Abstract:
Sodium-containing aluminosilicate and boroaluminosilicate glasses are described herein. The glasses can be used as substrates for photovoltaic devices, for example, thin film photovoltaic devices such as CIGS photovoltaic devices. These glasses can be characterized as having strain points ≧540° C., thermal expansion coefficient of from 6.5 to 9.5 ppm/° C., as well as liquidus viscosities in excess of 50,000 poise. As such, they are ideally suited for being formed into sheet by the fusion process.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
       [0001]    This application is a continuation of U.S. patent application Ser. No. 12/787,711 filed on May 26, 2010 which claims the benefit of U.S. Provisional Application No. 61/182,386 filed on May 29, 2009. 
     
    
     BACKGROUND 
       [0002]    Field 
         [0003]    Embodiments relate generally to sodium containing glasses and more particularly to fusion formable sodium containing glasses which may be useful in photochromic, electrochromic, Organic Light Emitting Diode (OLED) lighting, or photovoltaic applications, for example, thin film photovoltaics. 
         [0004]    Technical Background 
         [0005]    The fusion forming process typically produces flat glass with optimal surface and geometric characteristics useful for many electronics applications, for instance, substrates used in electronics applications, for example, display glass for LCD televisions. 
         [0006]    Over the last 10 years, Corning fusion glass products include 1737F™ 1737G™, Eagle2000F™, EagleXG™, Jade™, and Codes 1317 and 2317 (Gorilla Glass™). Efficient melting is generally believed to occur at a temperature corresponding to a melt viscosity of about 200 poise (p). These glasses share in common 200 p temperatures in excess of 1600° C., which can translate to accelerated tank and electrode corrosion, greater challenges for fining due to still more elevated finer temperatures, and/or reduced platinum system life time, particularly around the finer. Many have temperatures at 3000 poise in excess of about 1300° C., and since this is a typical viscosity for an optical stirrer, the high temperatures at this viscosity can translate to excessive stirrer wear and elevated levels of platinum defects in the body of the glass. 
         [0007]    Many of the above described glasses have delivery temperatures in excess of 1200° C., and this can contribute to creep of isopipe refractory materials, particularly for large sheet sizes. 
         [0008]    These attributes combine so as to limit flow (because of slow melt rates), to accelerate asset deterioration, to force rebuilds on timescales much shorter than product lifetimes, to force unacceptable (arsenic), expensive (capsule) or unwieldy (vacuum fining) solutions to defect elimination, and thus contribute in significant ways to the cost of manufacturing glass. 
         [0009]    In applications in which rather thick, comparatively low-cost glass with less extreme properties is required, these glasses are not only overkill, but prohibitively expensive to manufacture. This is particularly true when the competitive materials are made by the float process, a very good process for producing low cost glass with rather conventional properties. In applications that are cost sensitive, such as large-area photovoltaic panels and OLED lighting, this cost differential is so large as to make the price point of LCD-type glasses unacceptable. 
         [0010]    To reduce such costs, it is advantageous to drive down the largest overall contributors (outside of finishing), and many of these track directly with the temperatures used in the melting and forming process. Therefore, there is a need for a glass that melts at a lower temperature than those aforementioned glasses. 
         [0011]    Further, it would be advantageous to have a glass useful for low temperature applications, for instance, photovoltaic and OLED light applications. Further, it would be advantageous to have a glass whose processing temperatures were low enough that the manufacturing of the glass would not excessively consume the energy that these applications are aiming to save. 
       SUMMARY 
       [0012]    A compositional range of fusion-formable, high strain point sodium-containing aluminosilicate and boroaluminosilicate glasses useful, for example, for thin-film photovoltaic applications are described herein. More specifically, these glasses are advantageous materials to be used in copper indium gallium diselenide (CIGS) photovoltaic modules where the sodium required to optimize cell efficiency is to be derived from the substrate glass. Current CIGS module substrates are typically made from soda-lime glass sheet that has been manufactured by the float process. However, use of higher strain point glass substrates can enable higher temperature CIGS processing, which is expected to translate into desirable improvements in cell efficiency. Moreover, it may be that the smoother surface of fusion-formed glass sheets yields additional benefits, such as improved film adhesion, etc. 
         [0013]    Accordingly, the sodium-containing glasses described herein can be characterized by strain points ≧540° C. so as to provide advantage with respect to soda-lime glass and/or liquidus viscosity ≧50,000 poise to allow manufacture via the fusion process. In order to avoid thermal expansion mismatch between the substrate and CIGS layer, the inventive glasses are further characterized by a thermal expansion coefficient in the range of from 6.5 to 9.5 ppm/° C. In one embodiment, the glass is fusion formable and has a strain point of 540° C. or greater, a coefficient of thermal expansion of 50×10 −7  or greater, and having a liquidus viscosity of 150,000 poise or greater. 
         [0014]    One embodiment is a glass comprising, in weight percent:
       50 to 75 percent SiO 2 ;   1 to 20 percent Al 2 O 3 ;   0 to 3 percent TiO 2 ;   0 to 10 percent B 2 O 3 ;   8 to 25 percent total M 2 O; and   0 to 50 percent total RO;       
 
         [0021]    wherein, M is an alkali metal selected from Na, K, Li, Rb, and Cs and wherein the glass comprises at least 1 weight percent Na 2 O; and wherein, R is an alkaline earth metal selected from Mg, Ca, Ba, and Sr. 
         [0022]    Another embodiment is a glass consisting essentially of, in weight percent:
       50 to 75 percent SiO 2 ;   1 to 20 percent Al 2 O 3 ;   0 to 3 percent TiO 2 ;   0 to 10 percent B 2 O 3 ;   8 to 25 percent total M 2 O; and   0 to 50 percent total RO;       
 
         [0029]    wherein, M is an alkali metal selected from Na, K, Li, Rb, and Cs and wherein the glass comprises at least 1 weight percent Na 2 O; and wherein, R is an alkaline earth metal selected from Mg, Ca, Ba, and Sr. 
         [0030]    A glass comprising, in weight percent:
       50 to 75 percent SiO 2 ;   1 to 20 percent Al 2 O 3 ;   0 to 3 percent TiO 2 ;   0 to 4 percent MgO;   0 to 10 percent B 2 O 3 ;   8 to 25 percent total M 2 O; and   less than 14 percent total RO;       
 
         [0038]    wherein, M is an alkali metal selected from Na, K, Li, Rb, and Cs and wherein the glass comprises at least 1 weight percent Na 2 O; and wherein, R is an alkaline earth metal selected from Mg, Ca, Ba, and Sr, wherein the glass is fusion formable and has a strain point of 540° C. or greater, a coefficient of thermal expansion of 50×10 −7  or greater, and having a liquidus viscosity of 150,000 poise or greater. 
         [0039]    Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from the description or recognized by practicing the invention as described in the written description and claims hereof. 
         [0040]    It is to be understood that both the foregoing general description and the following detailed description are merely exemplary of the invention, and are intended to provide an overview or framework for understanding the nature and character of the invention as it is claimed. 
     
    
     DETAILED DESCRIPTION 
       [0041]    Reference will now be made in detail to various embodiments of the invention. 
         [0042]    As used herein, the term “substrate” can be used to describe either a substrate or a superstrate depending on the configuration of the photovoltaic cell. For example, the substrate is a superstrate, if when assembled into a photovoltaic cell, it is on the light incident side of a photovoltaic cell. The superstrate can provide protection for the photovoltaic materials from impact and environmental degradation while allowing transmission of the appropriate wavelengths of the solar spectrum. Further, multiple photovoltaic cells can be arranged into a photovoltaic module. Photovoltaic device can describe either a cell, a module, or both. 
         [0043]    As used herein, the term “adjacent” can be defined as being in close proximity. Adjacent structures may or may not be in physical contact with each other. Adjacent structures can have other layers and/or structures disposed between them. 
         [0044]    One embodiment is a glass comprising, in weight percent:
       50 to 75 percent SiO 2 ;   1 to 20 percent Al 2 O 3 ;   0 to 3 percent TiO 2 ;   0 to 10 percent B 2 O 3 ;   8 to 25 percent total M 2 O; and   0 to 50 percent total RO;       
 
         [0051]    wherein, M is an alkali metal selected from Na, K, Li, Rb, and Cs and wherein the glass comprises at least 1 weight percent Na 2 O; and wherein, R is an alkaline earth metal selected from Mg, Ca, Ba, and Sr. 
         [0052]    A glass comprising, in weight percent:
       50 to 75 percent SiO 2 ;   1 to 20 percent Al 2 O 3 ;   0 to 3 percent TiO 2 ;   0 to 4 percent MgO;   0 to 10 percent B 2 O 3 ;   8 to 25 percent total M 2 O; and   less than 14 percent total RO;   wherein, M is an alkali metal selected from Na, K, Li, Rb, and Cs and wherein the glass comprises at least 1 weight percent Na 2 O; and wherein, R is an alkaline earth metal selected from Mg, Ca, Ba, and Sr, wherein the glass is fusion formable and has a strain point of 540° C. or greater, a coefficient of thermal expansion of 50×10 −7  or greater, T 200  less than 1630° C., and having a liquidus viscosity of 150,000 poise or greater.       
 
