B 5/225  (2006.01)
(86)International application number:
PCT/US1997/012140
(87)International publication number:
WO 1998/003442 (29.01.1998 Gazette  1998/04)

(54)

ARSENIC-FREE GLASSES

ARSENFREIE GLÄSER

VERRES EXEMPTS D'ARSENIC


(84)Designated Contracting States:
DE FR GB NL

(30)Priority: 19.07.1996 US 22193 P
28.10.1996 US 742610

(43)Date of publication of application:
06.05.1999 Bulletin 1999/18

(73)Proprietor: Corning Incorporated
Corning NY 14831 (US)

(72)Inventors:
  • BANGE, James, C.
    Corning, NY 14830 (US)
  • DORFELD, William, G.
    Beaver Dams, NY 14812 (US)
  • HAYES, James, C.
    Painted Post, NY 14870 (US)
  • LAPP, Josef, C.
    Corning, NY 14830 (US)

(74)Representative: Oldroyd, Richard Duncan et al
Elkington and Fife LLP Prospect House 8 Pembroke Road
Sevenoaks, Kent TN13 1XR
Sevenoaks, Kent TN13 1XR (GB)


(56)References cited: : 
EP-A- 0 527 320
EP-A- 0 528 149
EP-A- 0 607 865
DE-A1- 4 321 373
US-A- 3 339 696
US-A- 3 849 097
EP-A- 0 528 114
EP-A- 0 538 568
EP-A1- 0 714 862
JP-A- 5 306 140
US-A- 3 673 049
US-A- 5 116 787
  
  • KEVER E DE ET AL: "INFLUENCE OF BATCH MOISTURE AND ATMOSPHERE ON THE MELTING BEHAVIOR OF AS2O3- AND SB2O3-CONTAINING GLASSES" GLASTECHNISCHE BERICHTE, vol. 65, no. 2, 1 February 1992, pages 64-66, XP000259763
  • 'Investigation into Glass Substrates for LCD Manufactured Before July, 1996' TECHNICAL REPORT 0156 02 April 2004,
  • CORNING BROCHURE "CODE 1737F 1996,
  • NAKAO ET AL: 'Properties of Alkali- free Aluminosilicate Glass AN' REPORTS RES. LAB. ASAHI GLASS CO. LTD. vol. 35, no. 2, 1985, pages 207 - 218
  • WADA: 'Promotion of Price Reduction of Glass Substrate by Downdraw Method and by Improving Acid Resistance and Thermal Properties' FLATPANEL DISPLAY 93 1993, pages 172 - 175
  • BÖTTGER D.: 'The use of Platinum in the glass industry' GLASS May 1985, pages 177 - 178
  • STRNAD Z. ET AL: 'Studium Chovani Pozpustene Vody Ve Skle Ve Vztahu K. Tvoreni Sekundarnich Bublin V Tazne Peci' SKLAR A KERAMIK vol. 144, 1970, pages 144 - 148
  • 'LCD Display Seminar' LCD INTERNATIONAL 12 October 1995,
  • SCHOLES S. R.: 'Modern Glass Practice', 1975, R.A.N. pages 240 - 249
  • VARSHNEYA A. K.: 'Fundamentals of Inorganic Glasses', 1994, ACADEMIC PRESS INC., HARCOURT BRACE & COMPANY, PUBLISHERS pages 534 - 543
  • SHELBY J. E.: 'Gas diffusion in Solids and Melts', May 1996, ASM INTERNATIONAL pages 201 - 216
  • BUDD S.M. ET AL: 'The formation of gas bubbles in glass at high temperature' GLASS TECHNOLOGY vol. 3, no. 4, August 1962, pages 124 - 129
  • SHAND E.B.: 'Glass engineering handbook', 1958, MC GRAW HILL BOOK COMPANY pages 380 - 389
  


Description

Field of the Invention



[0001] This invention is directed to arsenic-free glass compositions and methods of making such glasses which are suitable for use as substrates in flat panel display devices without having to use arsenic containing materials.

Background of the Invention



[0002] Liquid crystal displays (LCDs) are passive flat panel displays which depend upon external sources of light for illumination. They are manufactured as segmented displays or in one of two basic configurations. The substrate needs (other than being transparent and capable of withstanding the chemical conditions to which it is exposed during display processing) of the two matrix types vary. The first type is intrinsic matrix addressed, relying upon the threshold properties of the liquid crystal material. The second is extrinsic matrix or active matrix (AM) addressed, in which an array of diodes, metal-insulator-metal (MIM) devices, or thin film transistors (TFTs) supplies an electronic switch to each pixel. In both cases, two sheets of glass form the structure of the display. The separation between the two sheets is the critical gap dimension, of the order of 5-10 µm.

