Abstract:
The instant invention is directed to glasses manifesting solar transmissions (350-2100 nm) through a 2.54 mm thick sheet in excess of 90% which can be prepared from conventional glass batch materials containing up to 0.1% iron, expressed as Fe 2  O 3 , as impurities. The inventive glasses consist essentially, expressed in weight percent on the oxide basis as calculated from the batch, of 
     
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     Al 2  O 3      7-13B 2  O 3       7-10Na 2  O           6-11K 2  O            2-7CaO                  2-7TiO 2             0.1-1As 2  O 3      0-1Sb 2  O 3      0-1SiO 2             Balance______________________________________ 
     Part of the batch materials is added in the form of nitrates in a sufficient amount to virtually completely oxidize all the tramp iron present to the Fe +3  state.

Description:
BACKGROUND OF THE INVENTION 
     The solar transmission (T s ) of typical soda-lime glass is about 85%. For certain applications, for example, a solar heliostat glass for backside reflecting mirrors, glasses demonstrating greater solar transmissions would be highly desirable. Moreover, it has been recognized that some glass formulations are prone to develop discoloration (&#34;browning&#34;) therein after exposure to radiation, this coloration reducing the overall solar transmission of the glass. An interaction occurring between the glass and the radiation can cause electronic changes in the glass. If the source of the radiation is sunlight, the changes are commonly referred to as resulting from solarization. Solarization reactions within a glass appear to be caused by a transfer of electrons taking place between ions capable of donating and accepting charges. Damage to the glass network may also occur when the glass is exposed to very high energy radiation. However, such damage is beyond the scope of solarization. In any event, glasses subject to substantial solarization are self-evidently not useful for solar applications where high transmissions are demanded. 
     The spectral transmission of soda-lime glass over the visible region (˜400-780 nm) is essentially transparent for most applications and certainly &#34;clear&#34; to the eye unless long light path lengths are used such as, for example, viewing a large article &#34;edge on&#34;. The coloration of glass, when observed, is normally the result of contamination arising from the presence of tramp iron oxides in the composition. These iron oxides customarily have their source as contaminants in such batch ingredients as sand, feldspars, limestone, etc., or they may be inadvertently picked up during batch and cullet handling. 
     The iron oxide conventionally contains ferrous (Fe +2 ) and ferric (Fe +3 ) ions with characteristic absorptions in the near infrared region of the radiation spectrum, i.e., about 1100 nm, and in the ultraviolet region, i.e., about 380 nm. The presence of a high percentage of Fe +3  ions gives rise to a yellow to yellow-green coloration, whereas the presence of substantial amounts of Fe +2  ions yields a blue coloration and causes the glass to absorb strongly in the infrared region. A typical soda-lime glass contains about 0.1% iron, expressed as Fe 2  O 3 , with about 30% of the iron content being present in the Fe +2  state. The desire to transmit solar energy is not limited to the visible portion of the spectrum. Rather, the need is for high transmission over the spectral region of 350-2100 nm. Consequently, the strong absorption by Fe +2  ions in the near infrared portion of the spectrum is undesirable. 
     Numerous drawing processes are known to the art wherein glass sheet is formed directly from a melt and, in most of those processes, the surfaces of the glass sheet are not contacted by molds or rollers until after the glass has cooled sufficiently to resist surface marking. Three of the most widely known of those processes are the Colburn process, the Fourcault process, and the Pittsburgh Plate or Pennvernon process. Each operation utilizes rollers to draw sheet up from a glass melt but can provide glass of near-optical quality and without surface markings. A recently-developed downdraw process is described in U.S. Pat. Nos. 3,338,696 and 3,682,609 which is especially suitable for forming glass sheet of controlled uniform thickness and optical quality. 
     Unfortunately, however, each of those sheet drawing processes requires holding large volumes of glass at relatively low temperatures to secure the necessary sheet forming viscosities, viz., about 10 4  -10 6  poises. Moreover, those volumes of molten glass are required to be in extended contact with the refractory metals or ceramics utilized as the means for forming the drawn sheet. Accordingly, then, those processes impose severe constraints on operable glass compositions because of the formidable liquidus and glass stability problems associated with the handling and processing of glass at relatively low temperatures and high viscosities. 
