Method of manufacturing high strength glass fibers in a direct melt operation and products formed there from

Abstract

A method of forming high strength glass fibers in a glass melter substantially free of platinum or other noble metal materials, products made there from and batch compositions suited for use in the method are disclosed. One glass composition for use in the present invention includes 50-75 weight % SiO.sub.2, 13-30 weight % Al.sub.2O.sub.3, 5-20 weight % MgO, 0-10 weight % CaO, 0 to 5 weight % R.sub.2O where R.sub.2O is the sum of Li.sub.2O, Na.sub.2O and K.sub.2O, has a higher fiberizing temperature, e.g. 2400-2900 F. (1316-1593 C.) and/or a liquidus temperature that is below the fiberizing temperature by as little as 45 F. (25 C.). Another glass composition for use in the method of the present invention is up to about 64-75 weight percent SiO.sub.2, 16-24 weight percent Al.sub.2O.sub.3, 8-12 weight percent MgO and 0.25-3 weight percent R.sub.2O, where R.sub.2O equals the sum of Li.sub.2O, Na.sub.2O and K.sub.2O, has a fiberizing temperature less than about 2650 F. (1454 C.), and a T of at least 80 F. (45 C.). A forehearth for transporting molten glass from the glass melter to a forming position is disclosed. By using furnaces and/or forehearths substantially free of platinum or other noble metal materials, the cost of production of glass fibers is significantly reduced in comparison with the cost of fibers produced using a melting furnace lined with noble metal materials. High strength composite articles including the high strength glass fibers are also disclosed.

Claims

1. A method of forming high strength glass fibers in a continuous system having a glass melting furnace, a forehearth, and a bushing, the method comprising: supplying a glass batch to the furnace, wherein at least a portion of the furnace is lined with a material substantially free of noble metals thereby forming a furnace glass contact surface, the glass batch being capable of forming a fiberizable molten glass having a fiberizing temperature from 2,400 F. to 2,900 F. and comprising; 65-75 weight percent SiO.sub.2; 15-30 weight percent Al.sub.2O.sub.3; 5-20 weight percent MgO; 0-4 weight percent CaO; 1.0-3 weight percent Li.sub.2O; and trace impurities; melting the glass batch in the furnace by providing heat from a furnace heat source and forming a pool of molten glass in contact with the furnace glass contact surface; transporting the molten glass from the furnace to the bushing via the forehearth, wherein the forehearth is heated from a forehearth heat source, and wherein the forehearth is at least partially lined with a material substantially free of noble metal materials, forming a forehearth glass contact surface; discharging the molten glass from the forehearth into the bushing at a predetermined viscosity; and forming the molten glass into continuous glass fibers, the fibers having a pristine tensile strength greater than 700 kPsi.

2. The method of claim 1, wherein the transporting step includes flowing the molten glass through the forehearth at a depth of less than 8 inches.

3. The method of claim 2, wherein the transporting step includes flowing the molten glass through the forehearth at a depth of less than 3.5 inches.

4. The method of claim 1, wherein at least a portion of the furnace is lined with an oxide-based refractory material.

5. The method of claim 4, wherein at least a portion of the furnace is lined with a material selected from the group consisting of chromic oxide materials and zircon.

6. The method of claim 1, wherein at least a portion of the furnace is lined with externally cooled walls.

7. The method of claim 1, wherein at least a portion of the forehearth is lined with an oxide-based refractory material.

8. The method of claim 7, wherein at least a portion of the forehearth is lined with a material selected from the group consisting of chromic oxide materials and zircon.

9. The method of claim 1, wherein the furnace heat source comprises one or more oxy-fuel burners disposed in a roof, a sidewall, an endwall, or a bottom of the furnace, or combinations thereof.

10. The method of claim 1, wherein the forehearth heat source further comprises one or more oxy-fuel burners disposed in a roof, a sidewall, or an endwall of the forehearth, or combinations thereof.

