Abstract:
The present invention is a blue soda-lime-silica glass composition. The composition comprises 68 to 75% SiO 2 , 10 to 18% Na 2 O, 5 to 15% CaO, 0 to 10% MgO, 0 to 5% Al 2 O 3 , and 0 to 5% K 2 O, where CaO+MgO is 6 to 15% and Na 2 O+K 2 O is 10 to 20%, and colorants comprising: 0.3 to 0.8 wt. % total iron oxide as Fe 2 O 3  wherein the ratio of FeO/total Fe as Fe 2 O 3  is 0.35 to 0.62; 0.05 to 0.5 wt. % manganese compound as MnO 2 , 0 to 0.30 wt. % titanium oxide as TiO 2 ; and 0 to 0.8 wt. % cerium oxide as CeO 2 . The colored glass has the following spectral properties at 4.0 mm. thickness: 65 to 81% light transmittance using Illuminant A (LTA) and using Illuminant C has a dominant wavelength of 488 to 494 nanometers with an excitation purity of 4 to 11%.

Description:
TECHNICAL FIELD OF THE INVENTION 
     The invention is directed to a blue glass composition and method of producing; a blue glass with an improved infrared absorption. 
     BACKGROUND OF THE INVENTION 
     It would be extremely advantageous to improve the infrared absorption of glass products while maintaining a high level of visible transmission and to also have a good absorption in the ultraviolet portion of the spectrum. As is well known in the art, iron oxide is commonly used to provide a green color to glass. Iron oxide exists in two chemical forms in the glass, an oxidized form which is yellow: Fe 2 O 3 , and a reduced form which is blue FeO. Advantageously, the oxidized form of iron oxide absorbs a portion of the ultraviolet light passing through the glass product and the reduced form of iron oxide absorbs a portion of the infrared light passing through the glass product. Under typical furnace firing conditions arid batching conditions, when the total iron oxide in the glass product is within the range of about 0.3 to 0.8 wt. % as Fe 2 O 3 , the iron oxide equilibrium is such that the redox ratio of FeO/total Fe as Fe 2 O 3  is about 0.23-0.26. 
     It is desirable to increase the proportion of reduced iron oxide (FeO) in the glass to improve its infrared absorption. In addition, by shifting the iron oxide away from the oxidized form (Fe 2 O 3 ) the glass will change color from green to blue. The total iron oxide concentration may be decreased to maintain a high visible transmittance of the glass as the reduced iron absorbs more in the visible portion of the spectrum than the oxidized iron. 
     One way commonly employed to shift the redox equilibrium of iron oxide in the glass, and hence its UV and IR properties, is by increasing the fuel to the furnace. Increasing the amount of fuel, however, has several undesirable consequences: the combustion heating of the furnace becomes inefficient and requires an air increase or the unburnt fuel will burn in the checker system of the furnace. Excess fuel can also reduce the glass to an amber color that sharply lowers the visible transmittance of the glass product. 
     An amber color arises when the iron reacts with sulfur that has been reduced to form iron sulfide. Amber colored glass containers are normally melted in like manner by using anthracite coal together with iron oxide and sulfate. The amber iron sulfide chromophore, once produced, significantly decreases the visible transmittance of the glass and the glass could not be used where a high transmittance is required. 
     Therefore, there is a need in the glass industry to produce amber free blue glass that has high transmittance yet having an improved infrared light absorption and an ultra violet absorption. 
     SUMMARY OF THE INVENTION 
     The present invention is a blue soda-lime-silica glass composition that is heat absorbing. The composition comprises 68 to 75% SiO 2 , 10 to 18% Na 2 O, 5 to 15% CaO, 0 to 10% MgO, 0 to 5% Al 2 O 3 , and 0 to 5% K 2 O, where CaO+MgO is 6 to 15% and Na 2 O+K 2 O is 10 to 20%, and colorants consisting essentially of: 0.3 to 0.8 wt. % total iron oxide as Fe 2 O 3  wherein the ratio of FeO/total Fe as Fe 2 O 3  is greater than 0.35 but less than 0.62; 0.05 to 0.5 wt. % manganese compound as MnO 2 ; 0 to 0.30 wt. % titanium oxide as TiO 2 , and 0 to 0.8 wt. % cerium oxide as CeO 2 . 
     Glass products made according to the embodiment of the invention have the following spectral properties at 4.0 mm. Thickness 65 to 81% light transmittance using Illuminant A (LTA) and using Illuminant C has a dominant wavelength greater than 488 but less than or equal to 494 nanometers with an excitation purity greater than 4 and less than 11%. Generally, as the quantities of the colorants increase, both the % LTA and % IR transmittance will go down. Similarly, as the glass thickness increases for a given glass composition, the transmittance of the thicker glass will decrease. 
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
     Flat soda-lime-silica glass, used in the automotive and architectural industries and conveniently made by the float glass process, is generally characterized by the following basic composition, the amounts of the components being based on a weight percentage of the total glass composition: 
     
       
         
               
               
               
             
           
               
                   
                 TABLE I 
               
               
                   
                   
               
               
                   
                 Base Glass Components 
                 Weight % 
               
               
                   
                   
               
             
             
               
                   
                 SiO 2   
                 68 to 75 
               
               
                   
                 Al 2 O 3   
                 0 to 5 
               
               
                   
                 CaO 
                  5 to 15 
               
               
                   
                 MgO 
                  0 to 10 
               
               
                   
                 Na 2 O 
                 10 to 18 
               
               
                   
                 K 2 O 
                 0 to 5 
               
               
                   