     Because of its inherent capability to produce glass sheet of optical quality, the aforementioned recently-developed downdraw process is especially useful to produce glass sheet destined for solar applications or other utility where high transmission is the goal. That process requires a glass exhibiting a viscosity at its liquidus temperature of at least 10 4  poises and preferably about 10 5  poises, and demonstrating long term stability against devitrification and interfacial crystallization in contact with platinum and such refractory ceramics as mullite, sillimanite, zircon, and high density alumina-containing refractories customarily employed to contain or form the molten glass. The growth of a crystalline layer at the glass-refractory metal or ceramic interface not exceeding 10 microns in thickness over a contact period of 30 days when the glass melt is at a viscosity between about 10 4  -10 6  poises is deemed to be good long term stability. 
     Furthermore, inasmuch as a discoloration arising from solarization can be deleterious to the transmission of the glass, additives known to inhibit the action of that phenomenon will be advantageously included in the glass compositions. 
     Finally, because the primary application for the glasses involves exposure thereof to solar radiation in the ambient environment, good chemical durability and, in particular, high resistance to weathering is demanded. 
     OBJECTIVE OF THE INVENTION 
     The principal objective of the instant invention is to provide glass compositions, demonstrating solar transmissions (350-2100 nm) through a 2.54 mm thick sheet of at least 89% and, most preferably, in excess of 90%, which can be prepared from standard glass batch materials, i.e., the iron content therein expressed as Fe 2  O 3  can be as high as about 0.1%, and which have a viscosity at the liquidus between about 10 4  -10 6  poises, exhibit long term stability against devitrification when in contact with platinum and refractory ceramics, are virtually unaffected by solarization, and display excellent resistance to weathering. 
     SUMMARY OF THE INVENTION 
     The most obvious step to improve the solar transmission of an iron-containing glass is to reduce the amount of iron present. Such practice can, of course, be undertaken by utilizing extremely pure batch materials. However, it is equally evident that such practice will greatly increase the cost of the final product. 
     Our inventive glasses rely upon a second approach to the problem, viz., to oxidize the ferrous iron to ferric iron. It is not apparent that this action will aid in improving the transmission of the glass since the energy of solar radiation is near maximum in the ultraviolet-visible region of the spectrum. The absorption coefficient of Fe +2  ions, however, is greater than that of Fe +3  ions and the absorption peak is broader. Measurements have confirmed that, for a specified total iron concentration, an oxidized glass will transmit more total solar energy (350-2100 mm) than a reduced or partially reduced formulation. 
     Accordingly, the accomplishment of the above objective is founded in the development of compositions capable of achieving the other desired chemical, physical, and forming properties and including ingredients in the batch which will effectively oxidize the glass to convert Fe +2  ions to Fe +3  ions. In this manner, the T s  can be significantly improved even though the total iron level is relatively high. The invention removes the need to resort to scarce and very expensive low iron-containing raw materials. The oxidation of the glass is achieved through the addition of nitrates to the batch and, if fining of the molten batch is necessary, to utilize As 2  O 3  or, perhaps, Sb 2  O 3  to perform that function. The amount of nitrates necessary to essentially completely oxidize all the iron impurities to the Fe +3  state, i.e., in excess of 80% and preferably more than 90% of the iron will be present in the Fe +3  state, is, of course, dependent upon the total iron present. This can be calculated from the analyses of the batch materials. 
     The glass art has recognized that TiO 2  is one of the most effective inhibitors of solarization in glass. That material is also incorporated here for that purpose. 
