Use of mgo, zno, and rare earth oxides for making improved low dielectric fibers with improved low thermal expansion coefficient for high boron aluminosilicate compositions

Abstract

This invention discloses novel glass compositions and their applications. The glass compositions described herein may include 50% to 55% by weight of SiO2, 17% to 26% by weight of B2O3, 13% to 19% by weight of Al2O3, 0% to 8.5% by weight of MgO, 0% to 7.5% by weight of ZnO, 0% to 6% by weight of CaO, 0% to 1.5% by weight of Li2O, 0% to 1.5% by weight of F2, 0% to 1% by weight of Na2O, 0% to 1% by weight of Fe2O3, 0% to 1% by weight of TiO2, and 0% to 8% by weight of other components. Glass fibers formed from these compositions, composites comprising these glass compositions and / or glass fibers, and articles thereof are also described herein.

Description

Technical Field

[0001] This invention relates to glass compositions and their applications. Examples include glass compositions for forming fibers, fibers, and articles comprising fibers (e.g., printed circuit boards) having improved electrical performance and thermal stability. Prior Technology

[0002] Glass fiber has been used for many years to reinforce various polymer resins. Some commonly used glass compositions for reinforcing applications include compositions from the "E-glass" and "D-glass" series. Another commonly used glass composition is available from AGY (Aiken, South Carolina) under the trademark "L-glass". In reinforcement and other applications, certain electrical and thermal properties of glass fibers, or those of glass fiber-reinforced composites, can be crucial, especially for printed circuit board substrates. However, in many cases, the manufacture of glass fibers with modified electrical and thermal properties (e.g., low dielectric constant, low coefficient of thermal expansion) can lead to higher costs due to factors such as increased batch costs, increased manufacturing costs, or other factors. For example, the aforementioned "L-glass" has improved electrical and thermal properties compared to conventional E-glass, but its cost is significantly higher due to the substantially higher temperature and energy requirements for batch-to-glass conversion, melt clarification, and fiber drawing. Fiberglass manufacturers continue to seek glass compositions that can be used to form glass fibers with the desired performance-related properties in commercial manufacturing environments. Summary of the Invention

[0003] Various embodiments of the present invention provide glass compositions, fiberizable glass compositions, glass fibers formed from such compositions, and articles comprising such glass compositions and / or glass fibers. The glass compositions, fiberizable glass compositions, and glass fibers (e.g.) in embodiments of the present invention may have one or more of the following advantageous characteristics compared to currently commercially available glass compositions: a lower coefficient of thermal expansion (CTE) value, a lower dielectric constant (Dk), a lower melting and forming temperature, and / or a higher glass transition temperature. Additional benefits of embodiments of the present invention may include increased fiber strength, increased fiber Young's modulus, reduced fiber density, and / or reduced boron emissions. Embodiments of the present invention may be advantageous for printed circuit board applications, as well as other potential applications. Based on the description provided herein, the additional advantages of embodiments of the present invention will be apparent to those skilled in the art. The features and embodiments of the present invention are described in more detail in the following embodiments. Implementation

