Use of MgO, ZnO, and rare earth oxides to produce improved low dielectric constant fibers with improved low coefficient of thermal expansion for high boron aluminosilicate compositions

Abstract

To provide a novel glass composition and its use A novel glass composition and its uses are disclosed. The glass composition described herein is a glass composition containing 50 to 55 weight percent SiO2, 17 to 26 weight percent B2O3, and , 13 to 19 weight percent Al2O3, 0 to 8.5 weight percent MgO, 0 to 7.5 weight percent ZnO, 0 to 6 weight percent CaO, 0 to 1.5 weight percent Li2O, 0 to 1.5 weight percent F2, 0 to 1 weight percent Na2O, 0 to 1 weight percent Fe2O3, 0 to 1 weight percent TiO2, and 0 to 8 weight percent other components. Also described herein are glass fibers formed from such compositions, composites, and articles of manufacture comprising the glass compositions and / or glass fibers.

Description

[Technical Field]

[0001] Citation of 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.

[0002] FIELD OF THE INVENTION The present invention relates to glass compositions and their uses. Embodiments include glass compositions for forming fibers, fibers, and articles of manufacture (e.g., printed circuit boards) comprising the fibers, wherein the printed circuit boards have improved electrical performance and thermal stability. [Background technology]

[0003] Background of the Invention Glass fibers have been used for many years to reinforce various polymeric resins. Some commonly used glass compositions for use in reinforcement applications include the "E-glass" and "D-glass" families of compositions. Another commonly used glass composition is commercially available from AGY (Aiken, South Carolina) under the trade name "L-glass."

[0004] In reinforcement and other applications, certain electrical and thermal properties can be important for glass fibers or glass fiber-reinforced composites, particularly printed circuit boards. However, in many cases, producing glass fibers with improved electrical and thermal properties (e.g., lower dielectric constant, lower coefficient of thermal expansion, etc.) can result in higher costs, for example, due to higher batch material costs, higher manufacturing costs, or other factors. For example, the aforementioned "L-glass" has improved electrical and thermal properties compared to conventional E-glass, but also significantly higher costs as a result of significantly higher temperatures and energy demands for batch-to-glass conversion, melt fining, and fiber drawing. Fiberglass manufacturers continue to search for glass compositions that can be used to form glass fibers with desirable performance-related properties in a commercial manufacturing environment. Summary of the Invention [Means for solving the problem]

[0005] Abstract Various embodiments of the present invention provide glass compositions, fiberizable glass compositions, glass fibers formed from such compositions, and articles of manufacture including the glass compositions and / or glass fibers.

[0006] The glass compositions, fiberizable glass compositions, and glass fibers of embodiments of the present invention may have one or more of the following advantageous features, for example, compared to currently commercially available glass compositions: lower coefficient of thermal expansion (CTE) values, lower dielectric constants (Dk), lower melting and forming temperatures, and / or higher glass transition temperatures. Further advantages 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, among other potential applications. Further benefits of the embodiments will be apparent to those skilled in the art from the description provided herein.

[0007] The features and embodiments of the present invention are described in more detail in the detailed description that follows. DETAILED DESCRIPTION OF THE INVENTION

[0008] Detailed Description Unless otherwise indicated, the numerical parameters set forth in the following specification are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. While not attempting to limit the application of the doctrine of equivalents to the scope of the claims in any way, each numerical parameter should, at the very least, be construed as in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0009] 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. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Also, all ranges disclosed herein should be understood to encompass any and all subranges subsumed within those ranges. For example, a range stated as "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10 (including both endpoints), i.e., all subranges beginning with a minimum value of 1 or more (e.g., 1 to 6.1) and ending with 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 in its entirety.

[0010] As used herein, the term "substantially free" refers to any amount of a component present in a glass composition that is due to the component being present as a trace impurity in the batch materials and is present in an amount of only about 0.2 weight percent or less (e.g., 0.1 weight percent or less, 0.05 weight percent or less, 0.01 weight percent or less, or 0.005 weight percent or less).

[0011] Furthermore, it should be noted that as used herein, the singular forms "a," "an," and "the" include plural referents unless expressly and unambiguously limited to one referent.