         [0061]    According to one embodiment, the glass comprises:
       53 to 72 percent SiO 2 ;   2 to 17 percent Al 2 O 3 ;   0 to 3 percent TiO 2 ;   0 to 8 percent B 2 O 3 ;   8 to 25 percent total M 2 O; and   0 to 50 percent total RO.       
 
         [0068]    According to another embodiment, the glass comprises:
       55 to 72 percent SiO 2 ;   2 to 9 percent Al 2 O 3 ;   0 to 3 percent TiO 2 ;   0 to 8 percent B 2 O 3 ;   8 to 20 percent total M 2 O; and   0 to 30 percent total RO;       
 
         [0075]    wherein, the glass comprises at least 2 weight percent Na 2 O. 
         [0076]    In another embodiment, the glass comprises:
       1 to 8 percent Na 2 O;   5 to 16 percent K 2 O;   0 to 8 percent MgO;   0 to 7 percent CaO;   0 to 7 percent SrO; and   0 to 21 percent BaO.       
 
         [0083]    In another embodiment, the glass comprises:
       2 to 5 percent Na 2 O;   8 to 15 percent K 2 O;   0 to 5 percent MgO;   1 to 6 percent CaO;   0 to 6 percent SrO; and   0 to 12 percent BaO.       
 
         [0090]    In another embodiment, the glass comprises:
       53 to 71 SiO 2 ;   2 to 17 Al 2 O 3 ;   8 to 22 total M 2 O; and   0 to 40 total RO;       
 
         [0095]    wherein, M is an alkali metal selected from Na, K, Li, Rb, and Cs and wherein the glass comprises at least 1 weight percent Na 2 O; and wherein, R is an alkaline earth metal selected from Mg, Ca, Ba, and Sr. 
         [0096]    In another embodiment, the glass comprises:
       53 to 71 SiO 2 ;   2 to 17 Al 2 O 3 ;   8 to 22 total M 2 O; and   0 to 40 total RO;       
 
         [0101]    wherein, M is an alkali metal selected from Na, K, Li, Rb, and Cs and wherein the glass comprises at least 1 weight percent Na 2 O; and wherein, R is an alkaline earth metal selected from Mg, Ca, Ba, and Sr. 
         [0102]    In another embodiment, the glass comprises:
       65 to 76 SiO 2 ;   1 to 7 Al 2 O 3 ;   2.5 to 5 Na 2 O;   5.5 to 11 K 2 O;   0 to 8 MgO;   1 to 7 CaO; and   0 to 6 BaO.       
 
         [0110]    The glass, in one embodiment, is rollable. The glass, in one embodiment, is down-drawable. The glass can be slot drawn or fusion drawn, for example. According to another embodiment the glass can be float formed. 
         [0111]    The glass can further comprise 3 weight percent or less, for example, 0 to 3 weight percent, for example, greater than 0 to 3 weight percent, for example, 1 to 3 weight percent of TiO 2 , MnO, ZnO, Nb 2 O 5 , MoO 3 , Ta 2 O 5 , WO 3 , ZrO 2 , Y 2 O 3 , La 2 O 3 , HfO 2 , CdO, SnO 2 , Fe 2 O 3 , CeO 2 , As 2 O 3 , Sb 2 O 3 , Cl, Br, or combinations thereof. In some embodiments, the glass is substantially free of ZrO 2 . In some embodiments, the glass is substantially free of ZnO. The glass, in one embodiment, comprises 3 weight percent or less, for example, 0 to 3 weight percent, for example, greater than 0 to 3 weight percent, for example, 1 to 3 weight percent of TiO 2 . 
         [0112]    As mentioned above, the glasses, according some embodiments, comprise 0 to 10 weight percent, for example, greater than 0 to 10 weight percent B 2 O 3 , for example, 0.5 to 10 weight percent B 2 O 3 , for example 1 to 10 weight percent B 2 O 3 . B 2 O 3  is added to the glass to reduce melting temperature, to decrease liquidus temperature, to increase liquidus viscosity, and to improve mechanical durability relative to a glass containing no B 2 O 3 . 
         [0113]    The glass, according to one embodiment, comprises greater than 0 to 50 percent RO, for example, 0.5 to 50 percent RO, for example, 1 to 50 percent RO wherein, R is an alkaline earth metal. The glass, according to one embodiment, comprises less than 14 percent RO, for example, 0.5 to less than 14 percent RO, for example, 0.5 to 13 percent RO. 
         [0114]    The glass can comprise, for example, 0 to 8, greater than 0 to 8 weight percent, for example, 1 to 8 weight percent MgO. The glass can comprise, for example, 0 to 5, greater than 0 to 5 weight percent, for example, 1 to 5 weight percent MgO, for example, 1 to 4 percent MgO. MgO can be added to the glass to reduce melting temperature and to increase strain point. It can disadvantageously lower CTE relative to other alkaline earths (e.g., CaO, SrO, BaO), and so other adjustments may be made to keep the CTE within the desired range. Examples of suitable adjustments include increase SrO at the expense of CaO, increasing alkali oxide concentration, and replacing a smaller alkali oxide (e.g., Na 2 O) in part with a larger alkali oxide (e.g., K 2 O). 
         [0115]    According to another embodiment, the glass is substantially free of BaO. For example, the content of BaO can be 0.05 weight percent or less, for example, zero weight percent. 
         [0116]    In some embodiments, the glass is substantially free of Sb 2 O 3 , As 2 O 3 , or combinations thereof, for example, the glass comprises 0.05 weight percent or less of Sb 2 O 3  or As 2 O 3  or a combination thereof. For example, the glass can comprise zero weight percent of Sb 2 O 3  or As 2 O 3  or a combination thereof. 
         [0117]    The glasses, in some embodiments, comprise 0 to 7 weight percent CaO, for example, greater than 0, for example, 1 to 7 weight percent CaO, for example, 1 to 6 weight percent CaO. Relative to alkali oxides or SrO, CaO contributes to higher strain point, lower density, and lower melting temperature. It is a primary component of certain possible devitrification phases, particularly anorthite (CaAl 2 Si 2 O 8 ), and this phase has complete solid solution with an analogous sodium phase, albite (NaAlSi 3 O 8 ). High Na and Ca contents taken alone can cause liquidus temperatures to be unacceptably high. However, the chemical sources for CaO include limestone, a very inexpensive material, so to the extent that high volume and low cost are factors, it is typically useful to make the CaO content as high as can be reasonably achieved relative to other alkaline earth oxides. 
         [0118]    The glasses can comprise, in some embodiments, 0 to 7 weight percent SrO, for example, greater than zero to 7 weight percent, for example, 1 to 7 weight percent SrO, or for example, 0 to 6 weight percent SrO, for example, greater than zero to 6 weight percent, for example, 1 to 6 weight percent SrO. In some embodiments, the glass comprises less than 15 weight percent SrO, for example, 1 to 12 weight percent SrO. In certain embodiments, the glass contains no deliberately batched SrO, though it may of course be present as a contaminant in other batch materials. SrO contributes to higher coefficient of thermal expansion, and the relative proportion of SrO and CaO can be manipulated to improve liquidus temperature, and thus liquidus viscosity. SrO is not as effective as CaO or MgO for improving strain point, and replacing either of these with SrO tends to cause the melting temperature to increase. 
         [0119]    Also as mentioned above, the glasses, according to some embodiments, include 8 to 25 percent M 2 O, for example, 8 to 22 M 2 O, 8 to 20 M 2 O, where M is one of the alkali cations Li, Na, K, Rb and Cs. The alkali cations raise the CTE steeply, but also lower the strain point and, depending upon how they are added, increase melting temperatures. The least effective alkali oxide for CTE is Li 2 O, and the most effective alkali oxide is Cs 2 O. As noted above, sodium can participate in one of the possible devitrification phases of the inventive glasses, and while adjustments in other components can be used to counteract this, e.g., changing the CaO/(CaO+SrO) ratio, this tendency may make it advantageous to replace sodium with other alkalis, or to use a mix of alkalis instead of sodium alone. If high volume and low cost are important, then it is desirable to as much as possible confine the alkali oxides to Na 2 O and K 2 O or combinations thereof. 
         [0120]    In one embodiment, the glass comprises 1 to 8 weight percent Na 2 O, for example, 2 to 8 weight percent Na 2 O, for example, 3 to 8 weight percent Na 2 O, for example, 4 to 8 weight percent Na 2 O. In another embodiment, the glass comprises 1 to 5 weight percent Na 2 O, for example, 1 to 4 weight percent Na 2 O, for example, 1 to 3 weight percent Na 2 O, for example, 1 to 2 weight percent Na 2 O. 
         [0121]    In some embodiments, the weight percent of the combination of Na 2 O and K 2 O is greater than 3 percent, for example, greater than 5 percent, for example, greater than 10 percent, for example, greater than 12 percent. 
         [0122]    Another embodiment is a glass consisting essentially of, in weight percent:
       50 to 75 percent SiO 2 ;   1 to 20 percent Al 2 O 3 ;   0 to 3 percent TiO 2 ;   0 to 10 percent B 2 O 3 ;   8 to 25 percent total M 2 O; and   0 to 50 percent total RO;       
 