[0004] Cross-reference to related applications This application claims priority to U.S. Provisional Patent Application No. 62 / 160,709, filed May 13, 2015, which is incorporated herein by reference in its entirety. Unless otherwise indicated, the numerical parameters set forth in the following specification are approximations that may vary depending on the desired properties sought to be obtained by means of the present invention. At least, and without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be interpreted based on the number of significant digits reported and by applying general rounding techniques. While the numerical ranges and parameters used to illustrate the broad scope of this invention are approximate, the values ​​described in specific examples are reported as precisely as possible. However, any numerical value inherently contains some error that is necessarily caused by the standard deviation found in its individual test measurements. Furthermore, all ranges disclosed herein should be understood to encompass any and all subranges contained therein. For example, the stated range "1 to 10" should be considered to include any and all subranges between the minimum value 1 and the maximum value 10 (and including both the minimum value 1 and the maximum value 10); that is, all subranges starting at a minimum value of 1 or greater (e.g., 1 to 6.1) and ending at a maximum value of 10 or less (e.g., 5.5 to 10). Additionally, any reference referred to as "incorporated herein" should be understood to be incorporated herein in its entirety. As used herein, the term "substantially none" means any amount of a component present in the glass composition due to the component present as a trace impurity in the batch, which will be present only in an amount of about 0.2% by weight or less (e.g., 0.1% by weight or less, 0.05% by weight or less, 0.01% by weight or less, or 0.005% by weight or less). It should be further noted that, unless explicitly and definitively limited to a single indicator, the singular forms “a / an” and “the” used in this specification include a plurality of indicators. Embodiments of the present invention include glass compositions. In one embodiment, the present invention provides glass fibers formed from the glass compositions described herein. In some embodiments, the glass fibers of the present invention may have modified mechanical properties, such as a low dielectric constant and a low coefficient of thermal expansion, compared to L-glass fibers. Additionally, the composition has modified properties, such as a lower melting and forming temperature and a higher glass transition temperature. In some embodiments, the glass composition of the present invention is suitable for fiber forming and comprises about 50% to about 55% by weight of SiO2, about 17% to about 26% by weight of B2O3, about 13% to about 19% by weight of Al2O3, about 0% to about 8.5% by weight of MgO, about 0% to about 7.5% by weight of ZnO, about 0% to about 6% by weight of CaO, about 0% to about 1.5% by weight of Li2O, about 0% to about 1.5% by weight of F2, about 0% to about 1% by weight of Na2O, about 0% to about 1% by weight of Fe2O3, about 0% to about 1% by weight of TiO2, and about 0% to about 8% by weight of other components, all amounts being based on the weight of the glass composition. Some embodiments of the present invention can be characterized by the amount of SiO2 present in the glass composition. In some embodiments, SiO2 may be present in an amount of about 50% to about 55% by weight, based on the weight of the glass composition. In some embodiments, SiO2 may be present in an amount of about 51% to about 54% by weight. In some embodiments, the SiO2 content may be present in an amount of about 52% to about 54% by weight. In some embodiments, the SiO2 content may be present in an amount greater than 52% to about 53.5% by weight. Some embodiments of the present invention can be characterized by the amount of B₂O₃ present in the glass composition. In some embodiments, B₂O₃ may be present in an amount of about 17% by weight to about 26% by weight, based on the weight of the glass composition. In some embodiments, the B₂O₃ content may be about 17.5% by weight to about 25% by weight. In some embodiments, the B₂O₃ content may be about 19% by weight to about 24% by weight. In some embodiments, the B₂O₃ content may be about 17.5% by weight to about 22% by weight. In some embodiments, the B₂O₃ content may be about 22% by weight to about 26% by weight. Some embodiments of the present invention can be characterized by the amount of Al₂O₃ present in the glass composition. In some embodiments, Al₂O₃ may be present in an amount of about 13% by weight to about 19% by weight, based on the weight of the glass composition. In some embodiments, the Al₂O₃ content may be from about 14% by weight to about 18% by weight. In some embodiments, Al₂O₃ may be present in an amount greater than 13% by weight to about 16% by weight. In some embodiments, Al₂O₃ may be present in an amount of about 16% by weight to about 18.5% by weight. Some embodiments of the present invention can be characterized by the amount of MgO present in the glass composition. In some embodiments, the MgO content may be about 8.5% by weight or less, based on the weight of the glass composition. In some embodiments, the MgO content may be greater than 0% by weight to about 8.5% by weight. In some embodiments, the MgO content may be greater than 0% by weight to about 7.5% by weight. In some embodiments, the MgO content may be about 1% by weight to about 8.5% by weight. In some embodiments, the MgO content may be about 2% by weight to about 8.5% by weight. In some embodiments, the MgO content may be about 2% by weight to about 8% by weight. In some embodiments, the MgO content may be about 3% by weight to about 7% by weight. In some embodiments, the MgO content may be 1% by weight or less. Some embodiments of the present invention can be characterized by the combined content of Al₂O₃ and MgO (i.e., Al₂O₃ + MgO) present in the glass composition. In some embodiments, the Al₂O₃ + MgO content may be at least about 14 wt% based on the weight of the glass composition. In some embodiments, the Al₂O₃ + MgO content may be from about 14 wt% to about 26.5 wt%. In some embodiments, the Al₂O₃ + MgO content may be from about 14 wt% to about 26 wt%. In some embodiments, the Al₂O₃ + MgO content may be from about 14 wt% to about 21 wt%. In some embodiments, the Al₂O₃ + MgO content may be from about 20 wt% to about 26.5 wt%. Some embodiments of the present invention can be characterized by the amount of ZnO present in the glass composition. In some embodiments, the ZnO content may be from about 0% by weight to about 8% by weight, based on the weight of the glass composition. In some embodiments, the ZnO content may be from about 0% by weight to about 7.5% by weight. In some embodiments, the ZnO content may be greater than 0% by weight to about 5% by weight. In some embodiments, the ZnO content may be from about 2% by weight to about 7.5% by weight. In some embodiments, the ZnO content may be from about 2% by weight to about 5.5% by weight. In some embodiments, the composition may be substantially free of ZnO. [] Some embodiments of the present invention can be characterized by the combined content