[0012] Embodiments of the present invention include glass compositions. In one aspect, 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 improved mechanical properties, such as a lower dielectric constant and a lower coefficient of thermal expansion, compared to L-glass fibers. In addition, the compositions have improved properties, such as lower melting and forming temperatures and higher glass transition temperatures.

[0013] In some embodiments, the glass compositions of the present invention are suitable for fiber formation and comprise from about 50 to about 55 weight percent SiO, from about 17 to about 26 weight percent BO, from about 13 to about 19 weight percent AlO, from about 0 to about 8.5 weight percent MgO, from about 0 to about 7.5 weight percent ZnO, from about 0 to about 6 weight percent CaO, from about 0 to about 1.5 weight percent LiO, from about 0 to about 1.5 weight percent F, from about 0 to about 1 weight percent NaO, from about 0 to about 1 weight percent FeO, from about 0 to about 1 weight percent TiO, and from about 0 to about 1 weight percent SiO, all based on the weight of the glass composition. Contains 8 weight percent of other components.

[0014] 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 weight percent, based on the weight of the glass composition. In some embodiments, SiO2 may be about 51 to about 54 weight percent. In some embodiments, the SiO2 content may be about 52 to about 54 weight percent. In some embodiments, the SiO2 content may be greater than 52 to about 53.5 weight percent.

[0015] 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 to about 26 weight percent, based on the weight of the glass composition. In some embodiments, the B2O3 content may be about 17.5 to about 25 weight percent. In some embodiments, the B2O3 content may be about 19 to about 24 weight percent. In some embodiments, the B2O3 content may be about 17.5 to about 22 weight percent. In some embodiments, the B2O3 content may be about 22 to about 26 weight percent.

[0016] 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 to about 19 weight percent, based on the weight of the glass composition. In some embodiments, the Al2O3 content may be about 14 to about 18 weight percent. In some embodiments, Al2O3 may be present in an amount of greater than 13 to about 16 weight percent. In some embodiments, Al2O3 may be present in an amount of about 16 to about 18.5 weight percent.

[0017] 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 weight percent or less, based on the weight of the glass composition. In some embodiments, the MgO content may be greater than 0 to about 8.5 weight percent. In some embodiments, the MgO content may be greater than 0 to about 7.5 weight percent. In some embodiments, the MgO content may be about 1 to about 8.5 weight percent. In some embodiments, the MgO content may be about 2 to about 8.5 weight percent. In some embodiments, the MgO content may be about 2 to about 8 weight percent. In some embodiments, the MgO content may be about 3 to about 7 weight percent. In some embodiments, the MgO content may be 1 weight percent or less.

[0018] 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 weight percent, based on the weight of the glass composition. In some embodiments, the Al2O3 + MgO content may be about 14 to about 26.5 weight percent. In some embodiments, the Al2O3 + MgO content may be about 14 to about 26 weight percent. In some embodiments, the Al2O3 + MgO content may be about 14 to about 21 weight percent. In some embodiments, the Al2O3 + MgO content may be about 20 to about 26.5 weight percent.

[0019] 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 can be about 0 to about 8 weight percent based on the weight of the glass composition. In some embodiments, the ZnO content can be about 0 to about 7.5 weight percent. In some embodiments, the ZnO content can be about 0 to about 8 weight percent based on the weight of the glass composition. In some embodiments, the ZnO content may be from about 2 to about 7.5 weight percent. In some embodiments, the ZnO content may be from about 2 to about 5.5 weight percent. In some embodiments, the composition may be substantially free of ZnO.

[0020] 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 weight percent, based on the weight of the glass composition. In some embodiments, the Al2O3 + ZnO content may be about 14 to about 22 weight percent. In some embodiments, the Al2O3 + ZnO content may be about 14 to about 20 weight percent. In some embodiments, the Al2O3 + ZnO content may be about 14.5 to about 18 weight percent.