         [0129]    wherein, M is an alkali metal selected from Na, K, Li, Rb, and Cs and wherein the glass comprises at least 1 weight percent Na 2 O; and wherein, R is an alkaline earth metal selected from Mg, Ca, Ba, and Sr. 
         [0130]    The glass, according to some embodiments, is down-drawable; that is, the glass is capable of being formed into sheets using down-draw methods such as, but not limited to, fusion draw and slot draw methods that are known to those skilled in the glass fabrication arts. Such down-draw processes are used in the large-scale manufacture of ion-exchangeable flat glass. 
         [0131]    The fusion draw process uses a drawing tank that has a channel for accepting molten glass raw material. The channel has weirs that are open at the top along the length of the channel on both sides of the channel. When the channel fills with molten material, the molten glass overflows the weirs. Due to gravity, the molten glass flows down the outside surfaces of the drawing tank. These outside surfaces extend down and inwardly so that they join at an edge below the drawing tank. The two flowing glass surfaces join at this edge to fuse and form a single flowing sheet. The fusion draw method offers the advantage that, since the two glass films flowing over the channel fuse together, neither outside surface of the resulting glass sheet comes in contact with any part of the apparatus. Thus, the surface properties are not affected by such contact. 
         [0132]    The slot draw method is distinct from the fusion draw method. Here the molten raw material glass is provided to a drawing tank. The bottom of the drawing tank has an open slot with a nozzle that extends the length of the slot. The molten glass flows through the slot/nozzle and is drawn downward as a continuous sheet therethrough and into an annealing region. Compared to the fusion draw process, the slot draw process provides a thinner sheet, as only a single sheet is drawn through the slot, rather than two sheets being fused together, as in the fusion down-draw process. 
         [0133]    In order to be compatible with down-draw processes, the aluminoborosilicate glass described herein has a high liquidus viscosity. In one embodiment, the glass has a liquidus viscosity of 50,000 poise or greater, for example, 150,000 poise or greater, for example, 200,000 poise or greater, for example, 250,000 poise or greater, for example, 300,000 poise or greater, for example, 350,000 poise or greater, for example, 400,000 poise or greater, for example, greater than or equal to 500,000 poise. The liquidus viscosities of some exemplary glasses are closely correlated with the difference between the liquidus temperature and the softening point. For downdraw processes, some exemplary glasses advantageously have liquidus—softening point less than about 230° C., for example, less than 200° C. 
         [0134]    Accordingly, in one embodiment, the glass has a strain point of 540° C. or greater, for example, 540° C. to 600° C. In some embodiments, the glass has a coefficient of thermal expansion of 50×10 −7  or greater, for example, 60×10 −7  or greater, for example, 70×10 −7  or greater, for example, 80×10 −7  or greater. In one embodiment, the glass has a strain point of from 50×10 −7  to 90×10 −7 . 
         [0135]    In one embodiment, the glass has a coefficient of thermal expansion of 50×10 −7  or greater and a strain point of 540° C. or greater. 
         [0136]    According to one embodiment, the glass is ion exchanged in a salt bath comprising one or more salts of alkali ions. The glass can be ion exchanged to change its mechanical properties. For example, smaller alkali ions, such as lithium or sodium, can be ion-exchanged in a molten salt containing one or more larger alkali ions, such as sodium, potassium, rubidium or cesium. If performed at a temperature well below the strain point for sufficient time, a diffusion profile will form in which the larger alkali moves into the glass surface from the salt bath, and the smaller ion is moved from the interior of the glass into the salt bath. When the sample is removed, the surface will go under compression, producing enhanced toughness against damage. Such toughness may be desirable in instances where the glass will be exposed to adverse environmental conditions, such as photovoltaic grids exposed to hail. A large alkali already in the glass can also be exchanged for a smaller alkali in a salt bath. If this is performed at temperatures close to the strain point, and if the glass is removed and its surface rapidly reheated to high temperature and rapidly cooled, the surface of the glass will show considerable compressive stress introduced by thermal tempering. This will also provide protection against adverse environmental conditions. It will be clear to one skilled in the art that any monovalent cation can be exchanged for alkalis already in the glass, including copper, silver, thallium, etc., and these also provide attributes of potential value to end uses, such as introducing color for lighting or a layer of elevated refractive index for light trapping. 
         [0137]    According to another embodiment, the glass can be float formed as known in the art of float forming glass. 
         [0138]    In one embodiment, the glass is in the form of a sheet. 
         [0000]    The glass in the form of a sheet can be thermally tempered. 
         [0139]    In one embodiment, an Organic Light Emitting Diode device comprises the glass in the form of a sheet. 
         [0140]    The glass, according to one embodiment, is transparent. 
         [0141]    In one embodiment, a photovoltaic device comprises the glass in the form of a sheet. The photovoltaic device can comprise more than one of the glass sheets, for example, as a substrate and/or as a superstrate. In one embodiment, the photovoltaic device comprises the glass sheet as a substrate and/or superstrate, a conductive material adjacent to the substrate, and an active photovoltaic medium adjacent to the conductive material. In one embodiment, the active photovoltaic medium comprises a CIGS layer. In one embodiment, the active photovoltaic medium comprises a cadmium telluride (CdTe) layer. In one embodiment, the photovoltaic device comprises a functional layer comprising copper indium gallium diselenide or cadmium telluride. In one embodiment, the photovoltaic device the functional layer is copper indium gallium diselenide. In one embodiment, the functional layer is cadmium telluride. 
         [0142]    In one embodiment, the glass sheet is transparent. In one embodiment, the glass sheet as the substrate and/or superstrate is transparent. 
         [0143]    According to some embodiments, the glass sheet has a thickness of 4.0 mm or less, for example, 3.5 mm or less, for example, 3.2 mm or less, for example, 3.0 mm or less, for example, 2.5 mm or less, for example, 2.0 mm or less, for example, 1.9 mm or less, for example, 1.8 mm or less, for example, 1.5 mm or less, for example, 1.1 mm or less, for example, 0.5 mm to 2.0 mm, for example, 0.5 mm to 1.1 mm, for example, 0.7 mm to 1.1 mm. Although these are exemplary thicknesses, the glass sheet can have a thickness of any numerical value including decimal places in the range of from 0.1 mm up to and including 4.0 mm. 
         [0144]    In one embodiment, an electrochromic device comprises the glass in the form of a sheet. The electrochromic device can be, for example, an electrochromic window. In one embodiment, the electrochromic window comprises one or more of the glass sheets, such as in a single, double, or triple pane window. 
         [0145]    The fusion formable glasses of this invention, by virtue of their relatively high strain point, represent advantaged substrate materials for CIGS photovoltaic modules. When manufactured by the fusion process, their superior surface quality relative to that of float glass may also result in further improvements to the photovoltaic module making process. Advantageous embodiments of this invention are characterized by liquidus viscosity in excess of 400,000 poise, thereby enabling the fabrication of the relatively thick glass sheet that may be required by some module manufacturers. Finally, the most advantageous embodiments of this invention comprise glasses for which the 200 poise temperature is less than 1580° C., providing for the possibility of significantly lower cost melting/forming. 
       Examples 
       [0146]    The following is an example of how to fabricate a sample of an exemplary glass, according to one embodiment of the invention, as shown in Table 1. This composition corresponds to composition number 12 shown in Table 4. 
         [0000]                                              TABLE 1                       oxide   mol %                                        SiO 2     74.75           Al 2 O 3     1.76           MgO   5.23           CaO   5.66           SrO   2.78           Na 2 O   3.00           K 2 O   6.72           SnO 2     0.10                        
In some embodiments, the total does not add up to 100%, since certain tramp elements are present at non-negligible concentrations.
 