of Al₂O₃ and ZnO (i.e., Al₂O₃ + ZnO) present in the glass composition. In some embodiments, the Al₂O₃ + ZnO content may be at least about 14% by weight, based on the weight of the glass composition. In some embodiments, the Al₂O₃ + ZnO content may be from about 14% by weight to about 22% by weight. In some embodiments, the Al₂O₃ + ZnO content may be from about 14% by weight to about 20% by weight. In some embodiments, the Al₂O₃ + ZnO content may be from about 14.5% by weight to about 18% by weight. Some embodiments of the present invention can be characterized by the amount of CaO present in the glass composition. In some embodiments, the CaO content may be from about 0% by weight to about 6% by weight, based on the weight of the glass composition. In some embodiments, the CaO content may be greater than 0% by weight to about 5.5% by weight. In some embodiments, the CaO content may be greater than 0% by weight to about 4.5% by weight. In some embodiments, the CaO content may be from about 1.5% by weight to about 5.5% by weight. In some embodiments, the CaO content may be less than about 1% by weight. In some embodiments, the composition may be substantially free of CaO. Some embodiments of the present invention can be characterized by the combined content of MgO and CaO (i.e., MgO+CaO) present in the glass composition. In some embodiments, the total MgO+CaO content may be about 9% by weight or less, based on the weight of the glass composition. In some embodiments, the MgO+CaO content may be greater than 0% by weight to about 9% by weight. In some embodiments, the MgO+CaO content may be greater than 0% by weight to about 7.5% by weight. In some embodiments, the MgO+CaO content may be greater than 0% by weight to about 4% by weight. In some embodiments, the MgO+CaO content may be about 2% by weight to about 9% by weight. In some embodiments, the MgO+CaO content may be about 4% by weight to about 8.5% by weight. Some embodiments of the present invention can be characterized by the amount of Na₂O present in the glass composition. In some embodiments, the Na₂O content may be about 1% by weight or less, based on the weight of the glass composition. In some embodiments, the Na₂O content may be about 0.5% by weight or less. In some embodiments, the Na₂O content may be about 0.1% by weight or less. In some embodiments, the Na₂O content may be about 0.05% by weight or less. In some embodiments, the Na₂O content may be greater than 0% by weight or up to about 1% by weight. In some embodiments, the Na₂O content may be greater than 0% by weight or up to about 0.5% by weight. In some embodiments, the Na₂O content may be greater than 0% by weight or up to about 0.1% by weight. In some embodiments, the Na₂O content may be about 0.04% by weight or up to about 0.05% by weight. Some embodiments of the present invention can be characterized by the amount of Li₂O present in the glass composition. In some embodiments, the Li₂O content may be about 1.5% by weight or less based on the weight of the glass composition. In some embodiments, the Li₂O content may be about 1.2% by weight or less. In some embodiments, the Li₂O content may be about 0.8% by weight or less. In some embodiments, the Li₂O content may be about 0.5% by weight or less. In some embodiments, the Li₂O content may be greater than 0% by weight or up to about 1.5% by weight. In some embodiments, the Li₂O content may be greater than 0% by weight or up to about 0.8% by weight. In some embodiments, the Li₂O content may be about 0.4% by weight or up to about 0.7% by weight. In some embodiments, the composition may be substantially free of Li₂O. Some embodiments of the present invention can be characterized by the total amount of Na₂O and Li₂O present in the composition (i.e., Na₂O + Li₂O). In some embodiments, the Na₂O + Li₂O content may be less than about 1.5% by weight based on the weight of the glass composition. In some embodiments, the Na₂O + Li₂O content may be less than about 1.2% by weight. In some embodiments, the Na₂O + Li₂O content may be less than about 0.7% by weight. In some embodiments, the Na₂O + Li₂O content may be about 0.1% by weight or less. In some embodiments, the Na₂O + Li₂O content may be from about 0.4% by weight to about 0.7% by weight. [] Some embodiments of the present invention can be characterized by the amount of F2 present in the glass composition. In some embodiments, the F2 content may be about 1.5% by weight or less based on the weight of the glass composition. In some embodiments, F2 may be greater than 0% by weight to about 1.5% by weight. In some embodiments, F2 may be present in an amount from about 0.5% by weight to about 1.5% by weight. In some embodiments, F2 may be present in an amount from about 0.9% by weight to about 1.3% by weight. Some embodiments of the present invention can be characterized by the amount of Fe₂O₃ present in the glass composition. In some embodiments, the Fe₂O₃ content may be about 1% by weight or less, based on the weight of the glass composition. In some embodiments, the Fe₂O₃ content may be about 0.5% by weight or less. In some embodiments, Fe₂O₃ may be greater than 0% by weight or about 0.5% by weight. In some embodiments, Fe₂O₃ may be present in an amount from about 0.2% by weight to about 0.4% by weight. Some embodiments of the present invention can be characterized by the amount of TiO2 present in the glass composition. In some embodiments, the TiO2 content may be about 1% by weight or less, based on the weight of the glass composition. In some embodiments, TiO2 may be present in amounts greater than 0% by weight to about 0.7% by weight. In some embodiments, TiO2 may be present in amounts from about 0.4% by weight to about 1% by weight. In some embodiments, TiO2 may be present in amounts from about 0.4% by weight to about 0.7% by weight. In some embodiments, TiO2 may be present in amounts from about 0.45% by weight to about 0.6% by weight. Some embodiments of the present invention can be characterized by the amount of BaO and / or SrO present in the glass composition. These compositions may contain small amounts of BaO and / or SrO from impurities; the combined concentration of BaO and SrO may be about 0.2% by weight or less, based on the weight of the glass composition. In some embodiments, the composition may be substantially free of BaO. In some embodiments, the composition may be substantially free of SrO. Sulfates (represented as SO3) may also be present as purifying agents. In some embodiments, the composition is substantially free of SO3. Small amounts of impurities, such as Cl2, P2O5, Cr2O3, or NiO, may also be present due to contamination from raw materials or during the melting process, although not limited to these specific chemical forms. Other purifying agents and / or processing aids (such as As2O3, MnO2, Sb2O3, or SnO2) may also be present, although not limited to these specific chemical forms. These impurities and purifying agents (if present) are typically present in amounts of less than about 0.5% by weight based on the weight of the glass composition. [] Some embodiments of the present invention can be characterized by the amount of rare earth oxides (RE 2O 3) present in the glass composition. As understood by those skilled in this art, the term "rare earth oxide" refers to oxides containing rare earth