MX2008008939A - Colored glass compositions - Google Patents

Abstract

A glass composition is disclosed. The glass composition includes base glass composition including SiO2from 65 to 75 weight percent, Na2O from 10 to 20 weight percent, CaO from 5 to 15 weight percent, MgO from 0 to 5 weight percent, Al2O3from 0 to 5 weight percent, K2O from 0 to 5 weight percent, and BaO from 0 to 1 weight percent, and a colorant and property modifying portion including total iron from up to 0.02 weight percent, CeO2from 0.05 weight percent to 1.5 weight percent, CoO up to 50 PPM, Se up to 15 PPM, Cr2O3up to 500 PPM, CuO up to 0.5 weight percent, V2O5up to 0.3 weight percent, TiO2up to 1 weight percent, NiO up to 200 PPM, Er2O3up to 3 weight percent, MnO2up to 0.6 weight percent, and Nd2O3up to 2 weight percent, wherein the glass composition has a redox ratio up to 0.55.

Description

COLORED GLASS COMPOSITIONS FIELD OF THE INVENTION The present invention relates to glass compositions, in particular to glass compositions that include minimal amounts of dyes and other property modifying materials but which exhibit intense colors. BACKGROUND OF THE INVENTION Glass substrates are used in various applications such as automotive applications, architectural applications, aerospace applications, etc. Glass substrates are also used in furniture (ie, tabletops, shelves, etc.) and appliances. Depending on the end use of the glass substrate it is desirable that the glass substrate exhibit certain (a) aesthetic properties, such as, but not limited to, color and (b) solar control properties such as, but not limited to, total solar energy transmittance ("TSET"), visible light transmittance (Lta), etc. The aesthetic properties and solar control properties of a glass substrate can be modified in different ways. A first way involves depositing a coating on the surface of a glass substrate. A second way involves changing the chemical composition (ie, the type of materials that make up the glass composition and / or the percentages by weight of the various materials in the glass composition) that make up the glass substrate. Occasionally, colorants and / or other materials capable of modifying the solar properties of the glass composition are added to a well-known base glass composition, such as a soda-lime-silica base glass composition, to provide a substrate of glass capable of presenting unique performance properties. Although the effect of a dye or a material capable of modifying the solar properties of the glass composition can be known, (for example, it is known that adding FeO to a base glass composition increases the infrared absorption.