         [0147]    Batch materials, as shown in Table 2 were weighed and added to a 4 liter plastic container: 
         [0000]    
       
         
               
               
               
             
               
               
               
             
           
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                 Batch Components 
                 batch weight 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 sand 
                 1656.84 
               
               
                   
                 alumina 
                 65.71 
               
               
                   
                 Magnesia 
                 79.80 
               
               
                   
                 Limestone 
                 221.90 
               
               
                   
                 Strontium carbonate 
                 161.38 
               
               
                   
                 Sodium carbonate 
                 117.06 
               
               
                   
                 Potassium carbonate 
                 353.91 
               
               
                   
                 10% SnO 2  and 90% sand 
                 57.6 
               
               
                   
                   
               
             
          
         
       
     
         [0148]    It should be appreciated that in the batch, limestone, depending on the source can contain tramp elements and/or vary amounts of one or more oxides, for example, MgO and/or BaO. The sand is advantageously beneficiated so that at least 80% by mass passes 60 mesh, for example 80 mesh, for example 100 mesh. The SnO 2  added, in this example, was pre-mixed with sand at a level of 10% by weight so as to ensure homogeneous mixing with the other components. The bottle containing the batch materials was mounted to a tumbler and the batch materials were mixed so as to make a homogeneous batch and to break up soft agglomerates. The mixed batch was transferred to a 1800 cc platinum crucible and placed into a high-temperature ceramic backer. The platinum in its backer was loaded into a glo-bar furnace idling at a temperature of 1600° C. After 16 hours, the crucible+backer was removed and the glass melt was poured onto a cold surface, such as a steel plate, to form a patty, and then transferred to an annealer held at a temperature of 615° C. The glass patty was held at the annealer temperature for 2 hours, then cooled at a rate of 1° C. per minute to room temperature. 
         [0149]    Table 3, Table 4, Table 5, Table 6, Table 7, Table 8, and Table 9 show exemplary glasses, according to embodiments of the invention, and made according to the above example. Properties data for some exemplary glasses are also shown in Table 3, Table 4, Table 5, Table 6, Table 7, Table 8, and Table 9. 
         [0150]    In the Tables T str (° C.) is the strain point which is the temperature when the viscosity is equal to 10 14.7  P as measured by beam bending or fiber elongation. T ann (° C.) is the annealing point which is the temperature when the viscosity is equal to 10 13.18  P as measured by beam bending or fiber elongation. T s (° C.) is the softening point which is the temperature when the viscosity is equal to 10 7.6  P as measured by beam bending or fiber elongation. α(10 −7 /° C.) or a(10 −7 /° C.) in the Tables is the coefficient of thermal expansion (CTE) which is the amount of dimensional change from either 0 to 300° C. or 25 to 300° C. depending on the measurement. CTE is typically measured by dilatometry. r(g/cc) is the density which is measured with the Archimedes method (ASTM C693). T 200 (° C.) is the two-hundred Poise (P) temperature. This is the temperature when the viscosity of the melt is 200 P as measured by HTV (high temperature viscosity) measurement which uses concentric cylinder viscometry. T liq (° C.) is the liquidus temperature. This is the temperature where the first crystal is observed in a standard gradient boat liquidus measurement (ASTM C829-81). Generally this test is 72 hours but can be as short as 24 hours to increase throughput at the expense of accuracy (shorter tests could underestimate the liquidus temperature). η liq (° C.) is the liquidus viscosity. This is the viscosity of the melt corresponding to the liquidus temperature. 
         [0000]    
       
         
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                 Example 
                 1 
                 2 
                 3 
                 4 
                 5 
                 6 
                 7 
                 8 
                 9 
                 10 
                 11 
               
               
                   
               
             
             
               
                 Composition (mol %) 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 Na 2 O 
                 6 
                 2 
                 3 
                 3 
                 2 
                 3 
                 3.92 
                 3.92 
                 3.16 
                 3.16 
                 3.14 
               
               
                 K 2 O 
                 6 
                 10 
                 9 
                 9 
                 10.5 
                 9.5 
                 7.83 
                 7.83 
                 10.03 
                 9.03 
                 9.95 
               
               
                 MgO 
                 5.74 
                 5.74 
                 6.25 
                 5.5 
                 11 
                 11 
                 5.63 
                 5.62 
                 7.08 
                 7.07 
                 7.02 
               
               
                 CaO 
                 2.23 
                 2.23 
                 6.75 
                 5.9 
                 3.1 
                 3.1 
                 3.43 
                 3.43 
                 3.27 
                 3.93 
                 3.25 
               
               
                 SrO 
                 1.55 
                 1.55 
                 3.3 
                 2.9 
                 1 
                 1 
                 2.35 
                 2.35 
                 1.05 
                 1.39 
                 1.04 
               
               
                 BaO 
                 0 
                 0 
                 2 
                 4 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 TiO 2   
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 B 2 O 3   
                 0.8 
                 0.8 
                 0 
                 0 
                 1.65 
                 1.65 
                 0.78 
                 0.78 
                 0.72 
                 0.72 
                 1.5 
               
               
                 Al 2 O 3   
                 4.8 
                 4.8 
                 2.35 
                 2.35 
                 3.15 
                 3.15 
                 4.7 
                 6.66 
                 4.34 
                 4.35 
                 5.3 
               
               
                 SiO 2   
                 72.81 
                 72.81 
                 67.25 
                 67.25 
                 67.5 
                 67.5 
                 71.29 
                 69.34 
                 70.25 
                 70.25 
                 68.7 
               
               
                 SnO 2   
                 0.07 
                 0.07 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.07 
                 0.07 
                 0.1 
                 0.1 
                 0.1 
               
               
                 Composition (wt %) 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 Na 2 O 
                 5.81 
                 1.9 
                 2.81 
                 2.73 
                 1.95 
                 2.94 
                 3.74 
                 3.7 
                 3.03 
                 3.04 
                 2.99 
               
               
                 K 2 O 
                 8.84 
                 14.5 
                 12.8 
                 12.5 
                 15.6 
                 14.2 
                 11.4 
                 11.3 
                 14.7 
                 13.2 
                 14.4 
               
               
                 MgO 
                 3.62 
                 3.55 
                 3.81 
                 3.26 
                 6.98 
                 7.03 
                 3.51 
                 3.46 
                 4.43 
                 4.44 
                 4.36 
               