metals and including the following: scandium (Sc₂O₃), yttrium (Y₂O₃), and lanthanides (lanthanum (La₂O₃), cerium (Ce₂O₃ and CeO₂), tungsten (Pr₂O₃), neodymium (Nd₂O₃), protium (Pm₂O₃), samarium (Sm₂O₃), europium (Eu₂O₃ and EuO), thorium (Gd₂O₃), tbium (Tb₂O₃), dysprosium (Dy₂O₃), holmium (Ho₂O₃), erbium (Er₂O₃), thionium (Tm₂O₃), ytterbium (Yb₂O₃), and argonium (Lu₂O₃)). In some embodiments of the glass composition of the present invention, one or more rare earth oxides may be included in an amount exceeding that of rare earth oxides present only as impurities or contaminants in the batch of glass to provide another component. In some embodiments, the glass composition may comprise a combination of rare earth oxides (e.g., one or more of various rare earth oxides). In some embodiments, the one or more rare earth oxides comprise at least one of La₂O₃, CeO₂, Y₂O₃, and Sc₂O₃. In some embodiments, the glass composition of the present invention may contain one or more rare earth oxides (RE₂O₃) in an amount greater than about 0.1% by weight, based on the weight of the glass composition. In some embodiments, the total amount of the one or more rare earth oxides may be about 8% by weight or less. In some embodiments, the content of the one or more rare earth oxides may be greater than 0% by weight to about 8% by weight. In some embodiments, the content of the one or more rare earth oxides may be greater than 0% by weight to about 7.5% by weight. In some embodiments, the content of the one or more rare earth oxides may be present in an amount from about 3.5% by weight to about 7.5% by weight. In some embodiments, the composition may be substantially free of rare earth oxides. Some embodiments of the present invention may be characterized by the combined content of Al₂O₃ and rare earth oxides (i.e., Al₂O₃ + RE₂O₃) present in the glass composition. In some embodiments, the Al₂O₃ + RE₂O₃ content may be at least about 13% by weight, based on the weight of the glass composition. In some embodiments, the Al₂O₃ + RE₂O₃ content may be from about 13% by weight to about 22% by weight. In some embodiments, the Al₂O₃ + RE₂O₃ content may be from about 14 wt% to about 22 wt%. In some embodiments, the Al₂O₃ + RE₂O₃ content may be from about 14 wt% to about 18 wt%. In some embodiments, the Al₂O₃ + RE₂O₃ content may be from about 18 wt% to about 22 wt%. It should be understood that the description of the glass composition as any component present in an amount from about 0 wt% to another wt% is not necessarily required in all embodiments. In other words, in some embodiments, such components may naturally be present depending on the amount of other components included in the composition. Similarly, in some embodiments, the glass composition may be substantially free of such components, meaning that any amount of such component present in the glass composition would be generated by the component present as a trace impurity in the batch and would be present only in an amount of about 0.2 wt% or less. As noted above, the glass compositions according to some embodiments of the present invention are fiberizable. In some embodiments, the glass compositions of the present invention have a forming temperature (TF) suitable for commercial fiberglass manufacturing operations. As used herein, the term "forming temperature" or TF means the temperature at which the glass composition has a viscosity of 1000 poise (or "log 3 temperature"). In some embodiments, the TF of the glass compositions of the present invention ranges from about 1030°C to about 1350°C. In another embodiment, the TF of the glass compositions of the present invention ranges from about 1150°C to about 1300°C. [] In some embodiments, the liquidus temperature range of the glass composition of the present invention is from about 1030°C to about 1360°C. In another embodiment, the liquidus temperature range of the glass composition of the present invention is from about 1155°C to about 1255°C. [] In some embodiments, the difference between the forming temperature and the liquidus temperature of the glass composition of the present invention is suitable for commercial fiberglass manufacturing operations. For example, for some embodiments of the glass composition, the difference between the forming temperature and the liquidus temperature ranges from about 35°C to greater than 60°C. In some embodiments, the difference between the forming temperature and the liquidus temperature of the glass composition of the present invention is at least 65°C. [] As provided herein, glass fibers can be formed from some embodiments of the glass compositions of the present invention. Therefore, embodiments of the present invention may comprise glass fibers formed from any of the glass compositions described herein. In some embodiments, the glass fibers may be configured as fabrics. In some embodiments, the glass fibers of the present invention may be provided in other forms, including, for example, but not limited to, as continuous tows, chopped tows (dry or wet), yarns, rovings, prepregs, etc. In short, various embodiments of the glass compositions (and any fibers formed therefrom) can be used in a variety of applications. The glass fibers of this invention can be prepared by incorporating raw materials containing specific oxides for supplying the fiber composition, in a manner well known in the art. Glass fibers according to various embodiments of the invention can be formed using any method known in the art for forming glass fibers and, more preferably, any method known in the art for forming substantially continuous glass fibers. For example, although not limited herein, glass fibers according to non-limiting embodiments of the invention can be formed using direct melt or indirect melt fiber forming methods. These methods are well known in the art, and further discussion is deemed unnecessary in light of the invention. See, for example, KL Loewenstein, [The] [] [Manufacturing] [] [Technology] [] [of] [] [Continuous] [] [Glass] [] [Fibers], Elsevier, NY, 3rd edition, 1993, pp. 47-48 and 117-234. Some embodiments of the present invention relate to fiber glass filament bundles. Some embodiments of the present invention relate to yarns comprising fiber glass filament bundles. Some embodiments of the yarns of the present invention are particularly suitable for weaving applications. Additionally, some embodiments of the present invention relate to glass fiber fabrics. Some embodiments of the fiber glass fabrics of the present invention are particularly suitable for reinforcement applications, especially those where high modulus, high strength, and / or high elongation are important. Furthermore, some embodiments of the present invention relate to composites comprising fiber glass filament bundles, fiber glass yarns, and fiber glass fabrics, such as fiber-reinforced polymer composites. Further still, some embodiments of the present invention relate to fiber-reinforced composites for applications including (but not limited to) wind power, automotive, security / safety, aerospace, aviation, and high-pressure water tanks. Some embodiments of the present invention relate to printed circuit boards, where a lower coefficient of thermal expansion is particularly desirable, such as substrates for chip packaging. Some embodiments of the