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  Glass compositionsUSPTO Application #: 20070117708Title: Glass compositions Abstract: Disclosed are glass compositions and glass fibers formed from certain embodiments of the disclosed glass compositions. Certain embodiments of the glass compositions include, among other components, bismuth oxide. Certain embodiments of the glass composition include about 0.5-30% bismuth oxide of the composition by weight and silica oxide at about 54-70% of the composition by weight. Embodiments of the glass compositions may also include other components. For example, zinc oxide can make up about 0.01-5% of the composition by weight. (end of abstract) Agent: Klarquist Sparkman, LLP - Portland, OR, US Inventors: George Zguris, John Windisch, Patrick Svoboda, Yuri Vulfson USPTO Applicaton #: 20070117708 - Class: 501072000 (USPTO) Related Patent Categories: Compositions: Ceramic, Ceramic Compositions, Glass Compositions, Compositions Containing Glass Other Than Those Wherein Glass Is A Bonding Agent, Or Glass Batch Forming Compositions, Silica Containing, 40 Percent - 90 Percent By Weight Silica, And Divalent Metal Oxide (e.g., Oxides Of Zinc, Cadmium, Beryllium, Alkaline Earth Metal, Magnesium, Etc.) The Patent Description & Claims data below is from USPTO Patent Application 20070117708. Brief Patent Description - Full Patent Description - Patent Application Claims
CROSS REFERENCE TO RELATED APPLICATION [0001] Priority is claimed from provisional patent application No. 60/399,583, filed Jul. 29, 2002, which is also incorporated herein by reference. FIELD [0002] Disclosed are bismuth-containing glass compositions, glass fibers formed from the glass compositions, and applications of the same. BACKGROUND [0003] Two well-known glass fiber manufacturing methods are known as the rotary method and the flame blown method. Another well-known and widely used method is the CAT method, which is a modification of the rotary method. Manufacturing glass by these methods requires heating glass compositions past their melting temperatures into a working temperature range. Typical glass compositions used in making glass fibers have melting temperatures of about 2700.degree. F. (about 1482.degree. C.) and working temperatures (temperature ranges between glass viscosity 100 and 10000 poise) of about 2600.degree. F. (about 1427.degree. C.). Existing compositions have relatively narrow working ranges, making the forming of glass fibers of desirable diameters and lengths difficult because it is difficult to maintain the glass compositions in the workable range. Additionally, the relatively high melting temperatures require large amounts of energy to melt the compositions, which can be very costly. [0004] In addition, typical glass compositions used for making glass fibers have liquidus temperatures of about 1800.degree. F. (about 982.degree. C.). The liquidus temperature of typical compositions used for making glass fibers limits the useful life of fiberization equipment due to the high temperatures at which the equipment must operate. This is especially true when a spinner disc is employed in the fiberization equipment. A glass composition having a relatively low liquidus temperature also is useful for reducing or preventing crystallization of the glass during the fiberization process. [0005] Glass fibers are used in a variety of applications. For example, glass fibers are used in several manners in batteries. Glass fibers are typically used as a separator that is preferably inserted between negative and positive plates of the battery. In addition, glass fibers are used as a part of a modified material mixed with a paste on the negative or positive plates of a battery. Further, glass fibers are used as a pasting paper that is applied to the surface of the plates to reduce the liberation of lead dust during manufacture. [0006] Glass fibers