               
                 CaO 
                 1.96 
                 1.92 
                 5.73 
                 4.87 
                 2.74 
                 2.76 
                 2.97 
                 2.94 
                 2.84 
                 3.43 
                 2.81 
               
               
                 SrO 
                 2.52 
                 2.47 
                 5.18 
                 4.42 
                 1.64 
                 1.65 
                 3.76 
                 3.72 
                 1.69 
                 2.24 
                 1.66 
               
               
                 BaO 
                 0 
                 0 
                 4.64 
                 9.02 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 TiO 2   
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 B 2 O 3   
                 0.87 
                 0.86 
                 0 
                 0 
                 1.81 
                 1.82 
                 0.84 
                 0.83 
                 0.78 
                 0.78 
                 1.61 
               
               
                 Al 2 O 3   
                 7.66 
                 7.51 
                 3.63 
                 3.53 
                 5.07 
                 5.09 
                 7.4 
                 10.4 
                 6.86 
                 6.9 
                 8.32 
               
               
                 SiO 2   
                 68.5 
                 67.1 
                 61.1 
                 59.4 
                 63.9 
                 64.2 
                 66.2 
                 63.5 
                 65.4 
                 65.7 
                 63.5 
               
               
                 SnO 2   
                 0.17 
                 0.16 
                 0.23 
                 0.22 
                 0.24 
                 0.24 
                 0.16 
                 0.16 
                 0.23 
                 0.23 
                 0.23 
               
               
                 T str  (° C.) 
                 548 
                 581 
                 552 
                 544 
                 573 
                 559 
                 560 
                 577 
                 560 
                 567 
                 562 
               
               
                 T ann  (° C.) 
                 595 
                 632 
                 599 
                 591 
                 622 
                 607 
                 609 
                 627 
                 611 
                 617 
                 612 
               
               
                 T s  (° C.) 
                 824 
                 879 
                 796 
                 787 
                   
                   
                   
                   
                   
                   
                   
               
               
                 a (10 −7 /° C.) 
                 79.2 
                 80.5 
                 90.4 
                 92.5 
                 83 
                 83.9 
                 82.2 
                 82.2 
                   
                   
                   
               
               
                 r (gm/cc) 
                 2.457 
                 2.448 
                 2.635 
                 2.699 
                 2.474 
                 2.479 
                 2.489 
                 2.497 
                 2.467 
                 2.476 
                 2.469 
               
               
                 T 200  (° C.) 
                   
                   
                   
                 1392 
                   
                 1499 
                 1575 
                 1616 
                 1581 
                 1569 
                 1570 
               
               
                 T liq  (° C.) 
                 970 
                 995 
                 1015 
                 970 
                 1115 
                 1060 
                 1000 
                 1100 
                 1035 
                 1062 
                 1077 
               
               
                 h liq  (kp) 
                   
                   
                   
                 105 
                   
                 56 
                 351 
                 88 
                 175 
                 101 
                 71 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 4 
               
               
                   
               
               
                 Example 
                 12 
                 13 
                 14 
                 15 
                 16 
                 17 
                 18 
                 19 
                 20 
                 21 
                 22 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Composition (mol %) 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 Na 2 O 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3 
                 3.75 
                 3.75 
                 3.75 
                 4.61 
                 3.95 
               
               
                 K 2 O 
                 7.17 
                 7.17 
                 6.97 
                 6.65 
                 6.59 
                 6.59 
                 6.96 
                 6.69 
                 6.43 
                 6 
                 7.89 
               
               
                 MgO 
                 6.59 
                 6.59 
                 6.47 
                 5.18 
                 5.13 
                 5.13 
                 5.01 
                 4.82 
                 4.63 
                 4.31 
                 6.67 
               
               
                 CaO 
                 5.54 
                 5.54 
                 5.42 
                 5.6 
                 5.55 
                 5.55 
                 5.41 
                 5.2 
                 4.99 
                 4.66 
                 3.46 
               
               
                 SrO 
                 2.47 
                 2.47 
                 2.41 
                 2.75 
                 2.72 
                 2.72 
                 3.67 
                 3.53 
                 3.38 
                 3.16 
                 2.37 
               
               
                 BaO 
                 0 
                 0 
                 0 
                 1 
                 2 
                 2 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 TiO 2   
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 B 2 O 3   
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0.7 
                 0.67 
                 0.64 
                 0.6 
                 0 
               
               
                 Al 2 O 3   
                 1.88 
                 3.38 
                 2.38 
                 2.74 
                 1.72 
                 2.72 
                 4.18 
                 4.02 
                 3.86 
                 5.3 
                 4.39 
               
               
                 SiO 2   
                 73.25 
                 71.75 
                 73.25 
                 72.98 
                 73.19 
                 72.19 
                 70.24 
                 71.24 
                 72.24 
                 71.28 
                 71.2 
               
               
                 SnO 2   
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.08 
                 0.08 
                 0.08 
                 0.08 
                 0.07 
               
               
                 Composition (wt %) 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 Na 2 O 
                 2.94 
                 2.91 
                 2.94 
                 2.87 
                 2.85 
                 2.83 
                 3.58 
                 3.59 
                 3.6 
                 4.39 
                 3.8 
               
               
                 K 2 O 
                 10.7 
                 10.6 
                 10.4 
                 9.7 
                 9.54 
                 9.48 
                 10.1 
                 9.74 
                 9.39 
                 8.7 
                 11.6 
               
               
                 MgO 
                 4.22 
                 4.17 
                 4.13 
                 3.24 
                 3.18 
                 3.16 
                 3.12 
                 3.01 
                 2.9 
                 2.68 
                 4.18 
               
               
                 CaO 
                 4.93 
                 4.88 
                 4.81 
                 4.87 
                 4.79 
                 4.76 
                 4.67 
                 4.51 
                 4.34 
                 4.03 
                 3.02 
               
               
                 SrO 
                 4.07 
                 4.02 
                 3.96 
                 4.42 
                 4.34 
                 4.31 
                 5.86 
                 5.65 
                 5.42 
                 5.04 
                 3.82 
               
               
                 BaO 
                 0 
                 0 
                 0 
                 2.38 
                 4.72 
                 4.69 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 TiO 2   
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 B 2 O 3   
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0.75 
                 0.72 
                 0.69 
                 0.64 
                 0 
               
               
                 Al 2 O 3   
                 3.04 
                 5.42 
                 3.84 
                 4.33 
                 2.7 
                 4.24 
                 6.57 
                 6.33 
                 6.1 
                 8.32 
                 6.95 
               
               
                 SiO 2   
                 69.8 
                 67.7 
                 69.6 
                 67.9 
                 67.6 
                 66.3 
                 65.1 
                 66.2 
                 67.3 
                 65.9 
                 66.5 
               
               
                 SnO 2   
                 0.24 
                 0.24 
                 0.24 
                 0.23 
                 0.23 
                 0.23 
                 0.19 
                 0.19 
                 0.19 
                 0.19 
                 0.16 
               
               
                 T str  (° C.) 
                 567 
                 580 
                 573 
                 569 
                 557 
                 567 
                 563 
                 563 
                 563 
                 565 
                 564 
               
               
                 T ann  (° C.) 
                 618 
                 632 
                 623 
                 620 
                 607 
                 617 
                 611 
                 611 
                 611 
                 614 
                 615 
               
               
                 T s  (° C.) 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 a (10 −7 /° C.) 
                 79 
                 78.8 
                 79.2 
                 78.5 
                 79.9 
                 79.9 
                 81.7 
                 81.1 
                 78.9 
                 79.4 
                 83.3 
               
               
                 r (gm/cc) 
                 2.496 
                 2.503 
                 2.494 
                 2.541 
                 2.584 
                 2.584 
                 2.541 
                 2.529 
                 2.521 
                 2.516 
                 2.494 
               
               
                 T 200  (° C.) 
                 1542 
                 1570 
                 1559 
                 1549 
                 ~1520 
                 1529 
                 ~1530 
                 1546 
                 ~1565 
                 1585 
                 1585 
               
               
                 T liq  (° C.) 
                 1020 
                 1075 
                 1030 
                 1045 
                 955 
                 1015 
                 1055 
                 1055 
                 1050 
                 1030 
                 1020 
               