present invention relate to fiber glass bundles. In some embodiments, the fiber glass bundle of the present invention comprises a plurality of glass fibers and includes a glass composition comprising the following components: Approximately 50% to approximately 55% by weight of SiO₂; B₂O₃, approximately 17% by weight to approximately 26% by weight; From about 13 wt% to about 19 wt% Al₂O₃; From about 0% by weight to about 8.5% by weight of MgO; ZnO from about 0% by weight to about 7.5% by weight; From about 0% by weight to about 6% by weight of CaO; Li₂O: approximately 0% by weight to approximately 1.5% by weight; From about 0% by weight to about 1.5% by weight of F2; From about 0% by weight to about 1% by weight of Na₂O; From about 0% to about 1% by weight of Fe₂O₃; From about 0% by weight to about 1% by weight of TiO2; and Other components, totaling approximately 0% to approximately 8% by weight. This document discloses a variety of other glass compositions as part of the present invention, and other embodiments of the present invention relate to fiber glass bundles formed from such compositions. In some embodiments, the glass fibers of the present invention may exhibit desired mechanical and other properties. In some embodiments, the glass fibers of the present invention may exhibit one or more modified mechanical properties relative to glass fibers formed from L-glass. Examples of modified desired properties exhibited by some embodiments of the present invention include (but are not limited to) dielectric constant, coefficient of thermal expansion, melting and forming temperature, transition temperature, fiber strength, Young's modulus, density, and boron emission. [] In some embodiments, the glass fibers of the present invention may have a desired dielectric constant (DK) value. In some embodiments, fibers formed from the glass composition of the present invention may have a dielectric constant of less than 5 (at 1 GHz). In some embodiments, the glass fibers of the present invention may have a dielectric constant of less than 4.75 (at 1 GHz). In some embodiments, fibers formed from the glass composition of the present invention may have a dielectric constant of less than 4.0 (at 1 GHz). Unless otherwise stated herein, the dielectric constant values ​​discussed herein are determined using the procedures described in the Examples section below. In some embodiments, the glass fibers of the present invention may have a desired coefficient of thermal expansion (CTE) value. In some embodiments, fibers formed from the glass composition of the present invention may have a CTE of less than 3.5 ppm / °C. In some embodiments, the glass fibers of the present invention may have a CTE of less than 3.3 ppm / °C. In some embodiments, fibers formed from the glass composition of the present invention may have a CTE of less than 3.2 ppm / °C. Unless otherwise stated herein, the CTE values ​​discussed herein are determined using the procedures described in the Examples section below. The fiber glass bundle may contain glass fibers of various diameters, depending on the application. In some embodiments, the fiber glass bundle of the present invention contains at least one glass fiber with a diameter between about 5 µm and about 24 µm. In other embodiments, at least one glass fiber has a diameter between about 5 µm and about 10 µm. [] In some embodiments, the fiberglass filament bundles of the invention may be formed as yarns and coarse yarns. The rovings may contain assembled, multi-ended or single-ended direct traction rovings. The roving yarn comprising the fiberglass filament bundles of the present invention may depend on the application to be included directly traction single-ended roving yarn having various diameters and densities. In some embodiments, the roving yarn comprising the fiberglass filament bundle of the present invention exhibits a density of up to about 113 yards / lb. Some embodiments of the invention relate to yarns comprising at least one bundle of fiber glass filaments as revealed herein. In some embodiments, the yarns of the invention comprise at least one fiberglass filament bundle as revealed herein, wherein at least one fiberglass filament bundle is at least partially coated with a pulping composition. In some embodiments, the sizing composition is compatible with a thermosetting polymer resin. In other embodiments, the pulping composition may comprise a starch-oil pulping composition. The yarn has various linear mass densities depending on the application to be made. In some embodiments, the linear mass density of the yarns of the invention is from about 5,000 yards / lb to about 10,000 yards / lb. The yarn may have various degrees and directions depending on the application to be made. In some embodiments, the yarn of the present invention has a screw degree in the z direction from about 0.5 turns / inch to about 2 turns / inch. In other embodiments, the yarn of the present invention has a screw degree of about 0.7 turns / inch in the z direction. The yarn may be made from one or more bundles of yarns pinned together and / or plied together depending on the application to be applied. Yarns may be made from one or more bundles of yarns that are pinned together but not joined together; such yarns are called "single yarns." The yarn of the present invention may be made from one or more bundles of yarns that are held together but not joined together. In some embodiments, the yarn of the invention comprises 1-4 bundles of threads pinned together. In other embodiments, the yarn of the present invention comprises 1 bundle of adder threads. Some embodiments of the invention relate to fabrics comprising at least one bundle of fiber glass filaments. In some embodiments, the fabric of the invention may comprise at least one bundle of fiberglass filaments containing at least one of the glass compositions disclosed herein as part of the invention. In some embodiments, fabrics of the invention comprise yarns as disclosed herein. In some embodiments, the fabric of the invention may comprise at least one weft containing at least one bundle of fiber glass filaments as disclosed herein. In some embodiments, the fabric of the invention may comprise at least one warp yarn containing at least one bundle of fiber glass filaments as disclosed herein. In some embodiments, the fabric of the invention comprises at least one weft yarn containing at least one bundle of fiber glass filament as disclosed herein and at least one warp yarn containing at least one bundle of fiber glass filament as disclosed herein. In some embodiments of the invention that include fabrics, the glass fiber fabric is a fabric woven according to Industrial Fabric Pattern No. 7781. In other embodiments, the fabric includes plain weave, twill weave, claw weave, satin weave, stitch-knit (also known as non-crimped fabric), or "three-dimensional" woven fabric. Embodiments of the present invention may further include articles comprising embodiments of the glass composition of the present invention and / or embodiments of glass fibers. In some embodiments, the articles comprise: embodiments of the yarn of the present invention; embodiments of the fabric of the present invention; and / or embodiments of the composite of the present invention. Some embodiments of the articles of the