                   
               
             
          
         
       
     
     The blue glass composition of the present invention employs this basic soda-lime-silica glass composition wherein, additionally, CaO+MgO is 6 to 15 wt. % and Na 2 O+K 2 O is 10 to 20 wt. %. Preferably SO 3  is 0.02 to 0.20 wt. %, more preferably 0.02 to 0.10 wt. %. In addition, the blue glass composition consists essentially of the following coloring components: iron oxide; manganese compound; and optionally any of titanium dioxide or cerium oxide or both. 
     The total iron oxide as Fe 2 O 3  present in the invention composition in quantities of 0.3 to 0.8 wt. % Fe 2 O 3 . Typically, this ingredient is added with the batch ingredients in the oxide form, Fe 2 O 3 . The iron oxide incorporated in the composition lowers both the ultraviolet and the infrared transmittance of the glass products. When iron is used in a glass composition in normal commercial production, the redox ratio defined as equal to FeO/total Fe as Fe 2 O 3 is 0.23-0.26, while glass of the invention has a higher redox ratio of 0.35-0.62. If the redox ratio goes above 0.62, the undesirable amber chromophore may form. 
     The most important factor of glass of the invention is the one step batch admixing of the components to feed a conventional siemens float glass furnace. Sodium sulfate is mixed in the batch together with anthracite coal to shift the iron oxide equilibrium toward the reduced form of iron. Manganese dioxide is necessary in the batch to prevent the formation of the amber iron sulfide. All of the batch components are mixed together in a single step and then metered into the furnace. The glass product made with this method becomes blue and the infrared absorption of the product is measurably improved. When glass products made in this manner are used in vehicles, the blue glass absorbs solar heat and there is less total heat build up in the vehicle. The load on vehicle air conditioners is reduced such that there is less heat build up to cool and comfort to the passengers occurs quickly. Glass made with the instant invention can also be used for architectural products and provides a similar reduction in air conditioner load. 
     A manganese compound is present in an amount of 0.05 to 0.5 wt.% based on MnO 2  in the blue glass invention composition to prevent the formation of the amber color. This manganese compound can be added to the batch glass components in a variety forms, e.g., but not limited to MnO 2 , Mn 3 O 4 , MnO, MnCO 3 , MnSO 4 , MnF 2 , MnCl 2 , etc. 
     Table II discloses the amounts of raw material batch ingredients that are preferably used to form the embodiments of blue glass compositions according to the present invention. 
     
       
         
               
               
               
             
           
               
                   
                 TABLE II 
               
               
                   
                   
               
               
                   
                 Batch Material 
                 Range Mass (Lbs) 
               
               
                   
                   
               
             
             
               
                   
                 Sand 
                 1000 
               
               
                   
                 Soda Ash 
                 290 to 350 
               
               
                   
                 Limestone 
                 70 to 90 
               
               
                   
                 Dolomite 
                 215 to 260 
               
               
                   
                 Salt cake 
                  5 to 15 
               
               
                   
                 Rouge (97% Fe 2 O 3)   
                  3.5 to 11.5 
               
               
                   
                 Manganese Dioxide 
                 0.65 to 6.5  
               
               
                   
                 Titanium Dioxide 
                   0 to 4.2 
               
               
                   
                 Cerium Oxide 
                   0 to 11.5 
               
               
                   
                 Anthracite coal 
                   1 to 2.5 
               
               
                   
                 Nepheline Syenite 
                  0 to 150 
               
               
                   
                   
               
             
          
         
       