[0021] 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 about 0 to about 6 weight percent, based on the weight of the glass composition. In some embodiments, the CaO content may be greater than 0 to about 5.5 weight percent. In some embodiments, the CaO content may be greater than 0 to about 4.5 weight percent. In some embodiments, the CaO content may be about 1.5 to about 5.5 weight percent. In some embodiments, the CaO content may be less than about 1 weight percent. In some embodiments, the composition may be substantially free of CaO.

[0022] 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 content of MgO + CaO may be about 9 weight percent or less, based on the weight of the glass composition. In some embodiments, the content of MgO + CaO may be greater than 0 to about 9 weight percent. In some embodiments, the content of MgO + CaO may be greater than 0 to about 7.5 weight percent. In some embodiments, the content of MgO + CaO may be greater than 0 to about 4 weight percent. In some embodiments, the content of MgO + CaO may be about 2 to about 9 weight percent. In some embodiments, the content of MgO + CaO may be about 4 to about 8.5 weight percent.

[0023] Some embodiments of the present invention can be characterized by the amount of NaO present in the glass composition. In some embodiments, the NaO content may be about 1 weight percent or less, based on the weight of the glass composition. In some embodiments, the NaO content may be about 0.5 weight percent or less. In some embodiments, the NaO content may be about 0.1 weight percent or less. In some embodiments, the NaO content may be about 0.05 weight percent or less. In some embodiments, the NaO content may be greater than 0 to about 1 weight percent. In some embodiments, the NaO content may be greater than 0 to about 0.5 weight percent. In some embodiments, the NaO content may be greater than 0 to about 0.1 weight percent. In some embodiments, the NaO content may be about 0.04 to about 0.05 weight percent.

[0024] Some embodiments of the present invention can be characterized by the amount of LiO present in the glass composition. In some embodiments, the LiO content may be about 1.5 weight percent or less, based on the weight of the glass composition. In some embodiments, the LiO content may be about 1.2 weight percent or less. In some embodiments, the Li2O content may be about 0.8 weight percent or less. In some embodiments, the Li2O content may be about 0.5 weight percent or less. In some embodiments, the Li2O may be greater than 0 to about 1.5 weight percent. In some embodiments, the Li2O may be greater than 0 to about 0.8 weight percent. In some embodiments, the Li2O content may be about 0.4 to about 0.7 weight percent. In some embodiments, the composition may be substantially free of Li2O.

[0025] Some embodiments of the present invention can be characterized by the total amount of NaO and LiO present in the composition (i.e., NaO + LiO). In some embodiments, the NaO + LiO content may be less than about 1.5 weight percent, based on the weight of the glass composition. In some embodiments, the NaO + LiO content may be less than about 1.2 weight percent. In some embodiments, the NaO + LiO content may be less than about 0.7 weight percent. In some embodiments, the NaO + LiO content may be about 0.1 weight percent or less. In some embodiments, the NaO + LiO content may be about 0.4 to about 0.7 weight percent.

[0026] 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 weight percent or less, based on the weight of the glass composition. In some embodiments, F2 may be greater than 0 to about 1.5 weight percent. In some embodiments, F2 may be present in an amount of about 0.5 to about 1.5 weight percent. In some embodiments, F2 may be present in an amount of about 0.9 to about 1.3 weight percent.

[0027] 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 weight percent or less, based on the weight of the glass composition. In some embodiments, the Fe2O3 content may be about 0.5 weight percent or less. In some embodiments, Fe2O3 may be greater than 0 to about 0.5 weight percent. In some embodiments, Fe2O3 may be present in an amount of about 0.2 to about 0.4 weight percent.

[0028] 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 weight percent or less, based on the weight of the glass composition. In some embodiments, TiO2 may be present in an amount of greater than 0 to about 0.7 weight percent. In some embodiments, TiO2 may be present in an amount of about 0.4 to about 1 weight percent. In some embodiments, TiO2 may be present in an amount of about 0.4 to about 0.7 weight percent. In some embodiments, TiO2 may be present in an amount of about 0.45 to about 0.6 weight percent.

[0029] Some embodiments of the present invention can be characterized by the amount of BaO and / or SrO present in the glass composition. The composition may contain small amounts of BaO and / or SrO from impurities. The combined concentration of BaO and SrO in the composition may be about 0.2 weight percent 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.