present invention relate to printed circuit boards. In some embodiments, the printed circuit board comprises the yarns, fabrics, and / or composites of the present invention. Methods for manufacturing printed circuit boards are generally known to those skilled in the art. Some embodiments of the present invention relate to composites. In some embodiments, the composite of the present invention comprises a polymeric resin and a plurality of glass fibers disposed within the polymeric resin, wherein at least one of the plurality of glass fibers comprises any of the glass compositions disclosed herein as a part of the present invention. In some embodiments, the composite of the present invention comprises a polymeric resin and at least one fiber glass filament bundle disposed within the polymeric resin as disclosed herein. In some embodiments, the composite of the present invention comprises a polymeric resin and at least a portion of a roving comprising at least one fiber glass filament bundle disposed within the polymeric resin. In other embodiments, the composite of the present invention comprises a polymeric resin and at least one yarn disposed within the polymeric resin as disclosed herein. In still other embodiments, the composite of the present invention comprises a polymeric resin and at least one fabric disposed within the polymeric resin as disclosed herein. In some embodiments, the composite of the present invention comprises at least one weft yarn comprising at least one fiber glass filament bundle disclosed herein and at least one warp yarn comprising at least one fiber glass filament bundle disclosed herein. The composites of the present invention may comprise various polymeric resins depending on the desired properties and applications. In some embodiments of the composites of the present invention, the polymeric resin comprises epoxy resin. In other embodiments of the composites of the present invention, the polymeric resin may comprise polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenol, polyester, vinyl ester, polydicyclopentadiene, polyphenylene sulfide, polyetheretherketone, cyanate ester, dicis-butenediamide, and thermosetting polyurethane resins. The present invention will be described through a series of specific embodiments. However, those skilled in the art will understand that the principles of the present invention encompass many other embodiments. [Example] [] Table 1 provides information on a plurality of fiberizable glass compositions according to various embodiments of the present invention, as well as information related to various properties of such compositions. The glasses in these examples were prepared by melting a mixture of commercial and reagent-grade chemicals in powder form (reagent-grade chemicals were used only for rare earth oxides) in a 10% Rh / Pt crucible at a temperature between 1500°C and 1600°C (2732℉-2822℉) for four hours. Each batch was approximately 1000 grams. After the 4-hour melting period, the molten glass was poured onto a steel plate for quenching. Adjustments were made for the emission loss of volatile substances boron and fluorides in these batches. The compositions in the examples represent compositions as batch materials with the above adjustments. Commercial components were used to prepare the glass. In the batch calculations, a special raw material retention factor was considered to calculate the oxides in each glass. The retention factor was based on the glass batch melting and oxide yields in the measured glass over many years. Therefore, the compositions as batches described in the examples are considered to be close to the measured compositions. [surface] [1] [Example] 1 2 3 4 5 6 [SiO, 2, ] 52.76 52.91 53.84 53.52 53.02 53.04 [Al, 2, O, 3, ] 14.77 14.82 14.55 14.46 14.68 16.65 [Fe, 2, O, 3, ] 0.22 0.22 0.22 0.22 0.23 0.26 [CaO] 5.14 5.15 3.19 3.17 0.17 0.17 [MgO] 2.00 2.01 4.18 4.15 7.73 7.91 [By , 2, O ] 0.04 0.04 0.04 0.04 0.04 0.05 [ZnO] 0.00 0.00 0.00 0.00 0.00 0.00 [B , 2, O , 3, ] 23.46 22.83 22.38 22.25 22.52 20.34 [F , 2, ] 1.11 1.11 1.10 1.09 1.12 1.01 [TiO , 2, ] 0.50 0.50 0.49 0.49 0.50 0.57 [Li₂O] 0.01 0.41 0.00 0.61 0.00 0.00 [SO₃] 0.00 0.00 0.00 0.00 0.00 0.00 [Y₂O₃] 0.00 0.00 0.00 0.00 0.00 0.00 [La₂O₃] 0.00 0.00 0.00 0.00 0.00 0.00 [Total] 100.00 100.00 100.00 100.00 100.00 100.00 [T F , ( ] [℃)] 1314 1295 1350 1288 1298 1297 [T , L , ( ] [℃)] 1088 1024 1067 1041 1130 1186 [∆T (] [℃)] 226 271 283 247 168 111 [T , M , ( ] [℃)] 1541 1526 1584 1521 1540 1516 [T , soft , ( ] [℃)] 909 852 867 [T , g , ( ] [℃)] 625 598 636 655 666 [D , k , ] 4.57 4.80 4.60 4.79 4.68 [D, f , ] 0.0008 0.0012 0.0009 0.0016 0.0011 [CTE] [(ppm / ) [℃)] 3.32 3.47 3.21 3.28 3.04 [E (GPa)] 62.0 60.6 64.0 63.8 67.0 [density] [(g)] [ / cm, 3 , ] [)] 2.293 2.288 2.306 2.304 2.322 [surface] [1] [(] [Continued] [)] [] [Example] 7 8 9 10 11 12 [SiO, 2, ] 52.01 53.18 54.15 52.83 53.03 53.00 [Al , 2, O , 3, ] 17.01 17.40 17.71 14.82 14.76 14.45 [Fe , 2, O , 3, ] 0.26 0.27 0.28 0.23 0.21 0.20 [CaO] 0.17 0.18 0.18 0.14 4.19 5.13 [MgO] 8.08 8.26 8.41 6.37 0.08 0.09 [By , 2, O ] 0.05 0.05 0.05 0.04 0.04 0.04 [ZnO] 0.00 0.00 0.00 0.00 2.22 2.17 [B , 2, O , 3, ] 20.79 19.01 17.53 22.78 23.85 23.34 [F , 2, ] 1.03 1.05 1.07 1.12 1.12 1.09 [TiO , 2, ] 0.59 0.60 0.61 0.50 0.50 0.49 [Li , 2, O ] 0.00 0.00 0.00 1.16 0.01 0.01 [SO , 3, ] 0.00 0.00 0.00 0.00 0.00 0.00 [Y , 2, O , 3, ] 0.00 0.00 0.00 0.00 0.00 0.00 [Day , 2, O , 3, ] 0.00 0.00 0.00 0.00 0.00 0.00 [total] 100.00 100.00 100.00 100.00 100.00 100.00 [T, F , ( ] [℃)] 1273 1296 1307 1256 1333 1330 [T, L , ( ] [℃)] 1182 1192 1193 1081 1157 1167 [∆T (] [℃)] 91 104 114 175 176 163 [T, M , ( ] [℃)] 1489 1513 1520 1483 1563 1559 [T,soft , ( ] [℃)] 932 924 [T, g , ( ] [℃)] 668 673 675 592 624 616 [D, k , ] 4.89 4.58 4.73 [D, f , ] 0.0024 0.0006 0.0008 [CTE] [(ppm / , , ] [℃)] 3.05 3.02 3.12 3.42 3.16 3.12 [E (GPa)] 66.1 69.3 69.3 65.5 57.2 58.4 [density] [(g)] [ / cm, 3 , ] [)] 2.321 2.339 2.349 2.292 2.283 2.299 [surface] [1] [(] [Continued] [)] [Example] 13 14 15 16 17 18 [SiO, 2, ] 52.79 52.97 52.98 52.93 52.91 52.87 [Al, 2, O, 3, ] 14.69 14.44 14.68 14.79 14.75 14.73 [Fe, 2, O, 3, ] 0.21 0.20 0.20 0.22 0.21 0.21 [CaO] 4.17 2.17 0.00 2.16 0.07 2.57 [MgO] 0.08 0.05 0.02 3.22 3.20 1.01 [By , 2, O ] 0.04 0.04 0.04 0.04 0.04 0.04 [ZnO] 2.21 5.21 7.15 1.11 3.58 3.58 [B , 2, O , 3, ] 23.74 23.34 23.33 23.32 23.05 23.39 [F , 2, ] 1.11 1.09 1.09 1.12 1.11 1.10 [TiO , 2, ] 0.50 0.49 0.50 0.50 0.50 0.50 [Li , 2, O ] 0.45 0.00 0.00 0.58 0.58 0.00 [SO, 3, ] 0.00 0.00 0.00 0.00 0.00 0.00 [Y, 2, O, 3, ] 0.00 0.00 0.00 0.00 0.00 0.00 [La, 2, O, 3, ] 0.00 0.00 0.00 0.00 0.00 0.00 [Total] 100.00 100.00 100.00 100.00 100.00 100.00 [T , F , ( ] [°C] 1309 1330 1326 1288 1327 1323 [T , L , ( ] [°C] 1173 1297 1354 1130 1298 1295 [∆T (] [℃)] 136 33 -28 158 29 28 [T , M , ( ] [℃)] 1543 1561 1568 1517 1562 1579 [T , soft , ( ] [℃)] 848 849 908 [T , g , ( ] [℃)] 585 598 644 632 [D , k , ] 4.74 4.54 4.48 4.79 4.55 4.50 [D , f , ] 0.0008 0.0007 0.0006 0.0014 0.0009 0.0007 [CTE] [(ppm / , , ] [℃)] 3.24 3.33 3.02 2.97 [E (GPa)] 58.0 55.9 60.8 58.6 56.8 [density] [(g)] [ / cm, 3 , ] [)] 2.292 2.316 2.305 2.317 2.311 [surface] [1] [(] [Continued] [)] [] [Example] 19 20 twenty one twenty two twenty three twenty four [SiO, 2, ] 53.82 52.28 50.16 52.98 52.91 52.91 [Al, 