     
     CARBOCITE is anthracite coal from the Shamokin Filler Company. Graphite could be used as a substitute for anthracite coal in an amount of about 70% that of anthracite coal because anthracite coal contains about 70-72% carbon, the typical range would be from 0.7 to 2.1 pounds of graphite per 1000 pounds of sand. MELITE, a coal slag processed by Calumite Corporation could partially or wholly substitute for rouge in the batch up to about 55 pounds Melite per 1000 pounds of sand. MELITE has about 80% of the total iron oxide in the reduced form and thus would require less anthracite coal to generate similar spectral properties. 
     The equilibrium reactions that occur in the glass melt which cause a shift in the forms of iron oxide are included by the sodium sulfate used as a refining agent and carbon used to react with sodium sulfate at lower furnace temperatures. Generally, increasing the quantity of sodium sulfate in the glass tends to shift the iron oxide equilibrium slightly toward oxidizing while increasing carbon concentration in the glass batch shifts the iron oxide equilibrium toward reducing. Another influence on the iron oxide equilibrium is the peak furnace temperature which when increased will shift the iron oxide slightly toward the reduced state and lowering overall furnace temperature allows the iron oxide to shift toward the oxidized state. 
     Melts were made in the laboratory which demonstrate embodiments of this invention using the procedure as follows: 2″ inside diameter and dry mixed for 10 minutes each on a Turbula mixer, dry batch was placed into an 80% platinum 20% rhodium crucible that stands 2″ tall and has an inside diameter at the top of 2.5″ and is tapered to the base which has an inside diameter of 1.75″. An amount of 4.5 ml. of water is added to the dry batch in the crucible and mixed with a metal spoon. After such preparation, a group of six different batches is melted in a gas/air fired surface at the same time for 1 hour at 2600° F. and each crucible is removed in turn from the furnace and fritted. Fritting the glass involves coating the inside of the platinum/rhodium crucible by rolling the molten, glass around the inside of the crucible and then plunging the crucible into cold water. After removing, the crucible from the water and draining, the broken glass particles are removed from the sides of the crucible and mechanically mixed inside the crucible. All six samples are fritted in like manner and all crucibles are placed back into the furnace for another hour interval at 2600° F. and the fritting procedure is repeated. After the second fritting process, the crucibles are returned to the furnace for 4 hours at 2600° F. Each crucible is removed in turn from the furnace and each molten glass sample is poured into a graphite mold with an inside diameter of 2.5″. Each glass is cooled slowly, labeled, and placed into an annealing furnace where the temperature is quickly raised to 1050° F., held for 2 hours, and then slowly cooled by shutting off the furnace and removing the samples after 14 or more hours. The samples are ground and polished to about 4.0 mm. thickness and subsequently the spectral properties are measured for each sample. 
     All of the examples are made using the above batch only with no cullet (the broken pieces of glass that are added to the batch feed in production). There are two types of cullet that can be added to the batch to produce glass of the invention: reduced iron blue glass from glass of the invention and oxidized iron green glass. The reduced iron blue glass cullet has a redox ratio of about, 0.5 to 0.6 while the oxidized iron green glass has a redox ratio of about 0.25. The redox ratio is defined as the ratio of wt. % FeO/total Fe as wt. % Fe 2 O 3 . For example, if the desired glass of the invention uses 2 pounds of anthracite coal for 1000 pounds of sand, then an additional 1.5 pounds of anthracite coal must be added to the batch when the reduced iron blue glass cullet is added to make 50% of the batch feed to the furnace for a total of 3.5 pounds of anthracite coal per 1000 pounds of sand. For other cullet levels, the anthracite coal is increased or decreased proportionately. If the oxidized iron green glass cullet is used, more anthracite coal must be added to drive the oxidized cullet toward the reduced iron blue color. For example, if the desired glass of the invention uses 2 pounds of anthracite coal for 1000 pounds of sand, then an additional 2.5 pounds of anthracite coal must be added to the batch when the oxidized iron green glass cullet is added to make 50% of the batch feed to the furnace for a total of 4.5 pounds of anthracite coal per 1000 pounds of sand. When other reductants are used, they must be adjusted proportionately as the anthracite coal in the examples. 
     All laboratory melts made with above procedure use a base composition of 100 grams sand, 32.22 grams soda ash, 8.81 grams limestone, 23.09 grams dolomite, 0.5 to 2.0 grams of sodium sulfate, 0.1 to 0.25 grams of CARBOCITE, 2.64 grams of nepheline syenite, and the remainder of the batch includes rouge, manganese dioxide, and titanium dioxide and cerium oxide, if required. 
     In each of the following tables of examples with the glass composition includes spectral data at 4.0 mm., which is the control thickness. Some tables include thickness other than 4.0 mm. where the most preferred embodiment of the instant invention is with the % LTA greater than or equal to 70.0% and the TSET is less than or equal to 40.0%. 
    
    
     Table III below shows the improvement to infrared absorption by increasing anthracite coal and improvement in ultra violet absorption by increasing manganese dioxide. Glasses made with the same batch concentrations, but without anthracite coal are green and do not have the level of infrared absorption; this would put those glasses outside the scope of this invention. Glasses made without manganese dioxide develop the amber color and the transmittance is significantly lower. Example 1 demonstrates the amber glass generated when manganese dioxide is removed from the batch components. This is compared to Example 3 with manganese added to the glass. Example 1 is not included in glass of this invention and is used only to illustrate the difference in transmittance and with and without use of manganese oxide. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
           
               
                 TABLE III 
               
               
                   
               
               
                 Example 
                 1 
                 2 
                 3 
                 4 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Wt. % Fe 2 O 3   
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
               
                 Wt. % FeO 
                 0.312 
                 0.234 
                 0.293 
                 0.255 
               
               
                 Redox Ratio 
                 0.624 
                 0.468 
                 0.586 
                 0.510 
               
               
                 Wt. % MnO 2   
                 0 
                 0.1 
                 0.1 
                 0.4 
               
               
                 Wt. % CeO 2   
               
               
                 Wt. % TiO 2   
               
               
                 Salt Cake* 
                 10 
                 10 
                 10 
                 10 
               
               
                 Anthracite coal* 
                 2.08 
                 1.67 
                 2.08 
                 2.08 
               
               
                 Graphite* 
               
               
                 Melite* 
               
             
          
           
               
                 Spectral Properties @ 4.0 mm. control thickness 
               
             
          
           
               
                 % LTA 
                 67.3 
                 75.46 
                 71.37 
                 73.41 
               
               
                 % UV 
                 42.02 
                 57.14 
                 56.35 
                 57.38 
               
               
                 % IR 
                 13.62 
                 21.48 
                 15.14 
                 18.79 
               
               
                 % TSET 
                 36.1 
                 46.41 
                 40.63 
                 44.14 
               
               
                 Dominant wavelength 
                 549.8 
                 490.3 
                 493.5 
                 490.1 
               
               
                 % Excitation Purity 
                 7.7 
                 6 
                 6.2 
                 7.2 
               
             
          
           
               
                 Most Preferred Embodiment of Invention with Spectral 
               
               
                 Properties @ indicated thickness 
               
             
          
           
               
                 Thickness in mm. 
                   