[0003] Intrinsically addressed LCDs are fabricated using metal deposition techniques, typically at temperatures ≤350°C, followed by standard metal etching procedures. As a result, the substrate requirements therefor are often the same as those for segmented displays. Soda-lime-silica glass with a barrier layer has proven to be adequate for most needs. A high performance version of intrinsically addressed LCDs, the super twisted nematic (STN) type, has an added requirement of extremely precise flatness for the purpose of holding the gap dimensions uniform. Because of that requirement, soda-lime-silica glass made using the float glass manufacturing process must be polished. Such polishing processes are expensive and time consuming, and generate a large amount of glass particles which have the potential to negatively impact further processing of the glass sheets. Alternatively, glass can be formed using a process which does not require polishing, e.g. fusion downdraw.

[0004] Extrinsically addressed LCD's can be further subdivided depending upon the nature of the electrical switch located at each optical element (subpixel). Two of most popular types of extrinsically (or active matrix, AMLCD) addressed LCD's are those based on either amorphous (a-Si) or polycrystalline (poly-Si) silicon thin film transistors (TFT's).

[0005] U.S. Pat. No. 4,824,808 (Dumbaugh, Jr.) lists four desirable properties for a glass to exhibit in order to fully satisfy the needs of a substrate for extrinsically addressed LCD's:

First, the glass must be essentially free of intentionally added alkali metal oxide to avoid the possibility of alkali metal contamination of the TFT;

Second, the glass substrate must be sufficiently chemically durable to withstand the reagents used during the manufacture of the TFT;

Third, the expansion mismatch between the glass and the silicon present in the TFT array must be maintained at a relatively low level even as processing temperatures for the substrates increase; and

Fourth, the glass must be capable of being produced in high quality thin sheet form at low cost; that is, it must not require extensive grinding and polishing to secure the necessary surface finish.



[0006] That last requirement is most difficult to achieve inasmuch as it demands a sheet glass production process capable of producing essentially finished glass sheet. A process capable of meeting this requirement is a particular downdraw process known as the overflow downdraw, or fusion, sheet manufacturing process. The overflow downdraw process is described, for example, in U.S. Pat. No. 3,338,696 (Dockerty) and U.S. Pat. No. 3,682,609 (Dockerty). Fusion formed glass sheets, unlike float glass sheets, are sufficiently flat that they do not need to be polished after forming. Two glasses which meet the above requirements, Corning Incorporated Codes 7059 and 1737 sheet glass, are currently employed as substrates for extrinsically addressed LCD's. These glasses are made using the overflow downdraw process, and hence do not require polishing after forming.

[0007] Recent improvements in the resolution of extrinsically addressed LCD's have led to the development of a fifth glass requirement, that is, a high glass strain point. This property is used as an indication of the thermal shrinkage of the glass. As can be appreciated, the lower the strain point, the greater is this thermal shrinkage. Low thermal shrinkage is desirable for precise alignment during successive photolithographic and other patterning steps during the TFT processing. Consequently, glasses having higher strain points are generally preferred for extrinsically addressed LCD's, particularly those which employ poly-Si TFT technology. Thus, there has been considerable research to develop glasses demonstrating high strain points so that thermal shrinkage is minimized during device processing. Corning Code 1737 glass, which has the highest strain point (666° C) in the AMLCD substrate industry, is rapidly becoming an industry standard. Concurrent with their high strain points, these glasses often have high melting temperatures, e.g. on the order of 1550-1650° C.

[0008] Another technology termed "chip-on-glass" (COG) has further emphasized the need for the substrate glass to closely match silicon in thermal expansion. Thus, the initial LCD devices did not have their driver chips mounted on the substrate glass. Instead, the silicon chips were mounted remotely and were connected to the LCD substrate circuitry with compliant or flexible wiring. As LCD device technology improved and as the devices became larger and required finer resolutions, these flexible mountings became unacceptable, both because of cost and of uncertain reliability. This situation led to Tape Automatic Bonding (TAB) of the silicon chips. In that process the silicon chips and electrical connections to the chips were mounted on a carrier tape, that subassembly was mounted directly on the LCD substrate, and thereafter the connection to the LCD circuitry was completed. TAB decreased cost while improving reliability and increasing the permitted density of the conductors to a pitch of approximately 200 µm -- all significant factors. COG, however, provides further improvement over TAB with respect to those three factors. Hence, as the size and quality requirements of LCD devices increase, COG is demanded for those devices dependent upon the use of integrated circuit silicon chips. For that reason, the substrate glass preferably demonstrate a linear coefficient of thermal expansion closely matching that of silicon; i.e., a linear coefficient of thermal expansion (0° - 300°C) between about 32-46 X 10-7/°C, most preferably 32-40X10-7/°C.