     In summary, glasses capable of satisfying the above objective consist essentially, expressed in weight percent on the oxide basis as calculated from the batch, of 
     
         ______________________________________Al.sub.2 O.sub.3         7-13B.sub.2 O.sub.3         7-10Na.sub.2 O    6-11CaO           2-7K.sub.2 O     2-7TiO.sub.2     0.1-1As.sub.2 O.sub.3         0-1Sb.sub.2 O.sub.3         0-1Fe.sub.2 O.sub.3         no more than about 0.1SiO.sub.2     Balance______________________________________ 
    
     No iron is purposefully added to the batch. The amount noted, calculated in terms of Fe 2  O 3 , represents contaminants present in the batch materials. Sufficient nitrates, commonly in the form of NaNO 3  or KNO 3 , will be included in the glass batch to oxidize Fe +2  ions to Fe +3 . The NO 2  is essentially totally expelled from the melt so, therefore, is not reported in the above recital of operable glass compositions. 
     Al 2  O 3  imparts unusual viscosity behavior to the glass and generally improves the water durability thereof. Adjusting the Al 2  O 3  concentration provides an optimum for weatherability, liquidus temperature, and glass viscosity. 
     Higher B 2  O 3  levels permit the preparation of glasses having lower coefficients of thermal expansion through the removal of alkali metal oxides from the compositions. A low coefficient of thermal expansion is not necessary for the designed application of this invention, however, and will not be desirable due to expansion mismatches with soda-lime glass in those structures where the inventive glasses are bonded to soda-lime glasses. In such applications, a coefficient of thermal expansion over the temperature range of -30° C. to +50° C. of about 60-80×10 -7  /° C. will be preferred. 
     CaO increases the melting rate of the glasses by providing a fluxing action. As the melt cools, higher CaO concentrations cause the glasses to &#34;set up faster&#34;, i.e., have a steeper viscosity-temperature curve, than low CaO or CaO-free glasses. Nevertheless, care must be exhibited to avoid the development of pseudowollastonite (CaSiO 3 ) devitrification. At levels below about 5% CaO, the liquidus viscosity is satisfactory for forming glass sheet utilizing the above-described downdraw process without the formation of crystals. 
     Na 2  O and K 2  O perform as fluxes to secure easier melting and are highly effective as controls for the expansion and viscosity characteristics demonstrated by the glasses. Whereas higher alkali contents soften the glass for easier melting, the durability (weathering resistance) of the glass deteriorates substantially. On a weight percent basis, Na 2  O reduces the durability of the glass more than does K 2  O. 
     Borosilicate glasses are frequently refined utilizing chloride-containing batch ingredients. These materials appear to function by releasing a chlorine-containing gas, e.g., Cl 2 , HCl, etc., through the molten batch. We have determined that a combination of nitrates with As 2  O 3  and/or Sb 2  O 3  will not only effectively refine the inventive glass compositions, but will also oxidize the melt to virtually eliminate the absorption of the Fe +2  state of iron that remains in the glass. 
     The preferred compositions will exhibit a solar transmission through a 2.54 mm thick sheet in excess of 90%, a liquidus viscosity in excess of 10 5  poises, a softening point of no more than 760° C., an annealing point of no more than about 575° C., a strain point of no more than about 535° C., and better durability and weathering resistance than soda-lime glass. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Table I following reports several glasses, expressed in terms of parts by weight of the oxide basis as calculated from the batch, exemplary of the inventive compositions. The batch ingredients utilized were standard materials of glass manufacture, either the oxide or other compounds, which, when melted together with the other components, were converted to the desired oxide in the proper proportions. Because the sum of the individual constituents totals or approximately totals 100, for all practical purposes the values recited may be deemed to reflect weight percent. The Fe 2  O 3  content is estimated from the batched compositions. Inasmuch as it is not known with which cation(s) the fluoride is associated, it is simply reported as fluoride in accordance with conventional glass analysis practice. 
     The batch ingredients for the exemplary glasses were compounded, ballmilled together to assist in obtaining a homogeneous melt, and placed into platinum crucibles. After covering with a lid, the crucibles were moved to a furnace operating at 1550° C. and the batches melted for about 6 hours with occasional stirring. The melts were then poured into steel molds to form glass slabs having dimensions of about 6&#34;×6&#34;×1/2&#34; and those slabs immediately transferred to an annealer operating at 575°-600° C. 