11. The method of claim 1, wherein the forehearth heat source further comprises one or more air-fuel burners disposed in a roof, a sidewall, or an endwall of the furnace, or combinations thereof, at a spacing sufficient to prevent devitrification of the molten glass in the forehearth.

12. The method of claim 11, wherein the air-fuel burners are spaced at least 4 inches apart.

13. The method of claim 1, wherein the furnace includes one or more bubblers, electric boost electrodes, and combinations thereof.

14. The method of claim 1, wherein the forehearth includes one or more bubblers, electric boost electrodes, and combinations thereof.

15. The method of claim 1, wherein the predetermined viscosity is 1000 poise.

16. The method of claim 1, wherein the predetermined viscosity is 316 poise.

17. The method of claim 1, wherein the glass fibers have a density of 2.434-2.520 g/cc.

18. The method of claim 1, wherein the glass fibers have a measured modulus greater than 12.7 MPsi.

19. The method of claim 1, wherein the glass fibers have a density of 2.434-2.520 g/cc and a measured modulus greater than 12.7 MPsi.

20. The method of claim 1, wherein the glass fibers have a density of 2.434-2.486 g/cc.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a cross-sectional longitudinal view of a glass melting furnace useful with the method of the present invention;

(2) FIG. 2 is a cross-sectional plan view of the glass melting furnace of FIG. 1 taken along line 2-2;

(3) FIG. 3 is a cross-sectional view of the glass melting furnace of FIG. 1 taken along line 3-3 illustrating two burners adjacent the upstream end wall of the furnace;

(4) FIG. 4 is an alternate cross-sectional plan view of the glass melting furnace of FIG. 1 taken along line 3-3 illustrating one burner adjacent the upstream end wall of the furnace; and

(5) FIG. 5 is a side view, partially in cross section, of a bushing assembly/support structure arrangement for producing continuous glass filaments useful in the method of the present invention.

(6) FIG. 6 is a top plan view in cross-section of an exemplary forehearth useful in the method of the present invention for transporting molten glass from the glass melting furnace to the bushing assembly/support.

(7) FIG. 7 is a side elevation view in cross-section of another exemplary forehearth useful in the method of the present invention.

DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS OF THE INVENTION

(8) The present invention will now be described with occasional reference to the specific embodiments of the invention. This invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

(9) Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for describing particular embodiments only and is not intended to be limiting of the invention. As used in the description of the invention and the appended claims, the singular forms a, an, and the are intended to include the plural forms as well, unless the context clearly indicates otherwise.

(10) Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth as used in the specification and claims are to be understood as being modified in all instances by the term about. Accordingly, unless otherwise indicated, the numerical properties set forth in the specification and claims are approximations that may vary depending on the desired properties sought to be obtained in embodiments of the present invention. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical values, however, inherently contain certain errors necessarily resulting from error found in their respective measurements.

(11) Fiberizing properties of the glass composition used to form the glass fibers of the present invention include the fiberizing temperature, the liquidus, and delta-T. Unless otherwise defined herein, the fiberizing temperature is defined as the temperature that corresponds to a viscosity of 1000 poise (log 3 temperature). One skilled in the art will recognize that other fiberizing temperatures may be defined, e.g. a fiberizing temperature may be defined as the temperature that corresponds to a viscosity of 316 poise (log 2.5 temperature).

(12) As discussed in more detail below, in certain embodiments a lowered fiberizing temperature reduces the production cost of the fibers, allows for a longer bushing life, increases throughput, permits the glass to be melted in a melter substantially free of platinum or other noble metal materials, and reduces energy usage. For example, at a lower fiberizing temperature, a bushing operates at a cooler temperature and does not sag as quickly. Sag is a phenomenon that occurs in bushings that are held at an elevated temperature for extended periods of time. By lowering the fiberizing temperature, the sag rate of the bushing may be reduced and the bushing life can be increased. In addition, a lower fiberizing temperature allows for a higher throughput since more glass can be melted in a given period at a given energy input. As a result, production cost is reduced. In addition, a lower fiberizing temperature will also permit glass formed with the inventive method and composition to be melted in a refractory-lined melter, or a melter with externally cooled walls, since both its melting and fiberizing temperatures are below the upper use temperatures of many commercially available refractories or other materials when external cooling is supplied.