(IR) of the glass composition), the essence of the invention is to use various dyes and / or materials capable of modifying the solar properties of the glass composition, each dye or material capable of producing a unique effect individually to achieve a combination of properties collectively. In accordance with the present invention, specific materials capable of modifying the aesthetic and / or solar properties of a glass composition in specific amounts are added to a soda-lime-silica base glass composition to provide colored glass substrates. The glass substrates of the present invention may have various colors such as, but not limited to, blue, green, yellow, bronze and gray. The glass substrates of the present invention may also have a Lta equal to or greater than 80% which is generally desirable for glass substrates used in furniture and appliances. SUMMARY OF THE INVENTION In a non-limiting embodiment, the present invention is a glass composition comprising a base glass composition comprising: Si02 from 65 to 75 weight percent, Na20 from 10 to 20 weight percent, CaO from the 5 to 15 weight percent, MgO 0 to 5 weight percent A1203 from 0 to 5 weight percent, K20 from 0 to 5 weight percent and BaO from 0 to 1 weight percent and a dye and a property modification part comprising: total iron up to 0.02 weight percent, Ce02 from 0.05 to 1.5 weight percent, CoO up to 50 ppm, Se up to 15 ppm, Cr203 up to 500 ppm, CuO up to 0.5 percent by weight, V2Os up to 0.3 percent by weight, Ti02 up to 1 percent by weight, NiO up to 200 ppm, Er203 up to 3 percent by weight, Mn02 up to 0, 6 weight percent and Nd20 up to 2 weight percent, in which the glass composition has a redox ratio up to 0.55. In another non-limiting embodiment, the present invention is a glass sheet comprising a glass composition including: Si02 65 to 75 weight percent, Na20 from 10 to 20 weight percent, CaO from 5 to 15 weight percent, MgO from 0 to 5 weight percent, A1203 from 0 to 5 weight percent, K20 from 0 to 5 weight percent and BaO from 0 to 1 weight percent and a dye and a property modification part comprising: total iron up to 0.02 weight percent, Ce02 from 0.05 to 1.5 weight percent, CoO up to 50 ppm, up to 15 ppm, Cr203 up to 500 ppm, CuO up to 0.5 percent by weight, V2Os up to 0.3 percent by weight, Ti02 up to 1 percent by weight, NiO up to 200 ppm, Er203 up to 3 weight percent, MnO2 up to 0.6 weight percent and Nd203 up to 2 weight percent, in which the glass composition has a redox ratio up to 0.55 and in which the sheet of glass presents a Lta equal to or greater than 70 percent at a thickness of 0,223 inches (5,664 mm). In another non-limiting composition the present invention is a method of preparing a glass composition comprising: processing raw materials to form a glass composition comprising: Si02 from 65 to 75 weight percent, Na20 from 10 to 20 percent by weight, CaO from 5 to 15 percent by weight, MgO from 0 to 5 percent by weight, A1203 from 0 to 5 percent by weight, K20 from 0 to 5 percent by weight and BaO from 0 to 1 percent by weight and a dye and a property modification part comprising: total iron up to 0.02 weight percent, Ce02 from 0.05 weight percent to 1.5 weight percent, CoO up to 50 ppm, Up to 15 ppm, Cr203 up to 500 ppm, CuO up to 0.5 weight percent, V205 up to 0.3 weight percent, Ti02 up to 0.1 weight percent, NiO up to 200 ppm, Er203 up 3 percent by weight, Mn02 up to 0.6 percent by weight and Nd203 up to 2 percent by weight, in which the glass composition has a proportion of Redox ion up to 0.55. DETAILED DESCRIPTION OF THE INVENTION As used herein, all numbers expressing dimensions, physical characteristics, processing parameters, amounts of ingredients, reaction conditions and the like used in the specification and the claims should be understood as modified in all cases by the term "approximately". Accordingly, unless otherwise indicated, the numerical values indicated in the following specification and claims vary depending on the desired properties intended by the present invention. Finally, and not as an attempt to limit the application of the doctrine of equivalent to the scope of the claims, each numerical value must be understood at least in light of the number of significant digits presented and applying ordinary rounding techniques. In addition, all the intervals described in that document should be understood as included in the start and end values of the interval and all the subintervals contained within it. For example, an indicated range of "1 to 10" should be considered to include any of the subintervals between (and including) the minimum value of 1 and the maximum value of 10; that is, all subintervals that start with a minimum value of 1 or greater and end with a maximum value of 10 or less, for example 1.0 to 3.8, 6.6 to 9.7 and 5.5 to 10. The glass composition of the present invention comprises a part of base glass and colorants and materials capable of modifying the performance properties of glass. Both dyes and materials capable of modifying the solar control properties of glass are referred to herein as "dyes and materials for modifying the properties". Accordingly, the present invention the base glass part includes the components in the amounts shown in Table 1 below. Table 1. Part of base glass The base glass part described is referred to in the art as "soda-lime-silica" glass composition. In accordance with the present invention, various colorants and materials capable of modifying the solar performance properties of glass are added to the base glass composition. The dyes and property modification materials included in the glass composition of the invention include: iron oxides (both ferric oxide (Fe203) and ferrous oxide (FeO)) and cerium oxide (Ce02). According to the present invention, iron can be present in the glass composition both as ferric oxide (Fe203) and ferrous oxide (FeO). As is known in the art, Fe203 is a strong absorber of ultraviolet radiation and is a yellow dye. As is well known in the art, FeO is a strong absorber of infrared radiation and is a blue dye. The "total iron" present in the glass composition of the invention is expressed in terms of the percentage by weight of "Fe203 present in the glass composition according to the conventional technique in the industry." This does not imply that all the iron present in the composition of glass is in the form of Fe203 In accordance with the present invention, the total iron in the glass composition of the present invention varies up to and including 0.02 percent by weight based on the total weight of the glass composition, for example, from 0.05 to 0.02 weight percent The amount of iron present in the ferrous state in the glass composition of the present invention is expressed in terms of the weight percentage of "FeO" present in the composition. As the usual practice in the industry, although the amount of iron in the ferrous state is expressed as FeO, the total amount in the ferrous state may not actually be present in the glass as FeO. The glass composition of the present invention has a certain "redox ratio". As used herein, the "redox ratio" is the amount of iron in the ferrous state (expressed as "FeO") divided by the amount of total iron (expressed as "Fe203"). The glass compositions according to the present invention have a redox ratio of up to 0.55, for example 0.05 to 0.525 or 0.1 to 0.5. In accordance with the present invention, the glass composition of the present invention contains Ce02 in an amount ranging from 0.05 weight percent to 1.5 weight percent, for example 0.50 to 1.25, or from 0.75 weight percent to 1.0 weight percent where the weight percentage is based on the total weight of the glass composition. Ce02 is known in the art as a UV absorber. Ce02 is also known in the art as a powerful oxidizing agent that oxidizes the iron present in the raw materials to form Fe203, which is a less potent dye than FeO.