[0009] Many of the glasses manufactured for flat panel display applications, particularly those which are formed by downdraw processes (e.g., the fusion or slot draw processes), are melted or formed using manufacturing equipment comprised of refractory metals, e.g. platinum or platinum alloys, particularly in the fining and conditioning sections of the process, where refractory metals are employed in order to minimize the creation of compositional in homogenieties and gaseous inclusions caused by contact of the glass with oxide refractory materials. In addition, many of these manufacturing processes employ arsenic as a fining agent. This is because arsenic is among the highest temperature fining agents known, meaning that, when added to the molten glass bath, it allows for O2 release from the glass melt even at high melting temperatures (e.g. above 1450°C). This high temperature O2 release, (which aids in the removal of gases during the melting and fining stages of glass production), coupled with a strong tendency for O2 absorption at lower conditioning temperatures, (which aids in the collapse of any residual gaseous inclusions in the glass), results in a glass product essentially free of gaseous inclusions. In addition, the oxidizing nature of the arsenic fining package allows for protection of the platinum based metal systems by preventing contamination as a result of tramp metals reduction. Other fining agents typically melt and release their oxygen far too early when added as fining agents to high melting temperature glasses and reabsorb O2 too late during the conditioning process, thereby disabling their fining abilities. From an environmental point of view, it would be desirable to find alternative methods of making such high melting point and strain point glasses without having to employ arsenic as a fining agent. It would be particularly desirable to find methods for making such glasses via downdraw (especially fusion-like) processes. Unfortunately, previous efforts at doing so have been hindered by the production of unacceptable amounts of bubbles in the glass. This has been a particular problem with glasses which employ refractory metals such as platinum or platinum containing alloys in their molten glass delivery systems. This is because platinum can cause an electrochemical reaction to occur with the glass which results in bubble formation on or near the platinum (commonly referred to as blistering) contacting region of the glass.

Summary of the Invention



[0010] We have found that by maintaining a low amount of water in the glass during the glass forming process, other fining constituents which are normally less efficient at high melting temperatures (melting temperature is defined herein as the temperature at which the glass exhibits a viscosity of 20 Pa.s (200 poise), e.g. Sb2O3, CeO2, SnO2, Fe2O3, and mixtures thereof, can be employed if needed in place of As2O3 to facilitate successful fining of the glass. Maintaining a low amount of water in the glass thus enables the formation of high melting point glasses (i.e. glasses wherein the temperature at which the viscosity corresponds to 20 Pa.s (200 poise) is greater than about 1500°C) which are essentially or substantially arsenic-free. By substantially arsenic-free it is meant that such glasses have less than 0.02 mole percent As2O3 (such amounts are normally present as a result of raw material impurity). The invention also enables the formation of such high melting point glasses using manufacturing systems which employ platinum or platinum containing alloys which contact the glass during the melting or forming steps of the manufacturing process. These methods are particularly suited for forming glasses which are formed using a downdraw process, such as, for example, Coming Code 1737.

[0011] According to one aspect, the present invention provides a method according to claim 1.

[0012] One manner of measuring the water content in the glass is by measuring beta-OH (β-OH). β-OH, as used herein, is a measure of the hydroxyl content in the glass as measured by IR spectroscopy, and is determined using the fundamental hydroxyl absorption, which for this material occurs at about 2809 nm. The β-OH is the linear absorption coefficient (absorbance/mm thickness) of the material at 2809 nm. The equation below shows how β-OH is calculated from the sample's IR transmittance spectrum.

where X is the sample thickness in millimeters, T1 is the sample transmittance at the reference wavelength (2600 nm) and T2 is the minimum sample transmittance of the hydroxyl absorption wavelength (2809 nm). The reference wavelength compensates for signal loss due to surface reflections, scatter, and refraction in the sample, and is chosen from a region of no absorption and as close as possible to the absorption wavelength of interest.

[0013] In a preferred embodiment of the present invention for forming low arsenic containing glasses via a downdraw sheet forming process, the batch constituents are selected so that the resultant glass has a water content therein, as indicated by β-OH level, which is less than 0.35 mm-1

[0014] The glasses formed in accordance with the invention are essentially free of As2O3 in the resultant glass. We have found that silicate glasses (especially aluminosilicate and borosilicate glasses) formulated to result in such β-OH values in the resultant formed glass can be fined using less than 0.02 mole percent As2O3, expressed as the amount of As2O3 present in the resultant glass. Even when formed using a downdraw process employing a platinum or platinum alloy based metal delivery system, such glasses can be formed without any significant amounts of electrochemical blistering occurring. In the most preferred embodiment, in order to facilitate fining of these glasses, Sb2O3, CeO2, SnO2, Fe2O3, and mixtures thereof are added to such glasses alone or in combination, in an amount between 0.02-2 mole percent. In a preferred embodiment, Sb2O3 is added in an amount from 0.02 to 1 mole percent, preferably from 0.2 to 0.5 mole percent.