(13) The liquidus is defined as the highest temperature at which equilibrium exists between liquid glass and its primary crystalline phase. At all temperatures above the liquidus, the glass is free from crystals in its primary phase. At temperatures below the liquidus, crystals may form.

(14) Another fiberizing property is delta-T (T), which is defined as the difference between the fiberizing temperature and the liquidus. A larger T offers a greater degree of flexibility during the formation of the glass fibers and helps to inhibit devitrification of the glass (that is, the formation of crystals within the melt) during melting and fiberizing. Increasing the T also reduces the production cost of the glass fibers by allowing for a greater bushing life and by providing a wider process window for forming fibers.

(15) Conversely a higher fiberizing temperature and/or a smaller T means the fiber formation process is less forgiving, being more sensitive to temperature variations, cold spots and slow moving glass.

(16) The glass compositions employed in the present invention are advantageously suitable for melting in a furnace or glass melter substantially free of platinum or other noble metal materials and alloys thereof, including traditional, commercially available refractory-lined glass melters, and commercially available glass melters lined with externally cooled walls, e.g. water-cooled walls.

(17) Starting batch components typically include SiO.sub.2 (ground silica sand), and Al.sub.2O.sub.3 (calcined alumina), Li.sub.2CO.sub.3 (lithium carbonate), H.sub.3BO.sub.3 (boric acid), NaCaB.sub.5O.sub.9.8H.sub.2O (ulexite), 2CaO-3B.sub.2O.sub.3-5H.sub.2O (colemanite) as well as chain modifiers from source materials such as MgCO.sub.3 (magnesite), CaCO.sub.3 (limestone), SrCO.sub.3 (strontianite), BaCO.sub.3 (witherite), ZrSiO.sub.4 (zircon), and Na.sub.2CO.sub.3 (natrite). One skilled in the art will appreciate that other starting materials may be used. Additional nonlimiting examples of suitable starting batch components include kaolinite (Al.sub.2Si.sub.2O.sub.5(OH).sub.4), pyrophyllite (Al.sub.2Si.sub.4O.sub.10(OH).sub.2), bauxite (AlO(OH)), wollastonite (CaSiO.sub.3), spodumene (LiAlSi.sub.2O.sub.6), feldspar (CaAl.sub.2Si.sub.2O.sub.8), dolomite (CaMg(CO.sub.2).sub.2), lime (CaO), dolomitic quicklime (CaMgO.sub.2), and hydrated lime (Ca(OH).sub.2).

(18) Glass Melting Furnace

(19) FIGS. 1-4 depict a glass melting furnace (10) useful in the method of forming the glass fibers described herein and set forth in the examples and claims below. It may also be desirable to use oxygen-fired heating within the melting furnace, as disclosed in U.S. Pat. No. 7,509,819 entitled OXYGEN-FIRED FRONT END FOR GLASS FORMING OPERATION, inventors David J Baker et al., herein incorporated in its entirety by reference. The glass melting furnace (10) provides molten glass to a glass forehearth (12).

(20) In one exemplary embodiment, the molten glass is composed of 50-75 weight % SiO.sub.2, 13-30 weight % Al.sub.2O.sub.3, 5-20 weight % MgO, 0-10 weight % CaO, 0 to 5 weight % R.sub.2O where R.sub.2O is the sum of Li.sub.2O, Na.sub.2O and K.sub.2O. This exemplary embodiment includes glass compositions having a higher fiberizing temperature, e.g. 2400-2900 F. (1316-1593 C.) and/or a liquidus temperature that is below the fiberizing temperature by as little as 45 F. (25 C.).

(21) In another exemplary embodiment, the molten glass is composed of about 64-75 weight % SiO.sub.2, 16-26 weight % Al.sub.2O.sub.3, 8-12 weight % MgO and 0 to 3.0 weight % R.sub.2O where R.sub.2O is the sum of Li.sub.2O, Na.sub.2O and K.sub.2O.