tend to become brittle in humid environments, leach favorable and unfavorable components, and are unstable in acidic and/or alkaline environments. These characteristics of certain glass fibers can limit their usefulness in applications such as battery separators or filters. Ion leaching, for example, is a glass fiber surface phenomenon. The amount of ions lost from a glass fiber is proportional to the exposed surface area. Surface area considerations are typically greatest for glass fibers having diameters of less than about 5-7 .mu.m. In some glass fibers certain metal oxide impurities (e.g., platinum oxide, iron oxide) leach out of the fibers and have a detrimental effect on the life of the battery. [0007] Known glass compositions do not meet desired characteristics. SUMMARY [0008] Disclosed are glass compositions and glass fibers formed from certain embodiments of the disclosed glass compositions. Particular embodiments of the disclosed compositions and fibers have broad working temperature ranges and relatively low melting temperatures that can prolong the useful life of fiberization equipment and decrease the costs associated with producing glass fibers. Moreover, particular embodiments of the disclosed compositions and fibers have good acid and/or alkaline resistance and include beneficial ions, such that when leaching does occur, the leached ions have a positive effect in the particular application in which the fibers are used, such as in a battery separator. Also disclosed are certain applications for such glass fibers. [0009] Certain embodiments of the glass compositions include, among other components, bismuth oxide. Certain embodiments of the glass composition include about 0.5-30% bismuth oxide of the composition by weight and silica oxide at about 54-70% of the composition by weight. Embodiments of the glass compositions may also include other components. For example zinc oxide can make up about 0.01-5% of the composition by weight. DETAILED DESCRIPTION [0010] Disclosed are glass compositions including, among other components, bismuth and/or bismuth compounds. The disclosed glass compositions are the compositions of the glass at the molten stage, which composition is the same as that of resulting glass fibers formed from such glass compositions. The disclosed glass compositions may vary from example "ingredient lists" for forming such glass compositions as certain ingredients may change form once melted, becoming a part of the glass composition. Example glass composition ingredient lists are set forth below with the discussion of example methods for making particular embodiments of the disclosed glass compositions. [0011] Embodiments of the disclosed glass compositions may comprise one or more of the following components within, e.g., ranges set forth in Table 1. TABLE-US-00001 TABLE 1 Glass Composition Component Weight Percent SiO.sub.2 54-70 wt % Al.sub.2O.sub.3 1-5 wt % Bi.sub.2O.sub.3 0.5-30 wt % CaO 3-7 wt % MgO 1-5 wt % B.sub.2O.sub.3 4-9 wt % K.sub.2O 0-3 wt % Na.sub.2O 9-20 wt % NiO 0-2 wt % ZnO 0-5 wt % BaO 0-5 wt % Ag.sub.2O 0-1 wt % Li.sub.2O 0-1 wt % F.sub.2 0-1 wt % [0012] Further embodiments of the disclosed glass compositions may comprise one or more of the following components within, e.g., ranges set forth in Table 2. TABLE-US-00002 TABLE 2 Glass Composition Component Weight Percent SiO.sub.2 56-69 wt % Al.sub.2O.sub.3 2-4 wt % Bi.sub.2O.sub.3 1-15 wt % CaO 3-6 wt % MgO 2-4 wt % B.sub.2O.sub.3 4-7 wt % K.sub.2O 0.1-1.5 wt % Na.sub.2O 12-18 wt % NiO 0-1 wt % ZnO 0-3 wt % BaO 0-2 wt % Ag.sub.2O 0-0.1 wt % Li.sub.2O 0-0.3 wt % F.sub.2 0-0.8 wt % [0013] Particular embodiments of the glass compositions may comprise, for example, the components as set forth in Table 3. TABLE-US-00003 TABLE 3 Glass Com- position Com- ponent C-1 C-2 C-3 C-4 C-5 C-6 C-7 SiO.sub.2 64 63.6 59.8 59.5 56.7 68.5 68.5 Al.sub.2O.sub.3 3.4 3.3 3.2 3.2 3 3.8 