[0015] The water content or β-OH value of the glass can be reduced in a variety of ways. For example, simply by appropriate selection of batch materials, the water level in the glass can be adjusted to some extent. Further water reduction can be achieved by adding drying agents, such as halide materials. For example, halide containing materials may be added in an amount which results in the final glass having a composition between about 0.1 to 4 mole percent halide, more preferably 0.1 to 2 mole percent halide, and most preferably about 0.1 percent halide. In a preferred embodiment for forming the glass composition disclosed in the example, 0.4 mole percent chlorine is batched, e.g. as CaCl2, resulting in 0.15 to 0.19 mole percent Cl in the resultant glass.

[0016] Additionally, it is desirable to keep the sum of the partial pressures of all dissolved volatile gases below 1 atmosphere. One method of facilitating this result is by limiting the amount of sulfur in the resultant glass by appropriate selection of batch materials. Preferably, selection of batch materials should be made so that the sulfur, expressed as SO3, in the resultant formed glass is as low as possible, preferably less than 100 ppm, more preferably less than 50, and most preferably less than 25 ppm.

[0017] The methods in accordance with the present invention are particularly advantageous in forming high strain point aluminoborosilicate glasses having a composition, expressed in terms of mole percent on the oxide basis, of
SiO2 60-73 MgO 0-5
Al2O3 8-14 CaO 1-13
B2O3 5-17 SrO 0-8
TiO2 0-5 BaO 0-14
Ta2O5 0-5    


[0018] More preferably, the base glass has a composition, expressed in terms of mole percent on the oxide basis, of
SiO2 64-70 MgO 0-5
Al2O3 9.5-14 CaO 3-13
B2O3 5-12 SrO 0-5.5
TiO2 0-5 BaO 2-8
Ta2O5 0-5 MgO+CaO+SrO+BaO 10-20.


[0019] With the exception of the low water content, glasses within this preferred composition range are disclosed, for example, in U.S. Patent No. 5,374,595. Preferred glasses formed in accordance with the present invention exhibit linear coefficients of thermal expansion over the temperature range of 0°-300°C from 32 to 46 x 10-7/°C, more preferably from 32 to 40 x 10-7/°C, strain points higher than 630°C, more preferably higher than 640°C, and most preferably greater than 650°C, liquidus temperatures less than 1125°C, liquidus viscosities which are sufficient to enable formation by a downdraw manufacturing process, preferably greater than 40,000 Pa.s (400,000 poises), and more preferably greater than 60,000 Pa.s (600,000 poises), a weight loss of less than 2 mg/cm2 after immersion for 24 hours in an aqueous 5% by weight HCI solution at 95°C, long term stability against devitrification at melting and forming temperatures and melting viscosities of 20 Pa.s (200 poises) at less than 1675°C. The methods of the present invention may be employed in glasses having compositions within the boundaries set forth above, such as, for example, glasses listed as examples in US Patent No 5,374,595, thereby enabling such glasses to be fined and formed without having to use arsenic.

[0020] In the most preferred glasses, in addition to the low water level, the level of Al2O3 will exceed that of B2O3 and in the most preferred glasses the composition will consist essentially, expressed in terms of mole percent, of about
SiO2 65-69 MgO 1-5
Al2O3 10-12 CaO 3-9
B2O3 7-10 SrO 1-3
TiO2 0-3 BaO 2-5
Ta2O5 0-3 MgO+CaO+SrO+BaO 11-16
Preferably, the ratio Al2O3: B2O3 in such glasses is greater than 1.

[0021] The invention thus enables the formation of silicate sheet glasses having high melting points (greater than 1500°C), as well as the formation of silicate sheet glasses using manufacturing processes which employ refractory metals such as platinum in their forming regions. Forming region, as used herein, refers to the portion of the manufacturing process prior to which the final form of the glass is imparted to the glass, and includes the melting, conditioning, and fining portions of the manufacturing process.

BRIEF DESCRIPTION OF THE DRAWINGS



[0022] 

Figure 1 illustrates a humidity controlled enclosure for use in accordance with the present invention.


DETAILED DESCRIPTION OF THE INVENTION



[0023] The present invention relates to methods of making silicate glass compositions while employing little or no arsenic. The preferred glasses are aluminosilicate or borosilicate glasses. The manufacturing processes for such glasses is via a downdraw sheet manufacturing process. As used herein, downdraw sheet manufacturing process refers to any form of glass sheet manufacturing process in which glass sheets are formed while traveling in a downward direction. In the fusion or overflow downdraw forming process, molten glass flows into a trough, then overflows and runs down both sides of a pipe, fusing together at what is known as the root (where the pipe ends and the two overflow portions of glass rejoin), and is drawn downward until cool. The overflow downdraw sheet manufacturing process is described, for example, in U.S. Patent No. 3,338,696 (Dockerty) and U.S. Patent No. 3,682,609 (Dockerty). One advantage to the fusion forming process is that the glass sheet can be formed without the glass surface contacting any refractory forming surfaces. This provides for a smooth, contaminant-free surface. In addition, this technique is capable of forming very flat and thin sheets to very high tolerances. Consequently, fusion formed glass sheets, unlike float glass sheets, do not require costly polishing steps for TFT and STN LCD applications.