2, O, 3, ] 13.35 15.75 16.44 14.68 14.75 14.75 [Fe , 2, O , 3, ] 0.20 0.24 0.25 0.20 0.21 0.21 [CaO] 3.34 3.57 3.73 0.00 0.07 0.07 [MgO] 3.34 3.80 3.97 0.02 3.20 3.20 [By , 2, O ] 0.04 0.04 0.04 0.04 0.04 0.04 [ZnO] 3.34 3.56 3.72 0.00 0.00 0.00 [B , 2, O , 3, ] 21.11 19.27 20.13 23.33 23.05 23.05 [F , 2, ] 1.00 0.94 0.98 1.09 1.11 1.11 [TiO,2,] 0.45 0.54 0.57 0.50 0.50 0.50 [Li, 2, O] 0.00 0.00 0.00 0.00 0.58 0.58 [SO, 3, ] 0.00 0.00 0.00 0.00 0.00 0.00 [Y, 2, O, 3, ] 0.00 0.00 0.00 0.00 0.00 3.58 [La, 2, O, 3, ] 0.00 0.00 0.00 7.15 3.58 0.00 [Total] 100.00 100.00 100.00 100.00 100.00 100.00 [T , F , ( ] [℃)] 1315 1287 1265 1362 1322 1311 [T , L , ( ] [℃)] 1122 1157 1157 1246 1243 [∆T (] [℃)] 193 130 108 76 68 [T , M , ( ] [℃)] 1542 1496 1471 1593 1552 1543 [T , soft , ( ] [℃)] 873 867 815 851 840 [T , g , ( ] [℃)] 631 643 640 616 619 625 [D, k , ] 4.73 4.87 5.01 4.51 4.66 4.61 [D, f , ] 0.0010 0.0012 0.0012 0.0009 0.0007 0.0007 [CTE] [(ppm / , , ] [℃)] 3.16 2.69 3.21 3 3.12 3.1 [E (GPa)] 61.5 65.4 66.0 55.0 61.1 61.2 [density] [(g)] [ / cm, 3 , ] [)] 2.342 2.380 2.391 2.341 2.312 2.306 [surface] [1] [(] [Continued] [)] [] [Example] 25 26 27 28 29 30 [SiO, 2, ] 52.21 51.93 52.05 52.25 53.52 53.16 [Al, 2, O, 3, ] 14.04 14.69 14.51 14.34 15.70 16.26 [Fe, 2, O, 3, ] 0.22 0.23 0.22 0.22 0.23 0.23 [CaO] 3.61 3.79 3.83 3.77 1.94 1.98 [MgO] 5.07 5.04 4.76 4.76 3.06 1.84 [By , 2, O ] 0.04 0.04 0.04 0.04 0.04 0.04 [ZnO] 0.00 0.00 0.00 0.00 0.00 0.00 [B , 2, O , 3, ] 23.32 22.80 23.10 23.13 23.90 24.80 [F , 2, ] 1.00 0.98 0.99 0.99 1.07 1.11 [TiO , 2, ] 0.48 0.50 0.50 0.49 0.54 0.56 [Li , 2, O ] 0.00 0.00 0.00 0.00 0.00 0.00 [SO , 3, ] 0.00 0.00 0.00 0.00 0.00 0.00 [Y, 2, O, 3, ] 0.00 0.00 0.00 0.00 0.00 0.00 [La, 2, O, 3, ] 0.00 0.00 0.00 0.00 0.00 0.00 [Total] 100.00 100.00 100.00 100.00 100.00 100.00 [T, F , ( ] [℃)] 1278 1274 1279 1285 1326 1327 [T, L , ( ] [℃)] 1048 1035 1032 1035 1307 > 1350 [∆T (] [℃)] 230 239 247 250 19 [T, M , ( ] [℃)] 1492 1484 1492 1498 1546 1553 [T, soft , ( ] [℃)] [T, g , ( ] [℃)] [D, k , ] 4.82 4.89 4.83 4.85 4.62 4.54 [D, f , ] 0.0011 0.0013 0.0012 0.0011 0.0010 0.0008 [CTE] [(ppm / , , ] [℃)] [E (GPa)] [density] [(g)] [ / cm, 3 , ] [)] [surface] [1] [(] [Continue] [)] [] [Actual example] 31 32 33 34 [SiO , 2, ] 52.91 52.32 52.56 52.31 [Al, 2, O, 3, ] 16.67 18.42 14.51 14.83 [Fe, 2, O, 3, ] 0.23 0.26 0.20 0.21 [CaO] 2.01 3.07 4.05 3.81 [MgO] 0.98 1.10 0.57 0.07 [Na, 2, O] 0.04 0.05 0.04 0.04 [ZnO] 0.00 0.00 2.36 3.02 [B, 2, O, 3, ] 25.44 22.89 23.74 23.70 [F, 2,] 1.13 1.25 1.07 1.09 [TiO,2,] 0.57 0.63 0.50 0.51 [Li, 2, O] 0.00 0.00 0.41 0.41 [SO, 3, ] 0.00 0.00 0.00 0.00 [Y, 2, O, 3, ] 0.00 0.00 0.00 0.00 [La, 2, O, 3, ] 0.00 0.00 0.00 0.00 [Total] 100.00 100.00 100.00 100.00 [T ,F , ( ] [℃)] 1325 1320 1186 1158 [T , L , ( ] [℃)] > 1350 > 1350 1325 1317 [∆T (] [℃)] 139 159 [T , M , ( ] [℃)] 1556 1532 1562 1554 [T , soft , ( ] [℃)] [T , g , ( ] [℃)] [D , k , ] 4.44 4.69 4.73 4.74 [D , f , ] 0.0006 0.0007 0.0005 0.0005 [CTE] [(ppm / , , ] [℃)] [E (GPa)] [density] [(g)] [ / cm, 3 , ] [)] [Melting Properties] The melt viscosity as a function of temperature and the liquidus temperature was determined using ASTM test methods C965 "Standard Practice for Measuring Viscosity of Glass Above the Softening Point" and C829 "Standard Practices for Measurement of Liquidus Temperature of Glass by the Gradient Furnace Method," respectively. Glass softening was determined using ASTM C338-93 (2008) "Standard Test Method for Softening Point of Glass." Table 1 includes the measured liquidus temperature (TL), reference forming temperature (TF) defined by a melt viscosity of 1000 poise, and reference melting temperature (TM) defined by a viscosity of 100 poise for the glass composition. The difference between the forming temperature and the liquidus temperature (ΔT) is also shown. [Thermal Properties] [] The linear thermal expansion coefficient of the glass was determined using ASTM test method E228-11, "Standard Test Method for Linear Thermal Expansion of Solid Materials With a Push-Rod Dilatometer". The glass transition temperature Tg of the glass was determined using the same method. [Electrical properties] [] The dielectric constant (Dk) and dissipation factor (Df) of each glass were determined at 1 GHz using ASTM Test Method D150, "Standard Test Methods for AC Loss Characteristics and Permittivity (Dielectric Constant) of Solid Electrical Insulating Materials". Polished thin films of each glass sample with a diameter of 40 mm and a thickness of 1–1.5 mm were used for Dk and Df measurements at 1 GHz using an Agilent E4991A RF impedance / material analyzer. [Mechanical Properties] [] The Young's modulus of certain glass compositions in Table 1 was also measured using the following technique. Approximately 50 grams of glass shavings having a composition corresponding to a suitable example in Table 1 were remelted in a 90 Pt / 10 Rh crucible at a melting temperature defined as 100 poise for two hours. The crucible was then transferred to a vertical tube, electric furnace. The furnace temperature was preset to a fiber drawing temperature close to or equal to a melt viscosity of 1000 poise. The glass was equilibrated at this temperature for one hour before fiber drawing. The fiber drawing furnace was topped with a lid with a central hole, and a water-cooled copper coil was installed above the lid to regulate fiber cooling. A silica rod was then manually immersed into the melt via a cooling swirl tube, and fibers approximately 1–1.5 m in length were extracted and collected. The fiber diameter ranged from 100 µm to 1000 µm. The elastic modulus of fibers extracted from the glass melt was determined using ultrasonic pulse technology (from Panatherm 5010 unit, Panametrics, Inc., Waltham, Massachusetts). Extended wave reflection time was obtained using a 200 kHz pulse with a duration of 20 microseconds. Sample lengths were measured, and individual extended wave velocities (VE) were calculated. Fiber density (ρ) was measured using a Micromeritics AccuPyc 1330 hydrometer. Approximately 20 measurements were performed on each composition, and the average Young's modulus (E) was calculated using the following formula: The modulus tester uses a 1 mm diameter waveguide, with the fiber diameter on the contact side of the waveguide set to approximately the same as the waveguide diameter. In other words, a 1000 µm diameter fiber end is connected to the contact side of the waveguide. Young's modulus of fibers with various diameters was tested, and the results showed that fiber diameters from 100 µm to 1000 µm did not affect the fiber modulus. The specific modulus value was calculated by dividing the Young's modulus value by the corresponding density. It should be understood that this specification describes aspects of the invention relevant to a clear understanding of the invention. Certain aspects of the invention that will be readily apparent to those skilled in the art and therefore will not contribute to a better understanding of the invention have not been presented in order to simplify this specification. Although the invention has been described in conjunction with certain embodiments, the invention is not limited to the specific embodiments disclosed, but rather is intended to cover modifications within the spirit and scope of the invention.