3.8 CaO 5.5 5.6 5.1 4.8 4 5.7 5.7 MgO 2.7 2.6 2.4 2.0 2.4 2.8 2.8 B.sub.2O.sub.3 5.4 5.1 4.7 4.5 4.5 4.7 4.7 K.sub.2O 0.8 0.7 0.6 0.7 0.7 1.8 1.8 Na.sub.2O 16 14.7 14.3 13.4 12 11.9 11.9 ZnO 0.05 2.0 0.01 2.0 1.9 2* 0 BaO 0.05 0.02 0.01 0.01 0 F.sub.2 0.6 0.6 0.6 0.6 0 0.8 0.8 Li.sub.2O 0.0009 0.008 0.007 0.000 0.000 Bi.sub.2O.sub.3 1.8 1.8 9.3 9.3 14.9 2* 10* Fe.sub.2O.sub.3 0.05 0.05 0.05 0.05 0.05 BDL BDL Cr.sub.2O.sub.3 <0.0000 <0.000 0 0 0 BDL BDL TiO.sub.2 0.025 0.021 0.024 0.025 0.019 BDL BDL ZrO.sub.2 0.004 0.002 0.003 0.003 0.002 BDL BDL Amounts in wt % over 100% [0014] The disclosed glass compositions can be formulated using a variety of sources for 5 each desired component. For example, the following glass composition components can be obtained from the sources listed in Table 4. TABLE-US-00004 TABLE 4 Glass Composition Component Example Source Source Composition SiO.sub.2 Sand (or Silica) Sand contains 99.4% silica, 0.25% alumina; Silica contains 99.9% silica Al.sub.2O.sub.3 Syenite SiO.sub.2, Al.sub.2O.sub.3, K.sub.2O, Na.sub.2O, CaO CaO Burnt Dolomite (or CaO*MgO, CaF2 Fluorspar) MgO Burnt Dolomite CaO*MgO B.sub.2O.sub.3 Borax Na.sub.2B.sub.4O.sub.7.cndot.5H.sub.2O K.sub.2O Syenite K.sub.2CO.sub.3.cndot.1.5H.sub.2O Na.sub.2O Soda Ash or Na.sub.2CO.sub.3 Borax Na.sub.2B.sub.4O.sub.7.cndot.5H.sub.2O ZnO Zinc oxide ZnO BaO Barium carbonate BaCO.sub.3 F.sub.2 Fluorspar CaF.sub.2 Li.sub.2O impurity Bi.sub.2O.sub.3 Bismuth oxide Bi.sub.2O.sub.3 Fe.sub.2O.sub.3 impurity Typically from sand, syenite and dolomite Cr.sub.2O.sub.3 impurity Same TiO.sub.2 impurity Same ZrO.sub.2 impurity Furnace refractory materials [0015] Particular exemplary embodiments of the disclosed glass compositions and 5 ingredients for forming the same are listed in Table 5. Clearly, different sources, amounts, and combinations of glass composition components can be used to produce the glass compositions disclosed herein. TABLE-US-00005 TABLE 5 Glass Comp Source 1 Glass Source 2 Glass Source 3 Glass Source 4 Glass Source 5 Glass Component and wt % Comp 1 wt % Comp 2 wt % Comp 3 wt % Comp 4 wt % Comp 5 SiO.sub.2 Sand (and .about.64 50 63.6 46.9 59.8 47.0 59.5 45.2 56.7 syenite) 50.0 Al.sub.2O.sub.3 Syenite 3.43 12.0 3.3 11.7 3.2 11.8 3.2 11.1 3 12.3 Na.sub.2O Soda ash 16.26 16.9 14.7 16.7 14.3 15.5 13.4 13.6 12 18.0 (and borax) B.sub.2O.sub.3 See above 5.37 9.7 5.1 9.6 4.7 8.9 4.5 8.5 4.5 CaO Dolomite 5.47 6.3 5.6 5.8 5.1 4.9 4.8 6.2 4 6.5 (and fluorspar) MgO Dolomite 2.72 See 2.6 See 2.4 See 2.0 See 2.4 (see above) above above above above K.sub.2O Syenite 0.811 See 0.7 See 0.6 See 0.7 See 0.7 (see above) above above above above BaO Barium 0.0517 0 0 0 0 0 0 0 0 carbonate ZnO Zinc oxide 0.0477 1.8 2.0 0 0.01 1.8 1.95 1.6 2.0 Bi.sub.2O.sub.3 Bismuth n/a 1.6 1.8 8.4 9.3 8.5 9.3 13.8 14.9 oxide 1.6 Fe.sub.2O.sub.3 Impurity 0.05 Impurity Impurity Impurity Impurity from sand, syenite and dolomite F.sub.2 Fluorspare n/a 1.9 0.6 1.6 0.55 2.1 0.54 0 0.53 1.9 Cr.sub.2O.sub.3 Impurity 0.0000 Impurity Impurity Impurity Impurity TiO.sub.2 Impurity 0.0246 Impurity Impurity Impurity Impurity ZrO.sub.2 Impurity 0.0043 Impurity Impurity Impurity Impurity Li.sub.2O Impurity 0.0009 Impurity Impurity Impurity Impurity [0016] Embodiments of the disclosed glass compositions may contain various combinations of the disclosed components listed above. Each of the disclosed glass compositions, however, include a certain amount of bismuth, typically in the form of an oxide, present in an amount of from about 0.5 wt % to about 30 wt % Bi.sub.2O.sub.3. Good results have been obtained with a bismuth component present in the composition at from about 1 wt % to about 15 wt % Bi.sub.2O.sub.3. It is possible that there would be negligible amount of reduction of Bi.sub.2O.sub.3 into metallic form. However, whatever form of bismuth is used for the glass composition, the raw bismuth material will turn into