[0024] Other forms of downdraw sheet forming techniques include the slot draw and redraw forming techniques. In the slot draw technique, molten glass flows into a trough having a machined slot in the bottom The sheets of glass are pulled down through the slot. The quality of the glass is obviously dependent on the accuracy of the machined slot. Redraw processes generally involve preforming a glass composition into a block of some shape, then reheating and drawing the glass downwardly into a thinner sheet product.

[0025] The glasses have less than 0.02 mole percent As2O3 (an amount which is normally present as a result of raw material impurity).

[0026] It is believed that the method described herein are applicable to a wide variety of glasses, particularly those formed via downdraw manufacturing processes which employ platinum in their forming regions. Application of the invention to Coming Code 1737 glass, for example, is demonstrated as follows, with reference to Table I below. These glasses were prepared in a laboratory-scaled continuous melting unit similar to the overflow downdraw melting units typically used for commercial production of this type of product. This experimental melting unit employs a platinum/rhodium alloy refractory metal delivery system, wherein the molten glass contacts the platinum alloy metal. Example 4 of Table I corresponds closely to commercially available Coming Code 1737 glass, and was fined accordingly using an amount of arsenic which resulted in about 0.4 mole percent being present in the resultant glass. Examples 1, 2, and 3 illustrate the effect that decreasing amounts of water has on these compositions. As the β-OH values of the glass decrease, so do the gaseous inclusions (Inc/unit weight) in glass. In these examples, gaseous inclusions are primarily a result of electrochemical blistering caused by the platinum alloy pipes which deliver the molten glass, and consequently accurately mimic the manufacturing processes employing metals such as platinum. Gaseous inclusions were measured on a per unit weight basis over a period of two to three days. As illustrated by the examples, the inclusions per unit weight dropped significantly with each decrease of β-OH value. The fact that this was done without having to use As2O3 as a fining agent makes this accomplishment significant.

[0027] Table I records similar glass compositions of varying β-OH levels, expressed in terms of parts by weight on the oxide basis, illustrating the invention. Inasmuch as the sum of the individual constituents totals or very closely approximates 100, for all practical purposes the reported values may be deemed to represent weight percent. Table IA records the same glass compositions expressed in terms of mole percent on the oxide basis. The actual batch ingredients may comprise any materials, either oxides or other compounds, which, when melted together with the other batch components, will be converted into the desired oxide in the proper proportions. For example, SrCO3 and CaCO3 can provide the source of SrO and CaO, respectively. In Example 3, Cl was added as CaCl2 at a level of 0.2 weight percent in excess of the batch, resulting in about 0.087 weight percent Cl retained in the resultant glass. About 2.7 weight percen: water in excess of the batch was added to Examples 1 and 4.

[0028] Table I also lists measurements of several chemical and physical properties determined on the glasses in accordance with techniques conventional in the glass art. Thus, the linear coefficient of thermal expansion (CTE) over the temperature range 0°-300°C. expressed in terms of X10-7/°C., and the softening point (S.P.), annealing point (A.P.), and strain point (St.P.) expressed in terms of °C., were determined by fiber elongation. The durability (HCl Dur.) in HCl was determined by measuring the weight loss (mg/cm2) after immersion in a bath of aqueous 5% by weight HCl at 95°C. for 24 hours.

[0029] The liquidus temperatures (Liq.Temp.) of the glasses were measured using the standard liquidus method, which involves placing crushed glass particles in a platinum boat, placing the boat in a furnace having a region of gradient temperatures, heating the boat in an appropriate temperature region for 24 hours, and determining by means of microscopic examination the highest temperature at which crystals appear in the interior of the glass. The melting temperature (M.P., in °C) (defined as the temperature at which the glass melt demonstrates a viscosity of 20 Pa.s (200 poises) was calculated employing the Fulcher equation as fit to the high temperature viscosity data. The liquidus viscosity (Liq. Vis.) was also calculated using the Fulcher equation coefficients, and is expressed in terms of x100,000 Pa.s (x1,000,000 poises). SnO2 was added to examples 1-3 in an amount suitable to replicate melting conditions in production, wherein the tin electrodes employed in melting the glass result in residual tin oxide in the resultant glass.
TABLE I
 1234
SiO2 59.49 58.82 58.91 57.07
Al2O3 16.4 16.7 16.58 16.46
B2O3 8.29 8.3 8.21 8.35
MgO 0.737 0.739 0.765 0.77
CaO 4.109 4.111 4.116 4.21
SrO 1.889 1.883 1.887 1.88
BaO 8.6 8.59 8.61 9.49
SnO2 0.062 0.09 0.092  
Sb2O3 1.857 1.852 1.856 0
As2O3 0 0 0 1.11
% Added H2O 2.70 0 0 2.7
Cl 0 0 0.087 0
β-OH 0.481 0.41 0.358 0.440
Inc/kg (Inc/lb) 33.5 (15.2) 4.54 (2.06) 0.57 (0.26) 0.46 (0.21)
S.P. 973 976 977 968
M.P. 1641 1638 1644 1625
St.Pt. 660 665 664 658
A.P. 717 719 720 714
Liq.Temp. 1080 1080 1090 1050
Liq.Vis. 1.37 1.4 1.06 2.51
HCl Dur. 0.46 0.44 0.45 0.61
CTE 36.3 36.6 36.6 37.6
TABLE IA
 1234
SiO2 68.6 68.2 68.3 67.3
Al2O3 11.1 11.4 11.3 11.4
B2O3 8.25 8.31 8.22 8.5
MgO 1.27 1.28 1.32 1.35
CaO 5.08 5.11 5.11 5.32
SrO 1.26 1.27 1.27 1.28
BaO 3.89 3.9 3.91 4.39
SnO2 0.03 0.04 0.04 --
Sb2O3 0.44 0.44 0.44 --
As2O3       0.4