In various non-limiting embodiments, the glass composition of the present invention may include one or more of the following optional colorants and other property modifying materials that are present primarily to determine the color presented by the glass composition: cobalt oxide ( CoO), selenium (Se), chromium oxide (Cr203), copper oxide (CuO), vanadium oxide (V2? 5), titania (Ti02), nickel oxide (NiO), erbium oxide (Er203), manganese oxide (Mn02) and neodymium oxide (Nd203). According to the present invention, the glass composition can contain CoO in an amount of up to 50 ppm, for example, from 2 ppm to 35 ppm or from 5 ppm to 25 ppm. CoO functions as a blue dye and does not exhibit appreciable infrared or ultraviolet radiation absorption properties. In accordance with the present invention, the glass composition may contain Se in an amount of up to 15 ppm, for example 3 ppm to 14 ppm or 5 ppm to 12 ppm. The Se is known in the art as an ultraviolet and infrared radiation absorbing dye that confers a pink or brown color (the exact color depends on the valence state) to the soda-lime-silica glass. In accordance with the present invention, the glass composition can contain Cr203 in an amount of up to 500 ppm, for example from 10 ppm to 300 ppm, or from 20 ppm to 200 ppm. Cr203 is known in the art as a green dye. According to the present invention, the glass composition can contain CuO in an amount of up to 0.5 weight percent, for example up to 0.3 weight percent or up to 0.1 weight percent, where the percentage by weight is based on the total weight of the glass composition. CuO is known in the art as a blue dye. According to the present invention, the glass composition may contain V2O5 in an amount of up to 0.3 weight percent, for example up to 0.2 weight percent, or up to 0.1 weight percent , where the percentage by weight is based on the total weight of the glass composition. V2O5 is known in the art as a green dye. According to the present invention, the glass composition may contain Ti02 in an amount of up to 1 weight percent, for example up to 0.8 weight percent or up to 0.6 weight percent, where the Weight percentage is based on the total weight of the glass composition. Ti02 is known in the art as a yellow dye and an ultraviolet radiation absorber. In accordance with the present invention, the glass composition may contain NiO in an amount of up to 200 ppm, for example 5 ppm at 100 ppm or from 10 ppm to 50 ppm. Ni02 is known in the art as a brown colorant. According to the present invention, the glass composition may contain Er203 in an amount of up to 3 weight percent, for example 0.25 to 2 weight percent or 0.5 to 1.5 weight percent. weight, where the percentage by weight is based on the total weight of the glass composition. Er203 is known in the art as a pink dye. According to the present invention, the glass composition may contain Mn02 in an amount of up to 0.6 percent by weight, for example 0.1 to 0.5 percent by weight or 0.2 to 0, 4 percent by weight, where the percentage by weight is based on the total weight of the glass composition. Mn02 is known in the art as a purple dye. According to the present invention, the glass composition may contain Nd203 in an amount of up to 2 weight percent, for example 0.25 to 1.5 weight percent or 0.5 to 1 weight percent. weight, where the percentage by weight is based on the total weight of the glass composition. Nd203 is known in the art as a blue dye. Fusion and refining aids such as sulfates (S03) discussed above may be present in the glass composition of the invention.