     Although the above description involved laboratory scale melting, it will be appreciated that the molten glass may be formed employing any of the techniques well recognized in the glassmaking art such as blowing, casting, pressing, rolling, and spinning. Furthermore, the glasses are sufficiently stable from devitrification that they may also be formed into sheet by direct drawing from the melt and, particularly advantageously, direct drawing utilizing the downdraw method described above where platinum and/or other refractory ceramic forming means are used. 
     Table I also records the analysis of a commercial soda-lime glass made via the float glass process (F Glass) and a commercial aluminosilicate glass (AS Glass). 
     
                                           TABLE I__________________________________________________________________________1    2    3    4    5    6    7    8    9    10__________________________________________________________________________SiO.sub.262.67     63.16          64.87               65.36                    64.3 64.3 56.2 60.2 64.3 64.3Al.sub.2 O.sub.38.27 8.27 8.25 8.26 9.1  9.1  11.1 9.1  7.1  9.1Na.sub.2 O16.22     16.22          7.15 7.15 8.6  6.6  10.6 10.6 10.6 10.6K.sub.2 O1.62 1.62 5.49 5.49 4.6  6.6  6.6  6.6  2.6  2.6CaO  2.85 2.85 4.60 4.61 4.5  4.5  6.5  4.5  6.5  4.5B.sub.2 O.sub.33.53 3.53 8.87 8.87 8.2  8.2  8.2  8.2  8.2  8.2Fe.sub.2 O.sub.30.048     0.048          0.043               0.043                    0.02 0.02 0.02 0.02 0.02 0.02As.sub.2 O.sub.30.20 0.20 0.20 0.20 0.2  0.2  0.2  0.2  0.2  0.2TiO.sub.20.50 --   0.50 --   0.5  0.5  0.5  0.5  0.5  0.5MgO  4.08 4.08 --   --   --   --   --   --   --   --__________________________________________________________________________                                        F    As11   12   13   14   15   16   17   18   Glass                                             Glass__________________________________________________________________________SiO.sub.266.2 64.3 62.2 66.2 66.0 68.2 65.6 64.3 72.4 61.5Al.sub.2 O.sub.37.9  11.1 11.1 9.1  7.9  7.2  9.1  7.1  2.1  17.0Na.sub.2 O7.3  8.6  8.6  8.6  7.3  8.6  9.3  8.6  13.6 12.6K.sub.2 O5.0  4.6  4.6  4.6  5.0  4.6  4.6  4.6  --   3.4CaO  4.5  2.5  4.5  2.5  4.5  2.5  2.5  6.5  8.6  0.4B.sub.2 O.sub.38.9  8.2  8.2  8.2  8.9  8.2  8.2  8.2  --   --Fe.sub.2 O.sub.30.02 0.02 0.02 0.02 0.04 0.02 0.02 0.02 0.12 0.065As.sub.2 O.sub.3--   0.2  0.2  0.2  0.2  0.2  0.2  0.2  --   0.7TiO.sub.2--   0.5  0.5  0.5  --   0.5  0.5  0.5  --   0.75F    0.4  --   --   --   0.4  --   --   --   --   --MgO  --   --   --   --   --   --   --   --   3.2  3.7__________________________________________________________________________ 
    
     Table II records the softening point (Soft.), annealing point (Ann.), strain point (Str.), and liquidus temperature (Liq.), all in °C., for each exemplary composition. Table II also lists the coefficient of thermal expansion over the range of 0°-300° C. (Exp.) expressed in terms of ×10 -7  /°C., density (Den.) in grams/cm 3 , and the results of a powder durability test (Dur.) conducted in water measured in terms of ×10 -4  %. The first five tests were carried out utilizing methods conventional in the glass art. The durability test involved immersing a quantity of powder from each sample for four hours in distilled water at 90° C. The test is based upon ASTM method, designation C225, and measures a weight percent equivalent of Na 2  O. A typical soda-lime glass has a weight loss equivalent to be about 400×10 -4  % in this test. Finally, Table II recites the solar transmission (Solar) over the 350-2100 nm range of wavelength of several samples both before (Pre) and after (Post) a 24-hour exposure to a 325 watt mercury arc to examine the solarization resistance of each glass. ASTM method, designation E424-71, was employed to calculate the percent transmission of ground and polished samples having thicknesses normalized to 0.1 inch (2.54 mm). The theoretical transmission of the glasses (assuming an average refractive index of 1.50) is 92%. 