               
                 h liq  (kp) 
                 194 
                 92 
                 190 
                 121 
                 ~630 
                 194 
                 ~70 
                 80 
                 ~110 
                 175 
                 292 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 5 
               
               
                   
               
               
                 Example 
                 23 
                 24 
                 25 
                 26 
                 27 
                 28 
                 29 
                 30 
                 31 
                 32 
                 33 
               
               
                   
               
             
             
               
                 Composition (mol %) 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 Na 2 O 
                 3.1 
                 3.12 
                 3.62 
                 3.2 
                 3.33 
                 3.02 
                 4.3 
                 4 
                 3 
                 3.98 
                 4.3 
               
               
                 K 2 O 
                 8.59 
                 8.64 
                 7.25 
                 10.14 
                 7.52 
                 6.82 
                 7.6 
                 4.93 
                 6 
                 6.88 
                 9.75 
               
               
                 MgO 
                 10.06 
                 10.11 
                 6.25 
                 5 
                 3.12 
                 2.86 
                 3.3 
                 4.22 
                 0 
                 9.06 
                 4.5 
               
               
                 CaO 
                 2.85 
                 2.86 
                 4.55 
                 3.31 
                 5.22 
                 4.73 
                 5.6 
                 7.77 
                 0 
                 2.56 
                 1.75 
               
               
                 SrO 
                 0.91 
                 0.91 
                 2.18 
                 1.07 
                 0.36 
                 0.34 
                 1 
                 2.4 
                 0.21 
                 1.76 
                 0.8 
               
               
                 BaO 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 1.43 
                 10.12 
                 1.44 
                 1.05 
               
               
                 TiO 2   
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 1 
               
               
                 B 2 O 3   
                 1.51 
                 1 
                 1 
                 1.76 
                 2.71 
                 2.46 
                 2.4 
                 2.51 
                 7.83 
                 0.88 
                 1.15 
               
               
                 Al 2 O 3   
                 2.88 
                 2.9 
                 4.8 
                 5.36 
                 4.59 
                 4.54 
                 7.2 
                 5.42 
                 6 
                 4.44 
                 7.1 
               
               
                 SiO 2   
                 70 
                 70.36 
                 70.25 
                 70.08 
                 73.06 
                 75.24 
                 68.5 
                 66.89 
                 66.83 
                 68.9 
                 68.6 
               
               
                 SnO 2   
                 0.15 
                 0.15 
                 0.1 
                 0.08 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 0 
               
               
                 Composition (wt %) 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 Na 2 O 
                 3.05 
                 3.07 
                 3.48 
                 3.02 
                 3.21 
                 2.91 
                 4.05 
                 3.78 
                 2.47 
                 3.8 
                 3.96 
               
               
                 K 2 O 
                 12.9 
                 13 
                 10.6 
                 14.6 
                 11 
                 10 
                 10.9 
                 7.09 
                 7.52 
                 10 
                 13.7 
               
               
                 MgO 
                 6.46 
                 6.49 
                 3.92 
                 3.08 
                 1.96 
                 1.8 
                 2.03 
                 2.6 
                 0 
                 5.64 
                 2.7 
               
               
                 CaO 
                 2.54 
                 2.56 
                 3.97 
                 2.84 
                 4.56 
                 4.13 
                 4.78 
                 6.66 
                 0 
                 2.22 
                 1.46 
               
               
                 SrO 
                 1.5 
                 1.5 
                 3.51 
                 1.7 
                 0.58 
                 0.54 
                 1.58 
                 3.8 
                 0.29 
                 2.82 
                 1.23 
               
               
                 BaO 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 3.35 
                 20.7 
                 3.41 
                 2.4 
               
               
                 TiO 2   
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 1.19 
               
               
                 B 2 O 3   
                 1.67 
                 1.11 
                 1.08 
                 1.87 
                 2.94 
                 2.67 
                 2.55 
                 2.67 
                 7.26 
                 0.95 
                 1.19 
               
               
                 Al 2 O 3   
                 4.68 
                 4.71 
                 7.61 
                 8.35 
                 7.29 
                 7.22 
                 11.2 
                 8.44 
                 8.14 
                 6.99 
                 10.8 
               
               
                 SiO 2   
                 66.9 
                 67.3 
                 65.6 
                 64.3 
                 68.4 
                 70.5 
                 62.7 
                 61.4 
                 53.4 
                 63.9 
                 61.4 
               
               
                 SnO 2   
                 0.24 
                 0.24 
                 0.23 
                 0.18 
                 0.02 
                 0.23 
                 0.23 
                 0.23 
                 0.2 
                 0.23 
                 0 
               
               
                 T str  (° C.) 
                 560 
                 561 
                 571 
                 562 
                 561 
                 571 
                 565 
                 568 
                 551 
                 562 
                 553 
               
               
                 T ann  (° C.) 
                 609 
                 611 
                 620 
                 611 
                 607 
                 621 
                 610 
                 612 
                 590 
                 608 
                 601 
               
               
                 T s  (° C.) 
                   
                   
                   
                   
                   
                   
                 831 
                   
                   
                   
                   
               
               
                 a (10 −7 /° C.) 
                 81.6 
                 82.4 
                 79.7 
                 86 
                 76.7 
                 69.9 
                 80.2 
                 75.7 
                 74.9 
                 79.1 
                 87.3 
               
               
                 r (gm/cc) 
                 2.462 
                 2.462 
                 2.498 
                 2.463 
                 2.445 
                 2.421 
                 2.472 
                 2.582 
                 2.796 
                 2.538 
                 2.498 
               
               
                 T 200  (° C.) 
                 1558 
                 1549 
                 1595 
                 1610 
                 1613 
                 1660 
                 1584 
                   
                 1410 
                 1548 
                 1623 
               
               
                 T liq  (° C.) 
                 1065 
                 1070 
                 1095 
                 1010 
                 1020 
                 1040 
                 1070 
                 1090 
                 930 
                 1050 
                 1100 
               
               
                 h liq  (kp) 
                 90 
                 81 
                 71 
                 344 
                 142 
                 270 
                 69 
                   
                 124 
                 110 
                 67 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 6 
               
               
                   
               
               
                 Example 
                 34 
                 35 
                 36 
                 37 
                 38 
                 39 
                 40 
                 41 
                 42 
                 43 
                 44 
               
               
                   
               
             
             
               
                 Composition (mol %) 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 Na 2 O 
                 4.2 
                 3.5 
                 4.2 
                 4.2 
                 3 
                 3 
                 3.3 
                 4 
                 4 
                 6.42 
                 7.15 
               
               
                 K 2 O 
                 6.2 
                 7.5 
                 6.2 
                 6.2 
                 7 
                 7 
                 6.8 
                 7.5 
                 6.5 
                 6.06 
                 5.7 
               
               
                 MgO 
                 6 
                 0 
                 6 
                 6 
                 5.4 
                 5.4 
                 5.5 
                 4.9 
                 5.3 
                 0 
                 0 
               
               
                 CaO 
                 2.3 
                 0 
                 2.3 
                 2.3 
                 5.8 
                 5.8 
                 4.9 
                 4.9 
                 5.3 
                 5.34 
                 5.7 
               
               
                 SrO 
                 1.6 
                 0.18 
                 1.6 
                 1.6 
                 2.9 
                 2.9 
                 2.6 
                 0.05 
                 0.05 
                 0.05 
                 0.04 
               
               
                 BaO 
                 2.1 
                 8.62 
                 2.1 
                 2.1 
                 0 
                 0 
                 0.5 
                 2.35 
                 2.55 
                 2.29 
                 1.91 
               
               
                 TiO 2   
                 1 
                 0 
                 2 
                 2 
                 2 
                 2 
                 2 
                 0 
                 0 
                 0 
                 0 
               
               
                 B 2 O 3   
                 0.8 
                 6.6 
                 0.8 
                 0.8 
                 0 
                 0 
                 0.2 
                 0.8 
                 0.8 
                 3.36 
                 2.8 
               