[0030] Sulfate (expressed as SO3) may also be present as a refining agent. In some embodiments, the composition is substantially free of SO3. Also, sulfate may be present in the composition from raw materials or melt processes. Minor amounts of impurities such as Cl2, PO5, Cr2O3, or NiO may be present due to contamination during processing, but are not limited to these particular chemical forms. Other refining agents and / or processing aids such as As2O3, MnO2, Sb2O3, or SnO2 may also be present, but are not limited to these particular chemical forms. These impurities and refining agents, if present, are each typically present in an amount of less than about 0.5 weight percent, based on the weight of the glass composition.

[0031] Some embodiments of the present invention can be characterized by the amount of rare earth oxide (RE2O3) present in the glass composition. As will be understood by those skilled in the art, the term "rare earth oxide" refers to oxides incorporating rare earth metals, including oxides of scandium (ScO), oxide of yttrium (YO), and oxides of the lanthanide elements (lanthanum (LaO), cerium (CeO and CeO), praseodymium (PrO), neodymium (NdO), promethium (PmO), samarium (SmO), europium (EuO and EuO), gadolinium (GdO), terbium (TbO), dysprosium (DyO), holmium (HoO), erbium (ErO), thulium (TmO), ytterbium (YbO), and lutetium (LuO)).

[0032] In some embodiments of the glass compositions of the present invention, one or more rare earth oxides may be present in an amount greater than that in which the rare earth oxides are present solely as tramps or impurities in the batch materials included with the glass batch, resulting in another component. In some embodiments, the glass composition may include 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 include at least one of La2O3, CeO2, YO3, and Sc2O3.

[0033] In some embodiments, the glass compositions of the present invention may include one or more rare earth oxides (RE2O3) in an amount greater than about 0.1 weight percent, 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 weight percent or less. In some embodiments, the content of the one or more rare earth oxides may be greater than 0 to about 8 weight percent. In some embodiments, the content of the one or more rare earth oxides may be greater than 0 to about 7.5 weight percent. In some embodiments, the content of the one or more rare earth oxides may be present in an amount of about 3.5 to about 7.5 weight percent. 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 content of Al2O3 + RE2O3 may be at least about 13 weight percent, based on the weight of the glass composition. In some embodiments, the content of Al2O3 + RE2O3 may be about 13 to about 22 weight percent. In some embodiments, the content of Al2O3 + RE2O3 may be about 14 to about 22 weight percent. In some embodiments, the content of Al2O3 + RE2O3 may be about 14 to about 18 weight percent. In some embodiments, the content of Al2O3 + RE2O3 may be about 18 to about 22 weight percent. It should be understood that any component of the glass composition described as being present in an amount from about 0 weight percent to another weight percent is not necessarily required in all embodiments. In other words, such a component may be optional in some embodiments, depending, of course, on the amounts 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 the component present in the glass composition is due to the component being present as a trace impurity in the batch materials and is present in an amount of only about 0.2 weight percent or less.

[0034] As noted above, 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 (T F As used herein, "molding temperature" or T F The term refers to the temperature (or "log3 temperature") at which a glass composition has a viscosity of 1000 poise. In some embodiments, the glass compositions of the present invention have a T in the range of about 1030°C to about 1350°C. F In another embodiment, the glass composition of the present invention has a T in the range of about 1150°C to about 1300°C. F It has.

[0035] In some embodiments, the glass compositions of the present invention have a liquidus temperature in the range of about 1030° C. to about 1360° C. In other embodiments, the glass compositions of the present invention have a liquidus temperature in the range of about 1155° C. to about 1255° C.

[0036] In some embodiments, the difference between the forming temperature and the liquidus temperature of the glass compositions of the present invention is desirable for commercial fiberglass manufacturing operations. For example, for some embodiments of the glass compositions, 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 compositions of the present invention is at least 65° C.