     
                                           TABLE II__________________________________________________________________________  1   2   3   4   5   6   7   8   9     10__________________________________________________________________________Soft.  712 705 754 754 740 773 706 710 729   738Ann.   542 536 579 577 575 583 560 556 577   574Str.   503 498 540 539 538 545 528 522 542   539Exp.   92.8      93.6          72.6              72.3                  75.4                      73.6                          90.9                              88.6                                  78.4  75.7Dens.  2.472      2.491          2.447              2.441                  2.455                      2.418                          2.507                              2.492                                  2.487 2.459Liq.   837 867 933 938 923 866 858 &lt;675                                  903   865Dur.   150 160 --  --  22  15  41  35  31    24Solar    Pre  90.8      90.9          91.0              91.1                  --  --  --  --  --    --    Post  90.7      90.3          90.9              90.8                  --  --  --  --  --    --__________________________________________________________________________  11  12  13  14  15  16  17  18  F Glass                                        AS Glass__________________________________________________________________________Soft.  745 764 749 748 741 752 750 740 723   870Ann.   565 575 579 574 564 577 569 577 539   622Str.   526 541 543 537 527 540 529 542 496   574Exp.   70.1      73.5          76.0              72.5                  71.4                      74.5                          74.9                              75.0                                  86    88Dens.  2.423      --  2.451              2.434                  2.446                      2.438                          2.439                              2.456                                  2.50  2.46Liq.   --  851 932 &lt;750                  --  &lt;765                          &lt;700                              948 --    1040Dur.   --  20  25  20  --  20  26  27  400   35Solar    Pre  91.4      --  --  --  89.4                      --  90.9                              --  85.6  90.5    Post  90.4      --  --  --  89.0                      --  --  --  85.9  90.5__________________________________________________________________________ 
    
     As was observed above, the quantity of nitrate demanded to essentially completely oxidize all the iron present to the Fe +3  state can be determined empirically from analyses of the iron content present in the batch ingredients. In general, however, where iron is present in conventional impurity amounts, viz., about 0.1% by weight, at least about 0.5% by weight nitrate, expressed in terms of NaNO 3 , will be included in the batch. More than about 5% by weight nitrate, expressed in terms of NaNO 3 , may be innocuously incorporated into the batch. Nevertheless, such large additions are not only unnecessary as being far in excess of that required to substantially completely oxidize all the iron to the Fe +3  state, but also, because sources of nitrates are commonly more expensive than such batch materials as soda ash, large amounts of nitrates raise the cost of the batch and serve no compensating practical purpose. To determine the relative amounts of Fe +2  and Fe +3  in the final glass, chemical analyses can be conducted colorimetrically utilizing orthophenanthroline. 
     Table II illustrates the criticality of composition control. Hence, whereas the transmissions of Examples 1 and 2 are satisfactory, the chemical durabilities thereof are not as good as desired. That is, a weight loss equivalent to no more than 100×10 -4  % is believed desirable. The float glass demonstrates both inferior transmission and durability. The aluminosilicate glass displays good solar transmission but is too hard--a softening point of 870° C., an annealing point of 622° C., and a strain point of 574°. 
     Example 17 is deemed to constitute the most preferred embodiment of the inventive compositions. To test the resistance of the glass to weathering, a two-inch square thereof was placed into a heated cabinet operating at 50° C. and a relative humidity. After a residence period of 12 weeks, no visible change in appearance was observed even under intense illumination. In contrast, commercial soda-lime glasses are severely degraded in that test after only 4-6 weeks. Example 17 compares very favorably with the chemically resistant borosilicate glasses, for example, Corning 7740 laboratory glassware marketed by Corning Glass Works, Corning, N.Y.