               
                 Al 2 O 3   
                 5 
                 6 
                 6 
                 7 
                 1.9 
                 2.9 
                 3.4 
                 7 
                 7 
                 9.8 
                 11 
               
               
                 SiO 2   
                 70.8 
                 67.6 
                 68.8 
                 67.8 
                 72 
                 71 
                 70.8 
                 68.5 
                 68.5 
                 65.48 
                 64.7 
               
               
                 SnO 2   
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 Composition (wt %) 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 Na 2 O 
                 3.93 
                 2.92 
                 3.9 
                 3.87 
                 2.91 
                 2.89 
                 3.16 
                 3.7 
                 3.72 
                 5.76 
                 6.42 
               
               
                 K 2 O 
                 8.85 
                 9.55 
                 8.77 
                 8.71 
                 10.4 
                 10.3 
                 9.91 
                 10.6 
                 9.2 
                 8.29 
                 7.81 
               
               
                 MgO 
                 3.66 
                 0 
                 3.63 
                 3.61 
                 3.42 
                 3.4 
                 3.43 
                 2.96 
                 3.21 
                 0 
                 0 
               
               
                 CaO 
                 1.95 
                 0 
                 1.94 
                 1.92 
                 5.11 
                 5.07 
                 4.25 
                 4.12 
                 4.47 
                 4.35 
                 4.65 
               
               
                 SrO 
                 2.51 
                 0.25 
                 2.49 
                 2.47 
                 4.72 
                 4.69 
                 4.17 
                 0.08 
                 0.08 
                 0.08 
                 0.06 
               
               
                 BaO 
                 4.88 
                 17.9 
                 4.83 
                 4.8 
                 0 
                 0 
                 1.19 
                 5.4 
                 5.88 
                 5.1 
                 4.26 
               
               
                 TiO 2   
                 1.21 
                 0 
                 2.4 
                 2.38 
                 2.51 
                 2.49 
                 2.47 
                 0 
                 0 
                 1.39 
                 1.16 
               
               
                 B 2 O 3   
                 0.84 
                 6.21 
                 0.84 
                 0.83 
                 0 
                 0 
                 0.22 
                 0.83 
                 0.84 
                 3.4 
                 2.83 
               
               
                 Al 2 O 3   
                 7.72 
                 8.27 
                 9.18 
                 10.6 
                 3.04 
                 4.61 
                 5.37 
                 10.7 
                 10.7 
                 14.5 
                 16.3 
               
               
                 SiO 2   
                 64.4 
                 54.9 
                 62 
                 60.8 
                 67.9 
                 66.6 
                 65.8 
                 61.6 
                 61.9 
                 57.1 
                 56.5 
               
               
                 SnO 2   
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 T str  (° C.) 
                 563 
                 546 
                 571 
                 580 
                 567 
                 574 
                 568 
                 567 
                 574 
                 555 
                 559 
               
               
                 T ann  (° C.) 
                 611 
                 585 
                 618 
                 628 
                 615 
                 622 
                 616 
                 617 
                 623 
                 599 
                 603 
               
               
                 T s  (° C.) 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 a (10 −7 /° C.) 
                 77.2 
                 80.5 
                 77.3 
                 76.9 
                 77.2 
                 77 
                 77.3 
                 83.1 
                 78 
                 81.1 
                 82.9 
               
               
                 r (gm/cc) 
                 2.546 
                 2.747 
                 2.565 
                 2.566 
                 2.525 
                 2.532 
                 2.538 
                 2.536 
                 2.547 
                 2.543 
                 2.537 
               
               
                 T 200  (° C.) 
                 1597 
                 1423 
                 1595 
                 1603 
                 1513 
                 1536 
                 1555 
                 1596 
                 1587 
                 1571 
                 1611 
               
               
                 T liq  (° C.) 
                 1000 
                 950 
                 1040 
                 1070 
                 1015 
                 1065 
                 1020 
                 1100 
                 1125 
                 1030 
                 1060 
               
               
                 h liq  (kp) 
                 364 
                 78 
                 164 
                 111 
                 140 
                 67 
                 162 
                 65 
                 43 
                 98 
                 106 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 7 
               
               
                   
               
               
                 Example 
                 45 
                 46 
                 47 
                 48 
                 49 
                 50 
                 51 
               
               
                   
               
             
             
               
                 Composition (mol %) 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Na 2 O 
                 4 
                 4 
                 4.3 
                 3.93 
                 3.95 
                 3.2 
                 2.95 
               
               
                 K 2 O 
                 8 
                 6 
                 6.45 
                 7.86 
                 7.89 
                 9.81 
                 9.04 
               
               
                 MgO 
                 5.74 
                 5.74 
                 6.16 
                 5.65 
                 5.67 
                 0.51 
                 0.46 
               
               
                 CaO 
                 2.23 
                 2.23 
                 2.39 
                 3.44 
                 3.46 
                 5.09 
                 4.69 
               
               
                 SrO 
                 1.55 
                 1.55 
                 1.65 
                 2.36 
                 2.37 
                 0 
                 0 
               
               
                 BaO 
                 0 
                 2 
                 2.15 
                 0 
                 0 
                 0 
                 0 
               
               
                 TiO 2   
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 B 2 O 3   
                 0.8 
                 0.8 
                 0.86 
                 0.4 
                 0 
                 2.34 
                 2.15 
               
               
                 Al 2 O 3   
                 4.8 
                 4.8 
                 5.15 
                 4.72 
                 4.74 
                 5.06 
                 4.97 
               
               
                 SiO 2   
                 72.81 
                 72.78 
                 70.78 
                 71.57 
                 71.85 
                 74.01 
                 75.65 
               
               
                 SnO 2   
                 0.07 
                 0.1 
                 0.1 
                 0.07 
                 0.07 
                 0.1 
                 0.1 
               
               
                 Composition (wt %) 
                   
                   
                   
                   
                   
                   
                   
               
               
                 Na 2 O 
                 3.83 
                 3.76 
                 4.02 
                 3.75 
                 3.77 
                 3.02 
                 2.79 
               
               
                 K 2 O 
                 11.7 
                 8.6 
                 9.18 
                 11.4 
                 11.5 
                 14.1 
                 13 
               
               
                 MgO 
                 3.59 
                 3.52 
                 3.76 
                 3.52 
                 3.53 
                 0.31 
                 0.28 
               
               
                 CaO 
                 1.94 
                 1.9 
                 2.03 
                 2.98 
                 3 
                 4.35 
                 4.02 
               
               
                 SrO 
                 2.49 
                 2.45 
                 2.61 
                 3.78 
                 3.8 
                 0 
                 0 
               
               
                 BaO 
                 0 
                 4.67 
                 4.99 
                 0 
                 0 
                 0 
                 0 
               
               
                 TiO 2   
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 B 2 O 3   
                 0.86 
                 0.85 
                 0.91 
                 0.43 
                 0 
                 2.49 
                 2.29 
               
               
                 Al 2 O 3   
                 7.59 
                 7.45 
                 7.93 
                 7.43 
                 7.47 
                 7.87 
                 7.76 
               
               
                 SiO 2   
                 67.8 
                 66.5 
                 64.3 
                 66.4 
                 66.7 
                 67.8 
                 69.6 
               
               
                 SnO 2   
                 0.16 
                 0.23 
                 0.23 
                 0.16 
                 0.16 
                 0.02 
                 0.23 
               
               
                 T str  (° C.) 
                 560 
                 560 
                 555 
                 558 
                 564 
                 560 
                 565 
               
               
                 T ann  (° C.) 
                 609 
                 614 
                 605 
                 608 
                 616 
                 605 
                 613 
               
               
                 T s  (° C.) 
                 846 
                 856 
                 839 
                   
                   
                   
                   
               
               
                 a (10 −7 /° C.) 
                 80.4 
                 75.3 
                 77.7 
                 83.2 
                 83.3 
                 80.7 
                 77.4 
               
               
                 r (gm/cc) 
                 2.521 
                 2.528 
                 2.551 
                 2.489 
                 2.488 
                 2.435 
                 2.425 
               
               
                 T 200  (° C.) 
                 1630 
                 1613 
                 1588 
                 1607 
                 1622 
                 1603 
                 1660 
               