(22) In yet another exemplary embodiment, the molten glass is composed of about 64-75 weight % SiO.sub.2, 16-24 weight % Al.sub.2O.sub.3, 8-12 weight % MgO and 0.25 to 3.0 weight % R.sub.2O where R.sub.2O is the sum of Li.sub.2O, Na.sub.2O and K.sub.2O. A fiber formed in accordance with the method of this exemplary embodiment will have a fiberizing temperature of less than 2650 F. (1454 C.), and in certain embodiments less than about 2625 F. (1458 C.), in other embodiments less than about 2600 F. (1427 C.) and in certain embodiments less than about 2575 F. (1413 C.) and a liquidus temperature that is below the fiberizing temperature in certain embodiments by at least 80 F. (44 C.), and in other embodiments by at least about 120 F. (67 C.), and in yet other embodiments by at least about 150 F. (83 C.).

(23) In still another exemplary embodiment, the molten glass is composed of 50-75 weight % SiO.sub.2, 13-30 weight % Al.sub.2O.sub.3, 5-20 weight % MgO, 0-10 weight % CaO, 0 to 5 weight % R.sub.2O where R.sub.2O is the sum of Li.sub.2O, Na.sub.2O and K.sub.2O. This exemplary embodiment includes glass compositions having a liquidus temperature that is above the log 3 fiberizing temperature, i.e. a negative T such as 122 F. (68 C.). Such a composition may be fiberized at higher temperature, e.g. a log 2.5 fiberizing temperature corresponding to a viscosity of 316 poise.

(24) In certain exemplary embodiments, the composition does not contain more than about 5.0 weight % of oxides or compounds such as CaO, P.sub.2O.sub.5, ZnO, ZrO.sub.2, SrO, BaO, SO.sub.3, Fluorine, B.sub.2O.sub.3, TiO.sub.2, Fe.sub.2O.sub.3, K.sub.2O, CeO.sub.2 and BeO.sub.2. In other exemplary embodiments the composition is devoid of intentionally added CeO.sub.2 and BeO.sub.2.

(25) The fibers produced and used in the present invention are substantially less expensive to make and also have good strength and density properties. The density of the fibers used in the present invention range between 2.434-2.520 g/cc, and more preferably 2.434-2.486 g/cc. Further, the glass fibers of the present invention, in certain embodiments, will have a pristine fiber strength in excess of 680 KPSI, and in certain other embodiments a strength in excess of about 700 KPSI, and in yet other embodiments a strength in excess of about 730 KPSI. Further, the glass fibers will advantageously have a modulus greater than 12.0 MPSI, and in certain embodiments greater than about 12.18 MPSI, and in some embodiments greater than about 12.7 MPSI.

(26) The method of the present invention is preferably performed using the glass melting furnace (10), which includes an elongated channel having an upstream end wall (14), a downstream end wall (16), side walls (18), a floor (20), and a roof (22). Each of the components of the glass melting furnace (10) are made from appropriate refractory materials such as alumina, chromic oxide, silica, alumina-silica, zircon, zirconia-alumina-silica, or similar oxide-based refractory materials, in particular the surfaces that are in contact with the molten glass. The roof (22) is shown generally as having an arcuate shape transverse to the longitudinal axis of the composition the channel; however, the roof may have any suitable design. The roof (22) is typically positioned between about 3-10 feet above the surface of the glass batch (30). The glass batch (30) is a mixture of raw materials used in the manufacture of glass in accordance with the present invention.

(27) The glass melting furnace (10) may optionally include one or more bubblers (24) and/or electrical boost electrodes (not shown). The bubblers (24) and/or electrical boost electrodes increase the temperature of the bulk glass and increase the molten glass circulation under the batch cover.

(28) Bubblers (24) and/or electrical boost electrodes may be particularly useful in the second and third exemplary embodiments, which include glass compositions having a higher fiberizing temperature, e.g. 2400-2900 F. (1316-1593 C.) and/or a low T, e.g. as low as 45 C. (25 F.), or even a negative T such as 122 F. (68 C.), where the potential for devitrification is greater.