                 5.4 
                 4.2 
                 4.8 
               
               
                 % LTA 
                   
                 70.7 
                 70.6 
                 70.67 
               
               
                 % UV 
                   
                 51.3 
                 55.4 
                 53.75 
               
               
                 % IR 
                   
                 13.4 
                 14.1 
                 13.96 
               
               
                 % TSET 
                   
                 39.6 
                 39.6 
                 39.97 
               
               
                 Dominant Wavelength 
                   
                 490.2 
                 493.5 
                 490 
               
               
                 % Excitation Purity 
                   
                 8 
                 6.4 
                 8.6 
               
               
                   
               
               
                 *pounds per 1000 pounds sand  
               
             
          
         
       
     
     Table IV demonstrates further improvements in infrared absorption by increasing anthracite coal and in ultra violet absorption when MnO 2  is increased at constant Fe 2 O 3 . Generally, as anthracite coal is increased infrared absorption is increased while as manganese dioxide is increased the ultra violet absorption is increased. 
     
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
           
               
                 TABLE IV 
               
               
                   
               
               
                 Example 
                 5 
                 6 
                 7 
                 8 
                 9 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Wt. % Fe 2 O 3   
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
               
                 Wt. % FeO 
                 0.2 
                 0.249 
                 0.198 
                 0.241 
                 0.276 
               
               
                 Redox Ratio 
                 0.400 
                 0.498 
                 0.396 
                 0.482 
                 0.552 
               
               
                 Wt. % MnO 2   
                 0.05 
                 0.05 
                 0.45 
                 0.45 
                 0.45 
               
               
                 Wt. % CeO 2   
               
               
                 Wt. % TiO 2   
               
               
                 Salt Cake* 
                 10 
                 10 
                 10 
                 10 
                 10 
               
               
                 Anthracite coal* 
                 1.44 
                 1.67 
                 1.67 
                 2 
                 2.22 
               
               
                 Graphite* 
               
               
                 Melite* 
               
             
          
           
               
                 Spectral Properties @ 4.0 mm. control thickness 
               
             
          
           
               
                 % LTA 
                 76.96 
                 74.56 
                 75.36 
                 74 
                 72.32 
               
               
                 % UV 
                 57.94 
                 59.99 
                 50.56 
                 54.85 
                 55.79 
               
               
                 % IR 
                 26.03 
                 19.51 
                 26.33 
                 20.41 
                 16.63 
               
               
                 % TSET 
                 49.61 
                 45.12 
                 48.54 
                 45.01 
                 42.08 
               
               
                 Dominant wavelength 
                 490.1 
                 488.8 
                 493.4 
                 490.8 
                 491.3 
               
               
                 % Excitation Purity 
                 5.7 
                 7.8 
                 4.7 
                 6.6 
                 7.1 
               
             
          
           
               
                 Most Preferred Embodiment of Invention with Spectral Properties @ 
               
               
                 indicated thickness 
               
             
          
           
               
                 Thickness in mm. 
                   
                   
                   
                 5 
                 4.4 
               
               
                 % LTA 
                   
                   
                   
                 70.27 
                 70.7 
               
               
                 % UV 
                   
                   
                   
                 50.16 
                 53.9 
               
               
                 % IR 
                   
                   
                   
                 14.35 
                 14.4 
               
               
                 % TSET 
                   
                   
                   
                 39.81 
                 40 
               
               
                 Dominant Wavelength 
                   
                   
                   
                 490.7 
                 491.3 
               
               
                 % Excitation Purity 
                   
                   
                   
                 8.2 
                 7.8 
               
               
                   
               
               
                 *pounds per 1000 pounds sand  
               
             
          
         
       
     
     Table V demonstrates that slag from coal burning facilities, for example, MELITE processed by Calumite Corporation can be used as a partial or complete substitute for rouge to generate products within the scope of the invention. MELITE contains iron oxide where approximately 80% of the iron oxide is in the reduced form while about 98% of the iron is rouge is in the oxidized form. Less anthracite coal is required to reduce the glass batch using MELITE than batch with rouge. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
           
               
                 TABLE V 
               
               
                   
               
               
                 Example 
                 10 
                 11 
                 12 
                 13 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Wt. % Fe 2 O 3   
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
               
                 Wt. % FeO 
                 0.208 
                 0.236 
                 0.255 
                 0.303 
               
               
                 Redox Ratio 
                 0.416 
                 0.472 
                 0.510 
                 0.606 
               
               
                 Wt. % MnO 2   
                 0.1 
                 0.1 
                 0.1 
                 0.1 
               
               
                 Wt. % CeO 2   
               
               
                 Wt. % TiO 2   
               
               
                 Salt Cake* 
                 10.5 
                 10.5 
                 10.5 
                 10.5 
               
               
                 Anthracite coal* 
                 1.05 
                 1.16 
                 1.31 
                 1.5 
               
               
                 Graphite* 
               
               
                 Melite* 
                 34.2 
                 34.2 
                 34.2 
                 34.2 
               
             
          
           
               
                 Spectral Properties @ 4.0 mm. control thickness 
               
             
          
           
               
                 % LTA 
                 74.89 
                 73.64 
                 72.93 
                 69.85 
               
               
                 % UV 
                 54.37 
                 55.76 
                 57.78 
                 55.23 
               
               
                 % IR 
                 24.85 
                 21.07 
                 18.82 
                 14.32 
               
               
                 % TSET 
                 47.86 
                 45.34 
                 43.91 
                 39.57 
               
               
                 Dominant wavelength 
                 490.9 
                 489.9 
                 489.4 
                 492.3 
               
               
                 % Excitation Purity 
                 5.8 
                 7 
                 7.7 
                 7.2 
               
             
          
           
               
                 Most Preferred Embodiment of Invention with Spectral 
               
               
                 Properties @ indicated thickness 
               
             
          
           
               
                 Thickness in mm. 
                   