[0037] As provided herein, glass fibers may be formed from some embodiments of the glass compositions of the present invention. Accordingly, embodiments of the present invention may include glass fibers formed from any of the glass compositions described herein. In some embodiments, the glass fibers may be fabricated. In some embodiments, the glass fibers of the present invention may be provided in other forms, including, for example, but not limited to, continuous strands, chopped strands (dry or wet), yarns, rovings, prepregs, etc. In short, various embodiments of the glass compositions (and any fibers formed therefrom) may be used in a variety of applications.

[0038] The glass fibers of the present invention can be prepared in a conventional manner known in the art by blending raw materials used to provide the particular oxides that form the fiber composition. Glass fibers according to various embodiments of the present invention can be formed using any process known in the art for forming glass fibers, and more desirably, any process known in the art for forming essentially continuous glass fibers. For example, although not limiting herein, glass fibers according to non-limiting embodiments of the present invention can be formed using direct melt or indirect melt fiber-forming methods. These methods are well known in the art, and further discussion thereof is not believed necessary in light of the present disclosure. See, for example, K. L. Loewenstein, The Manufacturing Technology of Continuous Glass Fibers, 3rd Edition, Elsevier, NY, 1993, pp. 47-48 and 117-234.

[0039] Some embodiments of the present invention relate to fiberglass strands. Some embodiments of the present invention relate to yarns comprising fiberglass strands. Some embodiments of the yarns of the present invention are particularly suitable for weaving applications. Additionally, some embodiments of the present invention relate to fiberglass strands. Some embodiments of the fiberglass fabric of the present invention are particularly suitable for use in reinforcement applications, especially where high modulus, high strength, and / or high elongation are important. Additionally, some embodiments of the present invention relate to composites incorporating fiberglass strands, fiberglass yarns, and fiberglass fabrics, such as fiber-reinforced polymer composites. Still further, some embodiments of the present invention relate to fiber-reinforced composites for applications including, but not limited to, wind energy, automotive, safety / security, aerospace, aviation, and high-pressure tanks. Some ... lower-cost applications such as chip-mounting substrates. A low coefficient of thermal expansion is particularly desirable for printed circuit boards.

[0040] Some embodiments of the present invention relate to fiberglass strands. In some embodiments, the fiberglass strands of the present invention comprise the following components: about 50 to about 55 weight percent SiO2; about 17 to about 26 weight percent B2O3; about 13 to about 19 weight percent Al2O3; about 0 to about 8.5 weight percent MgO; about 0 to about 7.5 weight percent ZnO; about 0 to about 6 weight percent CaO; about 0 to about 1.5 weight percent LiO; about 0 to about 1.5 weight percent F2; about 0 to about 1 weight percent NaO; about 0 to about 1 weight percent Fe2O3; about 0 to about 1 weight percent TiO, and A total of about 0 to about 8 weight percent of other components The glass fiber further comprises a glass composition comprising:

[0041] Several other glass compositions are disclosed herein as part of the present invention, and other embodiments of the present invention relate to fiber glass strands formed from such compositions.

[0042] In some embodiments, the glass fibers of the present invention may exhibit desirable mechanical and other properties. In some embodiments, the glass fibers of the present invention may exhibit one or more improved mechanical properties relative to glass fibers formed from L-glass. Examples of improved desirable properties exhibited by some embodiments of the glass fibers of the present invention include, but are not limited to, dielectric constant, coefficient of thermal expansion, melting and forming temperatures, transition temperature, fiber strength, Young's modulus, density, and boron emission.

[0043] In some embodiments, the glass fibers of the present invention have a desirable dielectric constant (D k ) values. In some embodiments, fibers formed from the glass compositions of the present invention may have a dielectric constant of less than 5 (at 1 GHz). In some embodiments, 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 compositions of the present invention may have a dielectric constant of less than 4.0 (at 1 GHz). Unless otherwise indicated herein, the dielectric constant values ​​discussed herein are determined using the procedures set forth in the Examples section below.

[0044] In some embodiments, the glass fibers of the present invention may have desirable coefficient of thermal expansion (CTE) values. In some embodiments, fibers formed from the glass compositions 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 compositions of the present invention may have a CTE of less than 3.2 ppm / °C. Unless otherwise indicated herein, the CTE values ​​discussed herein are determined using the procedures set forth in the Examples section below.