[0030] These examples, which are meant to be illustrative and not limiting, demonstrate that aluminoborosilicate glasses such as those falling within the compositional ranges described above can be made using downdraw manufacturing processes.

[0031] The glass is formed in a manufacturing system which employs platinum, or an alloy thereof in contacting relationship with the glass, and the partial vapor pressure of hydrogen outside this portion of the manufacturing system relative to the partial vapor pressure of hydrogen in the glass or inside that manufacturing vessel. The partial pressure of hydrogen outside the vessel can be controlled, for example, by enclosing part of the vessel in an enclosure, and varying the partial pressure of hydrogen, or the dew point, inside the enclosure as desired. By so controlling the relative partial pressures of hydrogen inside versus outside the platinum containing portion of the glass manufacturing system, we can control, and if desired, reduce the amount of surface blisters which were heretofore problematic in such glass manufacturing systems which employed platinum. The partial vapor pressure of hydrogen inside and outside the system can be controlled, for example, by controlling the partial vapor pressure of water inside and outside the system.

[0032] Platinum is desirable for use in glass forming vessels primarily because of its inert properties. However, platinum enables hydrogen migration to occur from the glass melt through the platinum, thereby creating an oxygen rich layer at the glass/platinum interface which results in surface blisters. Consequently, for the platinum glass manufacturing vessels, it is most desirable to maintain the relative inside and outside partial pressures of hydrogen to be substantially equal, so that no migration of hydrogen, either in or out of the glass manufacturing vessel, occurs. However, if any migration is to occur, it is more desirable that it occur from the outside in, and thus in another embodiment the partial pressure of hydrogen outside the platinum manufacturing vessel is maintained at a higher level then is present inside the vessel.

[0033] In another preferred embodiment, a measurement device is used to measure the relative partial pressures of hydrogen inside versus outside the manufacturing vessel, and the humidity or dew point outside the vessel is then controlled accordingly. A preferred such measurement apparatus is shown in Figure 1. Platinum vessel 10 includes platinum walls 12 through which molten glass 13 is flowing. The platinum walls 12 of vessel 10 can have any shape (e.g. round or rectangular in cross-section), and the direction of flow of the molten glass through vessel 10 is not important. A platinum flag electrode 14 is immersed into the molten glass. By platinum flag, it is meant a flat sheet of platinum, so that the both sides of the platinum contact the molten glass, and therefore the flag does not experience hydrogen permeation. Also immersed into the molten glass 13 is a platinum tube 20, the interior of which is in contact with the atmosphere outside platinum vessel 10. Both flag electrode 14 and the platinum tube 20 are isolated from the platinum manufacturing vessel 10 via an insulating material 24. The flag electrode 14 and platinum tube 20 are then connected as illustrated in Fig. 1. Controller 15 is used to adjust the voltage from variable d.c. power source 16 necessary to maintain the target potential between electrodes 14 and 20. The current necessary to sustain this voltage is then read from ammeter 17 as an indicator of the flow of hydrogen through the platinum wall 20, and thus platinum wall 12 as well. For example, an increase in current indicates a net decrease in the rate of hydrogen migration out of the glass and into the atmosphere outside the Pt system. Conversely, a decrease in current would indicate a net increase in the rate of hydrogen migration out of the glass and into the atmosphere.