                   
                   
                 3.9 
               
               
                 % LTA 
                   
                   
                   
                 70.3 
               
               
                 % UV 
                   
                   
                   
                 55.7 
               
               
                 % IR 
                   
                   
                   
                 14.9 
               
               
                 % TSET 
                   
                   
                   
                 40 
               
               
                 Dominant Wavelength 
                   
                   
                   
                 492.3 
               
               
                 % Excitation Purity 
                   
                   
                   
                 7 
               
               
                   
               
               
                 *pounds per 1000 pounds sand  
               
             
          
         
       
     
     Table VI shows that graphite can be used to substitute for anthracite coal in glass of the invention. Other carbonaceous materials could substitute for anthracite coal or graphite where the ratio of carbon content would be compared to that of graphite or anthracite coal. 
     
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
           
               
                 TABLE VI 
               
               
                   
               
               
                 Example 
                 14 
                 15 
                 16 
                 17 
                 18 
                 19 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Wt. % Fe 2 O 3   
                 0.55 
                 0.55 
                 0.55 
                 0.65 
                 0.65 
                 0.65 
               
               
                 Wt. % FeO 
                 0.207 
                 0.226 
                 0.249 
                 0.27 
                 0.271 
                 0.295 
               
               
                 Redox Ratio 
                 0.376 
                 0.411 
                 0.453 
                 0.415 
                 0.417 
                 0.454 
               
               
                 Wt. % MnO 2   
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
               
               
                 Wt. % CeO 2   
               
               
                 Wt. % TiO 2   
               
               
                 Salt Cake* 
                 10 
                 10 
                 10 
                 10 
                 10 
                 10 
               
               
                 Anthracite 
               
               
                 coal* 
               
               
                 Graphite* 
                 1.17 
                 1.25 
                 1.34 
                 1.18 
                 1.25 
                 1.33 
               
               
                 Melite* 
               
             
          
           
               
                 Spectral Properties @ 4.0 mm. control thickness 
               
             
          
           
               
                 % LTA 
                 75.87 
                 74.44 
                 73.61 
                 72.15 
                 71.76 
                 71.12 
               
               
                 % UV 
                 55.82 
                 56.7 
                 57.56 
                 52.13 
                 51.94 
                 53.71 
               
               
                 % IR 
                 25.01 
                 22.32 
                 19.44 
                 17.27 
                 17.19 
                 14.96 
               
               
                 % TSET 
                 48.47 
                 46.59 
                 44.58 
                 42.47 
                 42.24 
                 40.87 
               
               
                 Dominant 
                 490.6 
                 489.8 
                 489.2 
                 490.1 
                 490.1 
                 489.4 
               
               
                 wavelength 
               
               
                 % Excitation 
                 5.7 
                 6.5 
                 7.5 
                 7.4 
                 7.5 
                 8.5 
               
               
                 Purity 
               
             
          
           
               
                 Most Preferred Embodiment of Invention with Spectral Properties @ 
               
               
                 indicated thickness 
               
             
          
           
               
                 Thickness in 
                   
                 4.9 
                   
                 4.4 
                 4.2 
               
               
                 mm. 
               
               
                 % LTA 
                   
                 70.3 
                   
                 70.1 
                 70.5 
               
               
                 % UV 
                   
                 53.6 
                   
                 50 
                 53.8 
               
               
                 % IR 
                   
                 14 
                   
                 15 
                 13.9 
               
               
                 % TSET 
                   
                 39.9 
                   
                 39.9 
                 39.9 
               
               
                 Dominant 
                   
                 489.1 
                   
                 490 
                 489.4 
               
               
                 Wavelength 
               
               
                 % Excitation 
                   
                 9 
                   
                 8.2 
                 8.9 
               
               
                 Purity 
               
               
                   
               
               
                 *pounds per 1000 pounds sand  
               
             
          
         
       
     
     Table VII indicates the impact of salt cake in glass of the invention. Salt cake is used to remove gaseous inclusions, from the glass in the furnace by growing bubbles larger, bubbles rising to the surface and then breaking open at the melt surface and releasing the accumulated gases. Increasing salt cake in the batch tends to oxidize the glass and requires increasing anthracite coal. Excess use of salt cake is discouraged because the excess salt cake releases SO x  emissions. Other sulfates can substitute for salt cake in glass of the invention. 
     
       
         
               
               
               
               
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
               
             
               
               
               
               
               
             
           
               
                 TABLE VII 
               
               
                   
               
               
                 Example 
                 20 
                 21 
                 22 
                 23 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Wt. % Fe 2 O 3   
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
               
                 Wt. % FeO 
                 0.257 
                 0.291 
                 0.204 
                 0.24 
               
               
                 Redox Ratio 
                 0.514 
                 0.582 
                 0.408 
                 0.480 
               
               
                 Wt. % MnO 2   
                 0.1 
                 0.45 
                 0.1 
                 0.45 
               
               
                 Wt. % CeO 2   
               
               
                 Wt. % TiO 2   
               
               
                 Salt Cake* 
                 10 
                 10 
                 15 
                 15 
               
               
                 Anthracite coal* 
                 1.9 
                 2.11 
                 1.82 
                 2.22 
               
               
                 Graphite* 
               
               
                 Melite* 
               
             
          
           
               
                 Spectral Properties @ 4.0 mm. control thickness 
               
             
          
           
               