(29) In addition, the glass melting furnace (10) may include two successive zones, an upstream melting zone (26) and a downstream refining zone (28). In the melting zone (26), the glass batch composition (30) may be charged into the furnace using a charging device (32) of a type well-known in the art.

(30) In one suitable melter configuration, the glass batch material (30) forms a batch layer of solid particles on the surface of the molten glass in the melting zone (26) of the glass melting furnace (10). The floating solid batch particles of the glass batch composition (30) are at least partially melted by at least one burner (34) having a controlled flame shape and length mounted within the roof (22) of the glass melting furnace (10).

(31) In one preferred embodiment, as shown in FIG. 1, the glass melting furnace (10) includes three burners (34). A single burner (34) is positioned upstream of two adjacently positioned downstream burners (34). However, it will be appreciated that any number of burners (34) may be positioned at any suitable location in the roof (22) of the furnace (10) over the batch to melt the glass batch (30). For example, two burners (34) may be positioned in a side-by-side relationship (FIG. 3) or a single burner may be used (FIG. 4).

(32) It is to be noted that the burners (34) of glass melting furnace (10) may be arranged in the crown (roof) of the furnace, in the side walls, the end walls, submerged within the batch or molten glass, or in combinations thereof.

(33) Other melters may be used without departing from the present invention. Suitable melters include Air-Gas melters, Oxygen-Gas melters, electrically heated melters, or any fossil fuel fired melter. It is possible to add electric boost or bubblers to any of the melting processes. It is also possible to include a separate refining zone (as shown in FIG. 1) or incorporate the refining zone into the main tank of the melter.

(34) Forehearth Arrangement

(35) The forehearth receives molten glass discharged from the glass melting furnace and transports the molten glass, discharging the molten glass in suitable condition to a forming position. The components of the forehearth may be lined with appropriate refractory materials such as alumina, chromic oxide, silica, alumina-silica, zircon, zirconia-alumina-silica, or similar oxide-based refractory materials, in particular the surfaces that are in contact with the molten glass. Preferably such forehearth glass contact surfaces are lined with chromic oxide materials, zircon or combinations thereof.

(36) For compositions having a fiberizing temperature of less than 2650 F. (1454 C.) and a liquidus temperature that is below the fiberizing temperature by at least 80 F. (44 C.), a conventional forehearth may be used.

(37) For other compositions where the fiberizing temperature is high and/or the T is low, other forehearth arrangements may be helpful in promoting an isothermal condition in the molten glass, thereby preventing devitrification. For example, transporting the molten glass through the forehearth at a shallow depth (D), e.g. less than about 8 inches, or preferably less than about 3.5 inches, will improve transmission of heat by radiation throughout the molten glass. Installed oxygen-fuel fired burners are particularly useful as a forehearth heat source in this regard. A typical oxygen-fuel firing system is supplied by BH-F (Engineering) Ltd. of England. As defined here, oxygen-fuel fired burners are burners that use oxygen (e.g., typically 90 to 99 percent purity with an impurity being a combination of nitrogen and argon) in a high purity as an oxidant, instead of ambient air used in air-fuel burners, and fossil fuel for a combustible hydrocarbon supply, but may include burners using oxygen-enriched air (e.g. 30 to 90 percent purity). The flame temperature of an oxygen-gas burner is about 4200 to about 5200 F. (about 2315 to about 2871 C.). At this temperature, the flame and products of combustion radiate energy at wavelengths that the molten glass can absorb. This promotes uniform glass temperature horizontally on the surface of the molten glass and vertically through the molten glass.

(38) Air-fuel burners may also be used a forehearth heat source, particularly when installed with a very tight spacing, e.g. 4 inches apart.