[0034] The apparatus illustrated in Fig. 1 is enclosed by enclosure 30 (shown schematically), which enables the control of the partial pressure of hydrogen surrounding the platinum vessel 10. Thus, if the measurement system described above indicates a change from the target potential, the humidity inside enclosure 30 can be adjusted to correct for this change. Other variations within the scope of the claimed invention will be apparent to those skilled in the art. For example, the potential between flag 14 and platinum tube 20 could be monitored simply by a voltage regulator, and a signal produced relative to the voltage measured, the signal then being sent to a control device capable of increasing or decreasing the humidity or dew point in the enclosure in response to the signal. In addition, while in Fig. 1, only a portion of the vessel 10 is enclosed, in a preferred embodiment the entire portion of the manufacturing process employing platinum vessels is enclosed. Clearly, a similar control system can be devised if the partial pressure of hydrogen is varied directly.

[0035] Such control of the relative partial pressures of hydrogen, as well as the measuring device described above, are explained in more detail in U.S. Patent No 5,785,726.


Claims

1. A method of making a silicate glass comprising melting and forming a silicate sheet glass using a sheet forming downdraw glass manufacturing process in which the glass is contacted with platinum or a platinum alloy during the melting or forming process, characterised in that the batch constituents are selected so that the resultant glass contains less than 0.02 mole percent arsenic expressed as As2O3, and the β-OH of said glass is below 0.4 mm-1,where β-OH = (1/X)log10 (T1/T2) where X is the thickness in millimetres of a sample of the glass, T1 is the sample transmittance at the reference wavelength of 2600 nm and T2 is the minimum sample transmittance of the hydroxyl absorption wavelength of 2809 nm, wherein the resultant glass comprises an aluminoborosilicate glass, expressed in terms of mole percent on the oxide basis, having:
SiO2 60-73 MgO 0-5
Al2O3 8-14 CaO 1-13
B2O3 5-17 SrO 0-8
TiO2 0-5 BaO 0-14
Ta2O5 0-5    
, and wherein the resultant glass is essentially free of alkali metal oxides and exhibits a strain point higher than 630°C., and a linear coefficient of thermal expansion over the temperature range 0°-300°C. between 32-46X10-7/°C.
 
2. A method according to claim 1, wherein said downdraw process in said melting step is a fusion process.
 
3. A method according to claim 1or 2, wherein the batch constituents and process control variables in said melting step are adjusted so that the β-OH value is below 0.35 mm-1.
 
4. A method according to any of claims 1 to 3, wherein said melting step further comprises employing a fining agent therein.
 
5. A method according to claim 4, wherein the fining agent is selected from Sb2O3, CeO2, SnO2, Fe2O3, halide containing compounds, and mixtures thereof.
 
6. A method according to any of claims 1 to 5, wherein the melting step comprises employing antimony containing material in an amount which results in the resultant glass having from 0.02 to 1 mole percent Sb2O3.
 
7. A method according to any of claims 1 to 6, wherein said melting step comprises employing a halide containing compound in an amount sufficient to result in 0.1 to 2 mole percent halide, in the resultant glass.
 
8. A method according to claim 7, wherein the halide is chloride.
 
9. A method according to claim 1, wherein the glass exhibits a strain point higher than 650°C.
 
10. Use of glass made by a method according to any of claims 1 to 9 as substrate in a flat panel display device.
 


Ansprüche

1. Verfahren zur Herstellung eines Silikatglases umfassend das Schmelzen und Formen eines Silikat-Flachglases unter Verwendung eines Flachglas-bildenden Downdraw-Glasherstellungsverfahrens, in dem das Glas während des Schmelz- oder Formprozesses mit Platin oder einer Platinlegierung in Kontakt gebracht wird,
dadurch gekennzeichnet,
dass die Ansatzbestandteile so ausgewählt werden, dass das sich ergebende Glas weniger als 0,02 Molprozent Arsen, ausgedrückt als As2O3, enthält, und das β-OH des Glases unter 0,4 mm-1 liegt, wobei β-OH = (1/X)log10 (T1/T2) ist, wobei X die Dicke einer Glasprobe in Millimetern ist, T1 die Probendurchlässigkeit bei der Referenzwellenlänge 2600 nm ist und T2 die minimale Probendurchlässigkeit der Hydroxylabsorptions-Wellenlänge 2809 nm ist, wobei das sich ergebende Glas ein Aluminoborosilikat-Glas enthält, umfassend, ausgedrückt in Molprozent auf der Oxid-Basis:
SiO2 60-73 MgO 0-5
Al2O3 8-14 CaO 1-13
B2O3 5-17 SrO 0-8
TiO2 0-5 BaO 0-14
Ta2O5 0-5    
und wobei das sich ergebende Glas im Wesentlichen frei von Alkalimetalloxiden ist, und einen Spannungspunkt oberhalb von 630°C aufweist, sowie einen linearen Wärmeausdehnungskoeffizienten über den Temperaturbereich von 0°-300°C von 32-46 x 10-7/°C.
 