                 % LTA 
                 73.89 
                 71.18 
                 76.46 
                 74.19 
               
               
                 % UV 
                 58.57 
                 54.25 
                 56.91 
                 54.93 
               
               
                 % IR 
                 18.66 
                 15.34 
                 25.44 
                 20.57 
               
               
                 % TSET 
                 44.25 
                 40.69 
                 48.99 
                 45.19 
               
               
                 Dominant wavelength 
                 489.2 
                 492.5 
                 490.4 
                 490.9 
               
               
                 % Excitation Purity 
                 7.8 
                 6.7 
                 5.7 
                 6.5 
               
             
          
           
               
                 Most Preferred Embodiment of Invention with Spectral 
               
               
                 Properties @ indicated thickness 
               
             
          
           
               
                 Thickness in mm. 
                 5 
                 4.2 
                 6 
                 5 
               
               
                 % LTA 
                 70.16 
                 70.3 
                 70.05 
                 70.05 
               
               
                 % UV 
                 54.34 
                 53.5 
                 48.75 
                 50.27 
               
               
                 % IR 
                 12.87 
                 14.3 
                 13.94 
                 14.49 
               
               
                 % TSET 
                 39.23 
                 39.6 
                 39.49 
                 39.98 
               
               
                 Dominant Wavelength 
                 489.1 
                 492.5 
                 490.2 
                 490.8 
               
               
                 % Excitation Purity 
                 9.6 
                 6.9 
                 8.5 
                 8 
               
               
                   
               
               
                 *pounds per 1000 pounds sand  
               
             
          
         
       
     
     Table VIII indicates the wide range of Fe 2 O 3  that can be used to demonstrate the instant invention. Products that follow the teachings of the, instant invention can vary in thickness from 1.5 to 8.0 mm. and can be used in architectural as well as automotive applications. Automotive applications include laminated products such as windshields. 
     
       
         
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
           
               
                 TABLE VIII 
               
               
                   
               
               
                 Example 
                 24 
                 25 
                 26 
                 27 
                 28 
                 28 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Wt. % Fe 2 O 3   
                 0.3 
                 0.35 
                 0.45 
                 0.6 
                 0.65 
                 0.7 
               
               
                 Wt. % FeO 
                 0.152 
                 0.179 
                 0.213 
                 0.334 
                 0.321 
                 0.352 
               
               
                 Redox Ratio 
                 0.507 
                 0.511 
                 0.473 
                 0.557 
                 0.494 
                 0.503 
               
               
                 Wt. % MnO 2   
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
               
               
                 Wt. % CeO 2   
               
               
                 Wt. % TiO 2   
               
               
                 Salt Cake* 
                 10 
                 10 
                 10 
                 10 
                 10 
                 10 
               
               
                 Anthracite 
                 1.81 
                 1.82 
                 1.81 
                 2.01 
                 1.82 
                 1.82 
               
               
                 coal* 
               
               
                 Graphite* 
               
               
                 Melite* 
               
             
          
           
               
                 Spectral Properties @ 4.0 mm. control thickness 
               
             
          
           
               
                 % LTA 
                 80.34 
                 78.75 
                 76.65 
                 69.26 
                 69.01 
                 67.83 
               
               
                 % UV 
                 68.86 
                 66.43 
                 61.33 
                 54.3 
                 51.57 
                 50.85 
               
               
                 % IR 
                 34.96 
                 29.66 
                 24.13 
                 11.97 
                 12.87 
                 10.87 
               
               
                 % TSET 
                 56.35 
                 52.77 
                 48.55 
                 38.08 
                 38.63 
                 36.97 
               
               
                 Dominant 
                 488.9 
                 488.7 
                 489.6 
                 490.7 
                 489.2 
                 489.2 
               
               
                 wavelength 
               
               
                 % Excitation 
                 4.9 
                 5.7 
                 6.2 
                 8.6 
                 9.4 
                 10.1 
               
               
                 Purity 
               
             
          
           
               
                 Most Preferred Embodiment of Invention with Spectral Properties @ 
               
               
                 indicated thickness 
               
             
          
           
               
                 Thickness in 
                 7.2 
                 6 
                 3.7 
                 3.5 
                 4.2 
               
               
                 mm. 
               
               
                 % LTA 
                 70.1 
                 70.32 
                 70.7 
                 70 
                 70.4 
               
               
                 % UV 
                 56.8 
                 53.97 
                 55.8 
                 53.7 
                 53.6 
               
               
                 % IR 
                 13 
                 12.91 
                 13.8 
                 14.1 
                 14 
               
               
                 % TSET 
                 39.5 
                 39.27 
                 39.7 
                 39.8 
                 40 
               
               
                 Dominant 
                 488.4 
                 489.5 
                 490.7 
                 489.3 
                 489.2 
               
               
                 Wavelength 
               
               
                 % Excitation 
                 10.1 
                 9.1 
                 7.9 
                 9.1 
                 8.9 
               
               
                 Purity 
               
               
                   
               
               
                 *pounds per 1000 pounds sand  
               
             
          
         
       
     
     Table IX indicates the improvement in ultra violet absorption that cerium oxide makes. Cerium oxide by itself does not sufficiently increase the ultra violet absorption alone but as manganese dioxide increases, the ultra violet absorption again increases. 
     