(39) Exemplary forehearth arrangements useful in the present invention are shown in FIGS. 6 and 7. Forehearth (322A) is adapted to deliver a molten substance (e.g., molten glass G) from a glass melting furnace to a point of production (i.e., a forming position, discussed below). Molten glass (G) does not contact an upper portion of the forehearth (322A). Consequently, this portion can be constructed from relatively inexpensive refractory material (i.e., a super structure refractory material, such as silica, mullite, or other materials that are not required to withstand corrosive effects of molten glass (G)).

(40) A lower portion of forehearth (322A) is below the glass level (L) and thus forms a glass contact surface that comes into contact with the molten glass (G). Consequently, this portion of forehearth (322A) is constructed of a more costly glass contact material. A ceramic refractory material (i.e., zircon, chromic oxide, or other suitable material) is a suitable glass contact refractory material because it can sustain the corrosive effects of molten glass (G).

(41) Forehearth (322A) may comprise a top or crown (not shown), a bottom (also not shown), and sidewalls (328A). Forehearth (322A) has an upstream end, generally indicated at (330A), and a downstream end, generally indicated at (332A). An open end (334) may be provided at the downstream end (332A) of forehearth (322A). An end wall (336A) may be provided at the upstream end (330A) of forehearth (322A). One or more glass orifices (338) may be provided in the bottom of forehearth (322A) proximate, adjacent or close to the end wall (336A). The forehearth of the front end, as introduced above, is that portion of the forehearth (322A) having end wall (336A) and glass orifices (338) in the bottom.

(42) Forehearth burners (344), such as oxygen-fuel burners, are positioned above the glass level (L), shown in FIG. 7. The forehearth burners (344) are oriented in a plane (e.g., a substantially horizontal plane) perpendicular to the surfaces (340) and at an acute angle relative to the surfaces (340). The forehearth burners (344) are pointed toward the downstream end 332A of forehearth (322A) at an angle between about 5 degrees to about 85 degrees relative to the surfaces (340), as shown in FIG. 6. Forehearth burners (344) may be staggered or alternatively spaced so that opposing forehearth burners (344) in the opposing sidewalls (328A) are laterally offset or do not laterally align (do not vertically align when viewing FIG. 6) with one another.

(43) The flame temperature of an oxygen-fuel burner is about 4200-5200 F. However, the flame is preferably very small. Consequently, the flame does not directly contact the sidewalls (328A). However, heat radiating from the flame is quite substantial. Although the flame does not directly contact the sidewalls (328A), the sidewalls (328A) are heated sufficiently by convection or heat otherwise radiating from the flame. This radiant heat is sufficient to properly condition the molten glass (G) and maintain the molten glass G at a desired temperature without compromising the integrity of forehearth (322A) by exposing forehearth (322A) to excessively high temperatures. This holds true even if the burners (344) are spaced about 1 foot to about 5 feet apart from one another.

(44) It is to be appreciated that other forehearth burner arrangements are possible and fall within the scope of the invention. For example, another exemplary burner arrangement is illustrated in FIG. 7. The forehearth burners (344) are oriented in a plane (e.g., a substantially vertical plane) perpendicular to the surface (346) and at an acute angle relative to the surface (346). The forehearth burners (344) may be pointed toward the upstream end 330C of the channel (322C) at an angle between about 5 degrees to about 85 degrees relative to the surface 346, as shown in FIG. 7. Alternatively, the forehearth burners (344) can be pointed toward the downstream end (332C) of the channel (322C) at an angle between about 95 degrees to about 175 degrees relative to the surface (346).

(45) It is to be noted that the burners may arranged in the crown (roof) of the forehearth, in the side walls, the end walls, submerged within the batch or molten glass, or in combinations thereof.

(46) Bushing Assembly

(47) As shown in FIG. 5, a bushing assembly 100 includes a bushing (110) and a bushing frame 210. The bushing (110) includes a bushing main body (120) with sidewalls (122) and a tip plate (124) extending between the sidewalls (122). The main body (120) is positioned below a bushing block (300) that, in turn, is positioned beneath a forehearth (310). In practicing the method of the present invention, a stream of molten glass is received by the main body (120) from the forehearth (310). The forehearth (310) receives the molten glass from a melter (10) (shown in FIG. 1). A delivery channel (40) is positioned between the melter (10) and the forehearth (310) to deliver the molten glass batch composition (30) from the melter (10) to the forehearth (310). The forehearth (310) and bushing block (300) may be conventional in construction and may be formed from refractory materials.