               
                 T liq  (° C.) 
                 930 
                 990 
                 1000 
                 905 
                 990 
                 910 
                 930 
               
               
                 h liq  (kp) 
                 2843 
                 705 
                 429 
                 5378 
                 781 
                 1524 
                 1679 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 8 
               
               
                   
               
               
                 Example 
                 52 
                 53 
                 54 
                 55 
                 56 
                 57 
                 58 
                 59 
               
               
                   
               
             
             
               
                 Composition (mol %) 
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 Na 2 O 
                 3.13 
                 3.2 
                 3 
                 3.95 
                 4.5 
                 4.2 
                 3.5 
                 3.5 
               
               
                 K 2 O 
                 9.93 
                 10.14 
                 6.72 
                 7.89 
                 6 
                 6.2 
                 7.5 
                 7.5 
               
               
                 MgO 
                 7 
                 5 
                 5.23 
                 5.67 
                 1.6 
                 6 
                 0 
                 0 
               
               
                 CaO 
                 3.24 
                 3.31 
                 5.66 
                 3.46 
                 3.4 
                 23 
                 3.9 
                 3.9 
               
               
                 SrO 
                 1.04 
                 1.07 
                 2.78 
                 3.37 
                 0.1 
                 1.6 
                 0.08 
                 0.08 
               
               
                 BaO 
                 0 
                 0 
                 0 
                 0 
                 5.2 
                 2.1 
                 3.82 
                 3.82 
               
               
                 TiO 2   
                 0 
                 0 
                 0 
                 0 
                 0 
                 2 
                 2 
                 2 
               
               
                 B 2 O 3   
                 1.72 
                 1.76 
                 0 
                 0 
                 7.1 
                 0.8 
                 5.6 
                 5.6 
               
               
                 Al 2 O 3   
                 3.29 
                 3.36 
                 1.76 
                 4.39 
                 6 
                 5 
                 5 
                 6 
               
               
                 SiO 2   
                 70.55 
                 72.06 
                 74.75 
                 71.2 
                 66.1 
                 69.8 
                 68.6 
                 67.6 
               
               
                 SnO 2   
                 0.1 
                 0.1 
                 0.1 
                 0.07 
                 0 
                 0 
                 0 
                 0 
               
               
                 Composition (wt %) 
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 Na 2 O 
                 3.02 
                 3.06 
                 2.93 
                 3.76 
                 3.98 
                 3.92 
                 3.13 
                 3.11 
               
               
                 K 2 O 
                 14.6 
                 14.8 
                 10 
                 11.4 
                 8.09 
                 8.82 
                 10.2 
                 10.2 
               
               
                 MgO 
                 4.4 
                 3.12 
                 3.34 
                 3.52 
                 0.92 
                 3.65 
                 0 
                 0 
               
               
                 CaO 
                 2.83 
                 2.87 
                 5.01 
                 2.99 
                 2.73 
                 1.95 
                 3.16 
                 3.14 
               
               
                 SrO 
                 1.68 
                 1.72 
                 4.56 
                 5.37 
                 0.15 
                 2.5 
                 0.12 
                 0.12 
               
               
                 BaO 
                 0 
                 0 
                 0 
                 0 
                 11.4 
                 4.86 
                 8.47 
                 8.42 
               
               
                 TiO 2   
                 0 
                 0 
                 0 
                 0 
                 0 
                 2.41 
                 2.31 
                 2.3 
               
               
                 B 2 O 3   
                 1.87 
                 1.9 
                 0 
                 0 
                 7.08 
                 0.84 
                 5.64 
                 5.6 
               
               
                 Al 2 O 3   
                 5.23 
                 5.3 
                 2.84 
                 6.88 
                 8.76 
                 7.7 
                 7.37 
                 8.79 
               
               
                 SiO 2   
                 66.1 
                 67 
                 71 
                 65.8 
                 56.9 
                 63.3 
                 59.6 
                 58.4 
               
               
                 SnO 2   
                 0.24 
                 0.23 
                 0.24 
                 0.16 
                 0 
                 0 
                 0 
                 0 
               
               
                 T str  (° C.) 
                 553 
                 549 
                 565 
                 559 
                 540 
                 564 
                 549 
                 549 
               
               
                 T ann  (° C.) 
                 600 
                 597 
                 615 
                 609 
                 580 
                 611 
                 589 
                 590 
               
               
                 T s  (° C.) 
                   
                   
                   
                   
                   
                   
                   
                   
               
               
                 a (10 −7 /° C.) 
                 84.8 
                 86.3 
                 77.4 
                 84.8 
                 78 
                 76.2 
                 77.5 
                 77.9 
               
               
                 r (gm/cc) 
                 2.466 
                 2.463 
                 2.498 
                 2.52 
                 2.468 
                 2.559 
                 2.604 
                 2.601 
               
               
                 T 200  (° C.) 
                 1529 
                 1553 
                 1568 
                 1578 
                 1425 
                 1566 
                 1476 
                 1485 
               
               
                 T liq  (° C.) 
                 910 
                 845 
                 995 
                 980 
                 865 
                 980 
                 880 
                 900 
               
               
                 h liq  (kp) 
                 1693 
                 9012 
                 422 
                 514 
                 650 
                 468 
                 933 
                 518 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 9 
               
               
                   
                   
               
               
                   
                 Example 
                 60 
                 61 
                 62 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Composition (mol %) 
                   
                   
                   
               
               
                   
                 Na 2 O 
                 3.2 
                 3.07 
                 3.71 
               
               
                   
                 K 2 O 
                 9.14 
                 8.77 
                 7.16 
               
               
                   
                 MgO 
                 5 
                 4.8 
                 5.28 
               
               
                   
                 CaO 
                 4.06 
                 3.89 
                 4.77 
               
               
                   
                 SrO 
                 1.32 
                 1.27 
                 0.94 
               
               
                   
                 BaO 
                 0 
                 0 
                 4 
               
               
                   
                 TiO 2   
                 0 
                 0 
                 0 
               
               
                   
                 B 2 O 3   
                 1.76 
                 5.76 
                 1.55 
               
               
                   
                 Al 2 O 3   
                 5.36 
                 5.14 
                 4.71 
               
               
                   
                 SiO 2   
                 70.08 
                 67.23 
                 67.8 
               
               
                   
                 SnO 2   
                 0.08 
                 0.08 
                 0.08 
               
               
                   
                 Composition (wt %) 
               
               
                   
                 Na 2 O 
                 3.03 
                 2.9 
                 3.39 
               
               
                   
                 K 2 O 
                 13.21 
                 12.63 
                 9.96 
               
               
                   
                 MgO 
                 3.09 
                 2.96 
                 3.14 
               
               
                   
                 CaO 
                 3.49 
                 3.34 
                 3.95 
               
               
                   
                 SrO 
                 2.1 
                 2.02 
                 1.44 
               
               
                   
                 BaO 
                 0 
                 0 
                 9.06 
               
               
                   
                 TiO 2   
                 0 
                 0 
                 0 
               
               
                   
                 B 2 O 3   
                 1.88 
                 6.14 
                 1.59 
               
               
                   
                 Al 2 O 3   
                 8.39 
                 8.01 
                 7.09 
               
               
                   
                 SiO 2   
                 64.6 
                 61.77 
                 60.16 
               
               
                   
                 SnO 2   
                 0.18 
                 0.18 
                 0.18 
               
               
                   
                 T str  (° C.) 
                 565 
                 558 
                 561 
               
               
                   
                 T ann  (° C.) 
                 614 
                 602 
                 609 
               
               
                   
                 T s  (° C.) 
               
               
                   
                 a (10 −7 /° C.) 
                 83.3 
                 75.2 
                 78 
               
               
                   
                 r (gm/cc) 
                 2.472 
                 2.46 
                 2.63 
               
               
                   
                 T 200  (° C.) 
                 1601 
                 1537 
                 1514 
               
               
                   
                 T liq  (° C.) 
                 1000 
                 1020 
                 980 
               
               
                   
                 h liq  (kp) 
                 405 
                 104 
                 257 
               
               
                   
                   
               
             
          
         
       
     
         [0151]    It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.