The glass composition of the present invention can be produced by conventional glass manufacturing processes. For example, the glass composition can be formed from raw materials by crucible melting, a sheet drawing process, a glass flotation process, etc. Typically, well-known raw materials are mixed with other components to form the starting materials that are processed in the glass compositions of the present invention. In a non-limiting embodiment of the present invention, dyes and property modification materials are added to the raw materials in the form of nanoparticles. In another non-limiting embodiment, the glass composition of the present invention is formed by a glass flotation process as is well known in the art. As a result of the raw materials and / or equipment used to produce the glass composition of the present invention, certain impurities may be present in the final glass composition. Said materials are present in the glass composition in minor amounts and are referred to herein as "capturing materials". The collecting materials do not contribute to the performance properties of the glass. The capturing materials include, but are not limited to, SrO and Zr02. In a non-limiting embodiment of the invention, the described glass composition is formed on a glass substrate and / or a laminated glass article as is well known in the art. Glass substrates having various thicknesses can be formed. For example, glass substrates having a thickness of up to 24 mm can be formed. In a non-limiting embodiment, a glass substrate according to the present invention has a Lta equal to or greater than 70 percent, for example equal to or greater than 75 percent or equal to or greater than 80 percent at a thickness of 0.223 inches (5.664 mm). In a non-limiting embodiment of the invention a glass substrate according to the present invention is used in furniture or apparatus. EXAMPLES The present invention is illustrated by the following non-limiting examples. Examples 1-4 were performed in the following manner. The raw materials shown in Table 2 were weighed, thoroughly mixed and placed in a 10.2 cm (4 inch) platinum crucible in an electric resistance oven set at a temperature of 2600 ° F (1427 ° C). ) and heated for 2 hours. The molten glass was then poured into water at room temperature (termed "glass frit") in the art to produce a glass frit. The glass frit was dried in an annealing oven set at a temperature of 1100 ° F (593 ° C) for 20 minutes. The glass frit was again placed in a crucible and the crucible was placed in an oven set at a temperature of 2600 ° F (1427 ° C) for 2 hours. The molten glass was molded on a metal table. The resulting glass sheet was placed in a lehr annealing tunnel set at 1125 ° F (607 ° C) for one hour. The lehr tunnel was disconnected and the glass sheet was allowed to remain in the lehr tunnel for 16 hours as it cooled to room temperature. The examples made from molten glasses were ground and polished. Table 2. Glass Raw Materials for Examples 1-4 • "• Crushed glass STARPHIRE® refers to glass that is available commercially at PPG Industries, Inc. (Pittsburgh, PA) under the name of STARPHIRE® glass, which is chunked and added to raw materials as has been The compositional information for exemplary glass compositions made in accordance with the present invention is shown below in Table 3. The concentration of the materials in the glass composition was determined by chemical analysis of x-ray fluorescence. Redox ratio was calculated from the concentration of iron oxides that were determined to be present in the glass composition Table 3. Glass Composition Data for Examples 1-4 1Ce02 and Cr203 are in the crushed STARPHIRE® glass. Table 4 shows various performance properties of exemplary glass substrates having a thickness of 0.223 inches (5.6642 mm). The spectral properties of the examples were measured using a Perkin Elmer Lambda 9 spectrophotometer. In accordance with the present invention, the aforementioned performance properties are measured as described below. All solar transmittance data are calculated using solar air mass data according to ASTM at 1.5 g (E892T.1) All transmittance values are integrated into a wavelength range using the trapezoidal rule as it is known well in the technique. The visible light transmittance (Lta) represents a calculated value based on the measurement data using the "A" illumination pattern of C.I.E. 1931 in a wavelength range of 380 to 770 nanometers at 10 nanometer intervals. The total solar ultraviolet transmittance (TSUV) represents a calculated value based on the data measured over the longitudinal range of 300 to 400 nanometers at 5 nanometer intervals using the SAE 1796 standard. The total solar infrared transmittance (TSIR) represents a calculated value based in the measured data over the wavelength range of 800 to 2100 nanometers at 50 nanometer intervals.

Total solar energy transmittance (TSET) represents a calculated value based on average transmittances from 300 to 2100 nanometers at 50 nanometer intervals. The color is described in terms of dominant wavelength (DW) and excitation purity (Pe) and represents calculated values based on average data using the "C" lighting pattern of C.I.E. 1931 with an observer of 2 °. The visible color was determined by a single observer and indicates the visible color observed by an average person. Table 4. Performance Properties for Examples 1-4 Based on Table 4, non-limiting examples of the glass composition of the present invention can be used to form glass substrates having a thickness of 0.223 inches (5.6642 mm) having various colors such as green and blue. The glass compositions according to the present invention may have one or more of the following performance properties of glass substrates having a thickness of 0.223 inches (5.664 mm): a Lta equal to or greater than 80%, for example equal to greater than 85%, a TSET less than 91%, for example equal to or less than 87%, a TSUV less than 72%, for example equal to or less than 67%; a DW that varies from 470 to 585 nm; and a Pe of up to 30%. Those skilled in the art will readily understand that modifications can be made to the invention without departing from the concepts described in the foregoing description. Said modifications should be considered included within the scope of the invention. Accordingly, the particular embodiments described in detail hereinbefore are illustrative only and not limiting of the scope of the invention which is given in all its breadth by the appended claims and by any of the equivalents thereof.

Claims (15)

1. A glass composition comprising a base glass composition comprising: sio2 from 65 to 75 weight percent, Na20 from 10 to 20 weight percent, Cao from 5 to 15 weight percent, MgO from 0 to 5 weight weight percent, A1203 from 0 to 5 percent by weight,? 2o from 0 to 5 percent by weight, BaO from 0 to 1 percent by weight, and a dye and a property modification part comprising: wherein the glass composition has a redox ratio of up to 0.55.