(48) The tip plate (124) contains a plurality of nozzles (124a) (also referred to as orifices) through which a plurality of streams of molten glass may be discharged. The streams of molten material may be mechanically drawn from the tip plate (124) to form continuous filaments (125) via a conventional winder device (400) such as a winder or chopper or other means of attenuation. The filaments (125) may be gathered into a single or multiple continuous strands (125a) after having received a protective coating of a sizing composition from a sizing applicator (410). The continuous filaments (125a) may be wound onto a rotating collet (402) of the winder device (400) to form a package (125b). The continuous filaments (125) may also be processed into other desired composite glass materials including, without limitation, wet use chopped strand fibers, dry use chopped strand fibers, continuous filament mats, chopped strand mats, wet formed mats or air laid mats.

(49) High strength articles of the present invention use the formed fibers described above as glass fiber reinforcement within a polymer matrix material. Typical matrix materials include epoxies, phenolic resins, vinylesters, and polyesters. The articles may be formed by any suitable manufacturing technique including compression molding, laminating, spray up, hand laying, prefabricated lay-up (prepreg), compression molding, vacuum bag molding, pressure bag molding, press molding, transfer molding, vacuum assisted resin transfer molding, pultrusion molding, filament winding, casting, autoclave molding, centrifugal casting resin transfer and continuous casting.

(50) Having generally described this invention, a further understanding can be obtained by reference to certain specific examples illustrated below which are provided for purposes of illustration only and are not intended to be all inclusive or limiting unless otherwise specified.

EXAMPLES

(51) The glasses in the examples listed in Tables IIA-IIC were melted in platinum crucibles or in a continuous platinum-lined melter for determining the mechanical and physical properties of the glass and fibers produced there from. The units of measurement for the physical properties are: Viscosity ( F.), Liquidus temperature ( F.) and T ( F.). In some examples the glasses were fiberized and Strength (KPsi), Density (g/cc), and Modulus (MPsi) were measured.

(52) The fiberizing temperature was measured using a rotating spindle viscometer. The fiberizing viscosity is defined as 1000 Poise. The liquidus was measured by placing a platinum container filled with glass in a thermal gradient furnace for 16 hours. The greatest temperature at which crystals were present was considered the liquidus temperature. The modulus was measured using the sonic technique on a single fiber of glass. The tensile strength was measured on a pristine single fiber.

(53) TABLE-US-00001 TABLE II-A Glass Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 SiO.sub.2 67.2 69 67 70 70 65 Al.sub.2O.sub.3 20 22 22 17 17 21 MgO 9.8 9 11 11 10 11 Li.sub.2O 3 0 0 2 3 3 Measured 2531 2761 2648 2557 2558 2461 Viscosity( F.) 1.sup.st Measured 2313 2619 2597 2332 2302 2296 Liquidus ( F.) 2.sup.nd Measured 2302 2620 2614 2346 2308 2318 Liquidus ( F.) T ( F.) 218 142 51 225 256 165 Measured 2.459 2.452 2.481 2.450 2.441 2.482 Density (g/cc)

(54) TABLE-US-00002 TABLE II-B Glass Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 SiO.sub.2 70 69 70 65 66 65 Al.sub.2O.sub.3 18 17 21 22 22 22 MgO 9 11 9 11 9 10 Li.sub.2O 3 3 0 2 3 3 Measured 2544 2496 2752 2525 2523 2486 Viscosity ( F.) 1.sup.st Measured 2311 2234 2597 2468 2391 2361 Liquidus ( F.) 2.sup.nd Measured 2324 2343 2603 2462 2394 2382 Liquidus ( F.) T ( F.) 233 262 155 57 132 125 Measured 2.434 2.455 2.443 2.486 2.460 2.474 Density (g/cc)