2. Verfahren nach Anspruch 1, wobei das Downdraw-Verfahren in dem Schmelzschritt ein Schmelzprozess ist.
 
3. Verfahren nach Anspruch 1 oder 2, wobei die Ansatzbestandteile und Verfahrenskontrollvariablen in dem Schmelzschritt eingestellt werden, so dass der β-OH Wert unter 0,35 mm-1 liegt.
 
4. Verfahren nach einem der Ansprüche 1 bis 3, wobei der Schmelzschritt weiterhin die Verwendung eines Läuterungsmittels darin umfasst.
 
5. Verfahren nach Anspruch 4, wobei das Läuterungsmittel aus Sb2O3, CeO2, SnO2, Fe2O3, Halogenid enthaltenden Verbindungen und Gemischen davon ausgewählt wird.
 
6. Verfahren nach einem der Ansprüche 1 bis 5, wobei der Schmelzschritt die Verwendung eines Antimon enthaltenden Materials in einer Menge umfasst, welche dazu führt, dass das sich ergebende Glas 0,02 bis 1 Molprozent Sb2O3 aufweist.
 
7. Verfahren nach einem der Ansprüche 1 bis 6, wobei der Schmelzschritt die Verwendung einer Halogenid enthaltenden Verbindung in einer Menge umfasst, die ausreicht, um zu 0,1 bis 2 Molprozent Halogenid in dem sich ergebenden Glas zu führen.
 
8. Verfahren nach Anspruch 7, wobei das Halogenid Chlorid ist.
 
9. Verfahren nach Anspruch 1, wobei das Glas einen Spannungspunkt oberhalb von 650°C aufweist.
 
10. Verwendung eines Glases, das durch ein Verfahren gemäß einem der Ansprüche 1 bis 9 hergestellt ist, als Substrat in einer Flachbildschirmanzeigevorrichtung.
 


Revendications

1. Procédé pour préparer un verre de silicate comprenant la fusion et le formage d'un verre de silicate en feuille au moyen d'un processus de fabrication de verre en feuille par étirage par le bas dans lequel le verre est mis au contact de platine ou d'un alliage de platine au cours du processus de fusion ou de formage, caractérisé en ce que les constituants du mélange sont sélectionnés afin que le verre résultant contienne moins de 0,02 pourcent molaire d'arsenic exprimé comme As2O3, et que le β-OH dudit verre soit inférieur à 0,4 mm-1, avec β-OH = (1/X)log10 (T1/T2) , X étant l'épaisseur en millimètres d'un échantillon du verre, T1 étant la transmittance de l'échantillon à la longueur d'onde de référence de 2600 nm et T2 est la transmittance minimum de l'échantillon à la longueur d'onde d'absorption de l'hydroxyle de 2809 nm, dans lequel le verre résultant comprend un verre d'aluminoborosilicate, exprimé en termes de pourcentage molaire rapporté aux oxydes, renfermant :
SiO2 60 - 73 MgO 0 - 5
Al2O3 8 - 14 CaO 1 - 13
B2O3 5 - 17 SrO 0 - 8
TiO2 0 - 5 BaO 0 - 14
Ta2O5 0 - 5    
et dans lequel le verre résultant est essentiellement exempt d'oxydes de métaux alcalins et exhibe un point de contrainte supérieur à 630° C, et un coefficient linéaire d'expansion thermique sur la gamme de températures de 0° à 300° C entre 32 et 46 x 10-7/°C.
 
2. Procédé selon la revendication 1, dans lequel ledit processus par étirage par le bas dans ladite étape de fusion est un processus de fusion.
 
3. Procédé selon la revendication 1 ou la revendication 2, dans lequel les constituants du mélange et les variables de commande du processus dans ladite étape de fusion sont réglés afin que la valeur β-OH soit inférieure à 0,35 mm-1.
 
4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel ladite étape de fusion comprend en outre l'utilisation d'un agent d'affinage dans celle-ci.
 
5. Procédé selon la revendication 4, dans lequel l'agent d'affinage est sélectionné parmi Sb2O3, CeO2, SnO2, Fe2O3, des composés contenant des halogénures, et des mélanges de ceux-ci.
 
6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel l'étape de fusion comprend l'utilisation d'un matériau contenant de l'antimoine dans une quantité telle que le verre résultant renferme de 0,02 à 1 pourcent molaire de Sb2O3.
 
7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel l'étape de fusion comprend l'utilisation d'un composé contenant un halogénure dans une quantité suffisante pour résulter en 0,1 à 2 pourcents molaires d'halogénure dans le verre résultant.
 
8. Procédé selon la revendication 7, dans lequel l'halogénure est du chlorure.
 
9. Procédé selon la revendication 1, dans lequel le verre exhibe un point de contrainte supérieur à 650° C.
 
10. Utilisation d'un verre préparé par un procédé selon l'une quelconque des revendications 1 à 9 comme substrat dans un dispositif d'affichage à écran plat.
 




Drawing






REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description