bismuth oxide upon melting of the composition. [0017] Alone, Bi.sub.2O.sub.3 will not form glass. Bismuth oxide may be used as part of a binary glass composition. For example, bismuth oxide can be added to SiO.sub.2 in a concentration up to about 40 mol %. Bi.sub.2O.sub.3 forms glass with several other oxides as well, for example K.sub.2O. Bi.sub.2O.sub.3 acts in a glass composition in a manner similar to B.sub.2O.sub.3, Al.sub.2O.sub.3, La.sub.2O.sub.3 or PbO, in that it decreases glass melting temperature, glass viscosity, and allows fiberization of the glass at lower temperatures. Bismuth oxide structural elements are incorporated into the glass matrix and act to strengthen the resulting glass structure, e.g., glass fibers. [0018] In addition, bismuth oxide acts to decrease the glass softening point and melting temperatures (as discussed below and shown in Table 8). Addition of about 1% Bi.sub.2O.sub.3 decreases the softening point by about 2.degree. F. Addition of about 1% Bi.sub.2O.sub.3 decreases the melting temperature by about 4.degree. F. The fiberization temperature, i.e., the temperature at which the glass composition viscosity is about 1000 poise is also decreased in certain embodiments of the glass compositions. Particular glass composition embodiments exhibit a fiberization temperature of about equal to or lower than 2000.degree. F. (about 1093.degree. C.) and certain embodiments exhibit a fiberization temperature of about equal to or lower than from about 1800 to about 2050.degree. F. (from about 982.degree. C. to about 1120.degree. C.). Glass composition embodiments having from about 2 to 10 wt% Bi.sub.2O.sub.3 decrease the fiberization temperatures of the glass compositions by about 50.degree. F. to about 100.degree. F. (about 10.degree. C. to about 38.degree. C.). [0019] Glass compositions including the levels of Bi.sub.2O.sub.3 indicated also improve the performance of glass fibers formed into hand sheets. Testing of such hand sheets indicates that certain embodiments of the glass fibers disclosed will produce superior battery separators or filter media. That is, such applications of the disclosed glass fibers are relatively easy to manufacture and have the tensile, elongation, basis weight, water wicking characteristics and other basic characteristics similar to or better than what is presently available with commercial fibers (such as EF M-glass illustrated in Tables 6 and 7 or JM 253 glass (available from, e.g., Johns Manville Corporation and illustrated in Table 6)). Accordingly, certain embodiments of the disclosed glass compositions do not compromise major media physical characteristics needed of glass fibers formed thereof but instead additionally provide enhanced performance due to particular enhanced or new glass properties, e.g., Bi ion leaching that decreases off gassing in battery applications. Continue reading... Full patent description for Glass compositions Brief Patent Description - Full Patent Description - Patent Application Claims Click on the above for other options relating to this Glass compositions patent application. ###  How KEYWORD MONITOR works... a FREE service from FreshPatents1. Sign up (takes 30 seconds). 2. Fill in the keywords to be monitored. 3. Each week you receive an email with patent applications related to your keywords. Start now! - Receive info on patent apps like Glass compositions or other areas of interest. ### Previous Patent Application: Glass plate and method for tempering a glass plate Next Patent Application: Catalyst for dimethyl ether synthesis and its preparation methods Industry Class: Compositions: ceramic ### FreshPatents.com Support Thank you for viewing the Glass compositions patent info. IP-related news and info Results in 0.55526 seconds Other interesting Feshpatents.com categories: Computers: Graphics , I/O , Processors , Dyn. 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