       
         
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE IX 
               
               
                   
               
               
                 Example 
                 30 
                 31 
                 32 
                 33 
                 34 
                 35 
                 36 
                 37 
                 38 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Wt. % Fe 2 O 3   
                 0.5 
                 0.5 
                 0.7 
                 0.8 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
               
                 Wt. % FeO 
                 0.286 
                 0.25 
                 0.309 
                 0.357 
                 0.275 
                 0.283 
                 0.25 
                 0.251 
                 0.203 
               
               
                 Redox Ratio 
                 0.572 
                 0.500 
                 0.441 
                 0.446 
                 0.550 
                 0.566 
                 0.500 
                 0.502 
                 0.406 
               
               
                 Wt. % MnO 2   
                 0.06 
                 0.12 
                 0.4 
                 0.4 
                 0.45 
                 0.05 
                 0.45 
                 0.05 
                 0.45 
               
               
                 Wt. % CeO 2   
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.2 
                 0.4 
                 0.4 
                 0.8 
                 0.8 
               
               
                 Wt. % TiO 2   
               
               
                 Salt Cake* 
                 10.5 
                 10.5 
                 10.5 
                 10.5 
                 10 
                 10 
                 10 
                 10 
                 10 
               
               
                 Anthracite 
                 2.1 
                 2.1 
                 2.1 
                 2.1 
                 2.22 
                 2 
                 2.22 
                 2 
                 2.23 
               
               
                 coal* 
               
               
                 Graphite* 
               
               
                 Melite* 
               
             
          
           
               
                 Special Properties @ 4.0 mm. control thickness 
               
             
          
           
               
                 % LTA 
                 72.21 
                 74.58 
                 68.32 
                 65.22 
                 72.46 
                 72.3 
                 72.77 
                 73.68 
                 75.58 
               
               
                 % UV 
                 47.46 
                 48.91 
                 38.04 
                 35.32 
                 50.32 
                 48.48 
                 45.47 
                 45.74 
                 41.37 
               
               
                 % IR 
                 15.81 
                 19.47 
                 13.78 
                 10.56 
                 16.77 
                 16.02 
                 19.31 
                 19.22 
                 25.58 
               
               
                 % TSET 
                 41.37 
                 44.75 
                 38.12 
                 34.83 
                 42.17 
                 41.49 
                 43.49 
                 44.11 
                 47.97 
               
               
                 Dominant 
               
               
                 Wavelength 
                 491.2 
                 489.5 
                 492.3 
                 492.3 
                 490.6 
                 491.6 
                 491.5 
                 489.4 
                 493.9 
               
               
                 % Excitation 
               
               
                 Purity 
                 7.1 
                 7.3 
                 7.3 
                 8.2 
                 7.4 
                 7 
                 6.5 
                 7.5 
                 4.6 
               
               
                   
               
               
                 *pounds per 1000 pounds sand  
               
             
          
         
       
     
     Lowering the ultra violet transmittance below 50% at 4.0 mm. control thickness requires greater than 0.2 wt. % MnO 2  and greater than 0.2 wt. % CeO 2  or the total of the components manganese dioxide and cerium, oxide to be 0.45 wt. % or greater. 
     Table X shows the improvement in ultra violet absorption made by the addition of titanium dioxide and that the dominant wavelength increases toward a green color. Titanium dioxide is capped at 0.3 wt. %. There is a trace amount of titanium dioxide in the sands that adds about 0.01. wt. % TiO 2  to the glass composition. 
     
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
           
               
                 TABLE X 
               
               
                   
               
               
                 Example 
                 39 
                 40 
                 41 
                 42 
                 43 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Wt. % Fe 2 O 3   
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
               
                 Wt. % FeO 
                 0.239 
                 0.238 
                 0.261 
                 0.26 
                 0.253 
               
               
                 Redox Ratio 
                 0.478 
                 0.476 
                 0.522 
                 0.520 
                 0.506 
               
               
                 Wt. % MnO 2   
                 0.2 
                 0.2 
                 0.2 
                 0.2 
                 0.4 
               
               
                 Wt. % CeO 2   
               
               
                 Wt. % TiO 2   
                 Tramp 
                 0.05 
                 0.1 
                 0.2 
                 0.3 
               
               
                 Salt Cake* 
                 10 
                 10 
                 10 
                 10 
                 10.5 
               
               
                 Anthracite coal* 
                 1.9 
                 1.9 
                 1.9 
                 1.9 
                 2.1 
               
               
                 Graphite* 
               
               
                 Melite* 
               
             
          
           
               
                 Spectral Properties @ 4.0 mm. control thickness 
               
             
          
           
               
                 % LTA 
                 75.22 
                 74.68 
                 73.82 
                 73.6 
                 73.35 
               
               
                 % UV 
                 59.38 
                 57.34 
                 57.52 
                 55.12 
                 50.08 
               
               
                 % IR 
                 20.77 
                 20.79 
                 18.25 
                 18.33 
                 19.13 
               
               
                 % TSET 
                 46.05 
                 45.7 
                 43.84 
                 43.61 
                 43.58 
               
               
                 Dominant wavelength 
                 489.4 
                 490 
                 490.4 
                 491.5 
                 494 
               
               
                 % Excitation Purity 
                 7.1 
                 6.8 
                 7.1 
                 6.5 
                 5.5 
               
             
          
           
               
                 Most Preferred Embodiment of Invention with Spectral Properties @ 
               
               
                 indicated thickness 
               
             
          
           
               
                 Thickness in mm. 
                 5.5 
                 5.1 
                 5 
                 4.8 
                 4.8 
               
               
                 % LTA 
                 70.1 
                 70.5 
                 70.07 
                 70.55 
                 70.25 
               
               
                 % UV 
                 53.4 
                 52.5 
                 53.02 
                 51.22 
                 45.78 
               
               
                 % IR 
                 12.6 
                 14.1 
                 12.52 
                 13.57 
                 14.26 
               