(55) TABLE-US-00003 TABLE II-C Glass Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18 SiO.sub.2 70 67.32 67.57 68.27 68.02 67.76 Al.sub.2O.sub.3 19 20.49 20.49 20.10 20.10 20.10 MgO 11 10.00 10.00 9.69 9.69 9.69 Li.sub.2O 0 2.00 1.75 1.75 2.00 2.25 Measured 2679 2563 2584 2598 2578 2547 Viscosity ( F.) 1.sup.st Measured 2596 2456 2486 2446 2431 2399 Liquidus ( F.) 2.sup.nd Measured 2582 2447 2469 2469 2437 2406 Liquidus ( F.) T ( F.) 83 111.5 106.5 140.5 144 144.5 Measured Density (g/cc) 2.453 2.461 2.452

(56) The compositions useful in the present invention may also include chain modifiers such as Na.sub.2O, CaO and B.sub.2O.sub.3. Such compositions are shown in Table II-D (below).

(57) TABLE-US-00004 TABLE II-D Glass Ex. 19 Ex. 21 Ex. 22 Ex. 22 Ex. 23 Ex. 24 SiO.sub.2 75 66 65 65 66 74 Al.sub.2O.sub.3 15 20 20 24 19 15 MgO 8 9 8 8 9 8 Li.sub.2O 1 1 2 0 0 0 Na.sub.2O 1 2 1 1 2 3 CaO 2 4 B.sub.2O.sub.3 2 4 Measured 2765 2607 2469 2669 2809 Viscosity ( F.) 1.sup.st Measured 2422 2729 2614 2630 2680 Liquidus ( F.) T ( F.) 343 122 55 129

(58) The fibers produced by the present invention have superior modulus and strength characteristics. The fibers of Example 1 have a Measured Modulus of 12.71 MPsi and a Measured Strength of 688 KPsi. The fibers of Example 3 have a Measured Modulus of 12.96 MPsi and a Measured Strength of 737 KPsi. The fibers of Example 17 have a Measured Modulus of 12.75 MPsi and a Measured Strength of 734 KPsi.

(59) As is understood in the art, the above exemplary inventive compositions do not always total 100% of the listed components due to statistical conventions (such as, rounding and averaging) and the fact that some compositions may include impurities that are not listed. Of course, the actual amounts of all components, including any impurities, in a composition always total 100%. Furthermore, it should be understood that where small quantities of components are specified in the compositions, for example, quantities on the order of about 0.05 weight percent or less, those components may be present in the form of trace impurities present in the raw materials, rather than intentionally added.

(60) Additionally, components may be added to the batch composition, for example, to facilitate processing, that are later eliminated, thereby forming a glass composition that is essentially free of such components. Thus, for instance, minute quantities of components such as fluorine and sulfate may be present as trace impurities in the raw materials providing the silica, lithia, alumina, and magnesia components in commercial practice of the invention or they may be processing aids that are essentially lost during manufacture.

(61) As is apparent from the above examples, certain glass fiber compositions useful in the invention have advantageous properties, such as low fiberizing temperatures and wide differences between the liquidus temperatures and the fiberizing temperatures (high T values). Other advantages and obvious modifications of the invention will be apparent to the artisan from the above description and further through practice of the invention.

(62) In certain embodiments the high-performance glass produced by the present invention melts and refines at relatively low temperatures, has a workable viscosity over a wide range of relatively low temperatures, and a low liquidus temperature range.

(63) In other embodiments the high-performance glass produced by the present invention melts and refines at relatively high temperatures, and has a workable viscosity over a relatively small temperature range.

(64) The invention of this application has been described above both generically and with regard to specific embodiments. Although the invention has been set forth in what is believed to be the preferred embodiments, a wide variety of alternatives known to those of skill in the art can be selected within the generic disclosure. Other advantages and obvious modifications of the invention will be apparent to the artisan from the above description and further through practice of the invention. The invention is not otherwise limited, except for the recitation of the claims set forth below.