Claims

1. A glass composition suitable for fiber forming, comprising: 50 wt% to 55 wt% SiO2; 17 wt% to 26 wt% B2O3; 13 wt% to 19 wt% Al2O3; greater than 0 wt% to 8.5 wt% MgO; 0 wt% to 7.5 wt% ZnO; 0 wt% to 6 wt% CaO; 0 wt% to 1.5 wt% Li2O; 0 wt% to 1.5 wt% F2; 0 wt% to 1 wt% Na2O; 0 wt% to 1 wt% Fe2O3; 0.4 wt% to 1 wt% TiO2; and one or more rare earth oxides (RE2O3) in total of 0 wt% to 8 wt%, wherein the composition is substantially free of P2O5.

2. The composition of claim 1, wherein the SiO2 content is 51% to 54% by weight.

3. The composition of claim 1, wherein the B2O3 content is from 17.5% to 25% by weight.

4. The composition of claim 3, wherein the B2O3 content is from 19% to 24% by weight.

5. The composition of claim 1, wherein the Al2O3 content is from 14% to 18% by weight.

6. The composition of claim 1, wherein the MgO content is greater than 0% by weight to 7.5% by weight.

7. The composition of claim 1, wherein the MgO content is from 2% to 8.5% by weight.

8. The composition of claim 1, wherein the Al2O3 + MgO content is from 14% to 26.5% by weight.

9. The composition of claim 8, wherein the Al2O3 + MgO content is from 14% to 26% by weight.

10. The composition of claim 1, wherein the ZnO content is greater than 0% by weight to 5% by weight.

11. The composition of claim 1, wherein the content of Al2O3 + ZnO is from 14% to 22% by weight.

12. The composition of claim 1, wherein the CaO content is greater than 0% by weight to 5.5% by weight.

13. The composition of claim 1, wherein the content of MgO + CaO is 9% by weight or less.

14. The composition of claim 13, wherein the MgO + CaO content is greater than 0% by weight to 9% by weight.

15. The composition of claim 1, wherein the Na2O content is greater than 0% by weight to 0.5% by weight.

16. The composition of claim 1, wherein the Li2O content is 0.8% by weight or less.

17. The composition of claim 16, wherein the Li2O content is greater than 0% by weight to 0.8% by weight.

18. The composition of claim 1, wherein the total Na2O + Li2O content is less than 1.5% by weight.

19. The composition of claim 1, wherein the F2 content is greater than 0% by weight to 1.5% by weight.

20. The composition of claim 1, wherein the Fe2O3 content is greater than 0% by weight to 0.5% by weight.

21. The composition of claim 1, wherein the TiO2 content is greater than 0.4% by weight to 0.7% by weight.

22. The composition of claim 21, wherein the TiO2 content is greater than 0.4% by weight to 0.6% by weight.

23. The composition of claim 1, wherein the glass composition comprises one or more rare earth oxides in an amount greater than 0.01% by weight.

24. The composition of claim 1, wherein the content of the one or more rare earth oxides is greater than 0% by weight to 8% by weight.

25. The composition of claim 24, wherein the content of the one or more rare earth oxides is greater than 0% by weight to 7.5% by weight.

26. The composition of claim 25, wherein the content of the one or more rare earth oxides is greater than 0% by weight to 7% by weight.

27. The composition of claim 1, wherein the content of RE2O3 + Al2O3 is from 13% to 22% by weight.

28. The composition of claim 1, wherein the one or more rare earth oxides comprise at least one of La2O3, CeO2, Y2O3 and Sc2O3.

29. The composition of claim 1, wherein the composition is substantially free of BaO.

30. The composition of claim 1, wherein the composition is substantially free of SrO.

31. A fiber formed from a composition of any one of claims 1 to 30.

32. A product comprising the fibers as claimed in claim 31.

33. The product of claim 32, wherein the product is a printed circuit board.

34. A composite product comprising a polymeric resin and a plurality of fibers as claimed in claim 31 disposed therein.