2. The glass composition according to claim 1, wherein the redox ratio ranges from 0.05 to 0.525.

3. The glass composition according to claim 1, wherein the Ce02 ranges from 0.75 weight percent to 1.0 weight percent.

4. The glass composition according to claim 1, wherein the redox ratio varies from 0.1 to 0.5.

5. The glass composition according to claim 1 wherein at least one of the following materials is present in the aforesaid amount: CoO from 2 to 35 ppm, Se from 3 to 14 ppm, Cr203 from 10 to 300 ppm, CuO up to 0.3 percent by weight, V205 up to 0.2 percent by weight, Ti02 from 0.15 to 0.8 percent by weight, NiO from 5 to 100 ppm, Er203 from 0.25 to 2 percent by weight, weight, Mn02 from 0.1 to 0.5 weight percent and Nd203 from 0.25 to 1.5 weight percent.

6. The composition according to claim 5 wherein at least one of the following materials is present in the quoted amount: CoO from 5 to 25 ppm, Se from 5 to 12 ppm, Cr203 from 20 to 200 ppm, CuO up to 0 , 1 weight percent, V2O5 up to 0.1 weight percent, Ti02 0.2 to 0.6 weight percent, and NiO 10 to 50 ppm, Er203 0.5 to 1.5 percent by weight, Mn02 from 0.2 to 0.4 percent by weight and Nd203 from 0.5 to 1 percent by weight.

7. A glass sheet made from the composition according to claim 1.

8. A sheet of glass according to claim 7, having a Lta greater than or equal to 70% at a thickness of 0.223 inches (5.664 mm).

9. A sheet of glass according to claim 8, having a Lta greater than or equal to 85% at a thickness of 0,223 inches (5,664 mm).

10. A sheet of glass comprising a composition that includes: sio2 from 65 to 75 weight percent, Na20 from 10 to 20 weight percent, CaO from 5 to 15 weight percent, MgO from 0 to 5 weight percent, A1203 from 0 to 5 weight percent, 2o from 0 to 5 weight percent, BaO from 0 to 1 weight percent, and a dye and a property modification part comprising: wherein the glass composition has a redox ratio of up to 0.55 and wherein the glass sheet has a Lta equal to or greater than 70 percent at a thickness of 0.223 inches (5.664 mm).

11. The glass composition according to claim 10 wherein at least one of the following materials is present in the aforesaid amount: CoO from 2 to 35 ppm, Se from 3 to 14 ppm, Cr203 from 10 to 300 ppm, CuO up to 0.3 percent by weight, V205 up to 0.2 percent by weight, Ti02 from 0.15 to 0.8 percent by weight, NiO from 5 to 100 ppm, Er203 from 0.25 to 2 percent by weight, Mn02 from 0.1 to 0.5 weight percent and Nd203 from 0.25 to 1.5 weight percent.

12. A method of manufacturing the glass composition comprising: processing the raw materials to form a glass composition comprising: s? o2 from 65 to 75 percent by weight. Na20 from 10 to 20 weight percent, Cao from 5 to 15 weight percent, MgO from 0 to 5 weight percent, A1203 from 0 to 5 weight percent, 2o from 0 to 5 weight percent, Bao from 0 to 1 weight percent, and a dye and a property modification part comprising: wherein the glass composition has a redox ratio of up to 0.55.

13. The method according to claim 12 wherein at least one of the following materials is present in the glass composition in the aforementioned amount: CoO from 2 to 35 ppm, Se from 3 to 14 ppm, Cr203 from 10 to 300 ppm , CuO up to 0.3 percent by weight, V205 up to 0.2 percent by weight, Ti02 from 0.15 to 0.8 percent by weight, NiO from 5 to 100 ppm, Er203 from 0.25 to 2 percent by weight, Mn02 from 0.1 to 0.5 percent by weight and Nd203 from 0.25 to 1.5 percent by weight.

14. The method according to claim 13 wherein at least one of the following materials is present in the glass composition in the aforesaid amount: CoO from 5 to 25 ppm, Se from 5 to 12 ppm, Cr203 from 20 to 200 ppm , CuO up to 0.1 percent by weight, V2Os up to 0.1 percent by weight, Ti02 from 0.2 to 0.6 percent by weight and NiO from 10 to 50 ppm, Er203 from 0.5 to 1.5 percent by weight, Mn02 from 0.2 to 0.4 percent by weight and Nd203 from 0.5 to 1 percent by weight.

15. The method according to claim 14 further comprising forming the glass composition in a flat sheet.