               
                 % TSET 
                 39 
                 40 
                 38.8 
                 39.42 
                 39.28 
               
               
                 Dominant Wavelength 
                 489.2 
                 489.9 
                 490.3 
                 491.4 
                 493.9 
               
               
                 % Excitation Purity 
                 9.6 
                 8.6 
                 8.8 
                 7.8 
                 6.5 
               
               
                   
               
               
                 *pounds per 1000 pounds sand  
               
             
          
         
       
     
     Table XI indicates the ultraviolet absorption improvements when cerium oxide and titanium dioxide are used in combination. Lowering the ultra violet transmittance below 50% at 4.0 mm. control thickness requires greater than 0.05 wt. % MnO 2 , greater than 0.2 wt. % CeO 2  and greater than 0.1 wt. % TiO 2  or the total of the components manganese dioxide, cerium oxide and titanium dioxide to be 0.55 wt. % or greater. 
     
       
         
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE XI 
               
               
                   
               
               
                 Example 
                 44 
                 45 
                 46 
                 47 
                 48 
                 49 
                 50 
                 51 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Wt. % Fe 2 O 3   
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
                 0.5 
               
               
                 Wt. % FeO 
                 0.263 
                 0.246 
                 0.255 
                 0.254 
                 0.25 
                 0.261 
                 0.231 
                 0.255 
               
               
                 Redox Ratio 
                 0.526 
                 0.492 
                 0.510 
                 0.508 
                 0.500 
                 0.522 
                 0.462 
                 0.450 
               
               
                 Wt. % MnO 2   
                 0.12 
                 0.05 
                 0.15 
                 0.2 
                 0.2 
                 0.2 
                 0.2 
                 0.2 
               
               
                 Wt. % CeO 2   
                 0.5 
                 0.25 
                 0.25 
                 0.025 
                 0.05 
                 0.1 
                 0.2 
                 0.3 
               
               
                 Wt. % TiO 2   
                 0.1 
                 0.25 
                 0.25 
                 0.025 
                 0.05 
                 0.1 
                 0.2 
                 0.1 
               
               
                 Salt Cake* 
                 10.5 
                 10.5 
                 10 
                 10 
                 10 
                 10 
                 10 
                 10 
               
               
                 Anthracite coal* 
                 2.1 
                 1.75 
                 1.91 
                 1.9 
                 1.9 
                 1.9 
                 1.9 
                 1.9 
               
             
          
           
               
                 Spectral Properties @ 4.0 mm. control thickness 
               
             
          
           
               
                 % LTA 
                 73.47 
                 74.01 
                 73.04 
                 73.78 
                 74.25 
                 73.4 
                 74.71 
                 75.2 
               
               
                 % UV 
                 46.4 
                 47.82 
                 46.06 
                 57.3 
                 56.01 
                 53.05 
                 47.83 
                 48.2 
               
               
                 % IR 
                 18.03 
                 19.8 
                 18.7996 
                 18.96 
                 19.41 
                 18.25 
                 21.68 
                 22.47 
               
               
                 % TSET 
                 43.22 
                 44.4 
                 43.27 
                 44.32 
                 44.72 
                 43.52 
                 45.71 
                 46.47 
               
               
                 Dominant Wavelength 
                 490.6 
                 491.4 
                 492.2 
                 489.5 
                 489.7 
                 490.5 
                 492.3 
                 491.2 
               
               
                 % Excitation Purity 
                 7 
                 6.2 
                 6.1 
                 7.4 
                 7.2 
                 7.1 
                 5.6 
                 5.9 
               
             
          
           
               
                 Most Preferred Embodiment of Invention with Spectral Properties @ 
               
               
                 indicated thickness 
               
             
          
           
               
                 Thickness in mm. 
                 4.8 
                 5 
                 4.8 
                 5 
                 5 
                 4.8 
                 5.2 
                 5.5 
               
               
                 % LTA 
                 70.39 
                 70.28 
                 69.89 
                 70.01 
                 70.57 
                 70.31 
                 70.4 
                 70.1 
               
               
                 % UV 
                 43.08 
                 43.39 
                 42.3 
                 53.06 
                 51.8 
                 49.52 
                 42.5 
                 41.9 
               
               
                 % IR 
                 13.3 
                 13.83 
                 13.96 
                 13.11 
                 13.5 
                 13.5 
                 14.3 
                 13.9 
               
               
                 % TSET 
                 39.08 
                 39.23 
                 39.01 
                 39.25 
                 39.65 
                 39.36 
                 39.4 
                 39.2 
               
               
                 Dominant Wavelength 
                 490.6 
                 491.4 
                 492.2 
                 489.4 
                 489.7 
                 490.4 
                 492.3 
                 491.1 
               
               
                 % Excitation Purity 
                 8.3 
                 7.7 
                 7.3 
                 10.9 
                 8.9 
                 8.4 
                 7.2 
                 8 
               
               
                   
               
               
                 *pounds per 1000 pounds sand  
               
             
          
         
       
     
     As can be seen from the examples above, the glass in accordance with the present invention provides for high transmittance, an improved infrared light absorption and an ultra violet absorption. Further, the use of anthracite coal and magnesium dioxide shifts the iron oxide equilibrium towards the reduced form of iron (FeO). Manganese oxide also prevents excessive reduction of sulfate to form iron sulfide that is amber in color and will decrease the transmittance of the glass. 
     As any person skilled in the art will recognize from the previous description and from the figures and claims, modifications and changes can be made to the preferred embodiment of the invention without departing from the scope of the invention as defined in the following claims.