[0045] Fiber glass strands can include glass fibers of various diameters depending on the desired application. In some embodiments, the fiber glass strands of the present invention include at least one glass fiber having a diameter between about 5 and about 24 μm. In other embodiments, the at least one glass fiber has a diameter between about 5 and about 10 μm.

[0046] In some embodiments, the fiberglass strands of the present invention can be formed into yarns and rovings, which can be assembled, multi-end, or single-end. Rovings comprising the fiberglass strands of the present invention may include directly drawn single-end rovings having a variety of diameters and densities depending on the desired application. In some embodiments, rovings comprising the fiberglass strands of the present invention exhibit a density of up to about 113 yards / pounds.

[0047] Some embodiments of the present invention relate to yarns comprising at least one fiberglass strand as disclosed herein. In some embodiments, the yarns of the present invention comprise at least one fiberglass strand as disclosed herein, wherein the at least one fiberglass strand is at least partially coated with a sizing composition. In some embodiments, the sizing composition is compatible with thermosetting polymeric resins. In other embodiments, the sizing composition is a starch-oil sizing composition. sizing composition).

[0048] The yarns can have a variety of linear mass densities depending on the desired application. In some embodiments, the yarns of the present invention have a linear mass density of from about 5,000 yards / pound to about 10,000 yards / pound.

[0049] The yarns can have various twist levels and twist directions depending on the desired application. In some embodiments, the yarns of the present invention have a twist in the z-direction of about 0.5 to about 2 twists per inch. In other embodiments, the yarns of the present invention have a twist in the z-direction of about 0.7 twists per inch.

[0050] A yarn can be made from one or more strands twisted together and / or plied, depending on the desired application. A yarn can be made from one or more strands twisted together but not plied; such a yarn is known as a "single yarn." A yarn of the present invention can be made from one or more strands twisted together but not plied. In some embodiments, a yarn of the present invention comprises 1 to 4 strands twisted together. In other embodiments, a yarn of the present invention comprises one twisted strand.

[0051] Some embodiments of the present invention relate to a fabric comprising at least one fiberglass strand. In some embodiments, the fabric of the present invention may comprise at least one fiberglass strand comprising at least one of the glass compositions disclosed herein as part of the present invention. In some embodiments, the fabric of the present invention comprises a yarn as disclosed herein. In some embodiments, the fabric of the present invention may comprise at least one weft yarn comprising at least one fiberglass strand as disclosed herein. In some embodiments, the fabric of the present invention may comprise at least one warp yarn comprising at least one fiberglass strand as disclosed herein. In some embodiments, the fabric of the present invention comprises at least one weft yarn comprising at least one fiberglass strand as disclosed herein and at least one warp yarn comprising at least one fiberglass strand as disclosed herein.

[0052] In some embodiments of the invention that include a fabric, the fiberglass fabric is a fabric woven according to industrial fabric style No. 7781. In some embodiments, the fabric may be a plain weave, a twill weave, a crowfoot weave, a satin weave, a stitchbonded fabric (also known as a non-crimp fabric), or a "three-dimensional" woven fabric.

[0053] Embodiments of the present invention may further include articles of manufacture comprising glass composition embodiments and / or glass fiber embodiments of the present invention. In some embodiments, the articles of manufacture comprise yarn embodiments of the present invention, fabric embodiments of the present invention, and / or composite embodiments of the present invention.

[0054] Some embodiments of the articles of manufacture of the present invention relate to printed circuit boards. In some embodiments, the printed circuit boards comprise 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.

[0055] Some embodiments of the present invention relate to composites. In some embodiments, the composites of the present invention comprise a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, at least one of the plurality of glass fibers comprising any of the glass compositions disclosed herein as part of the present invention. In some embodiments, the composites of the present invention comprise a polymeric resin and at least one fiberglass strand as disclosed herein disposed in the polymeric resin. In some embodiments, the composites of the present invention comprise a polymeric resin and at least a portion of a roving comprising at least one fiberglass strand as disclosed herein disposed in the polymeric resin. In other embodiments, the composites of the present invention comprise a polymeric resin and at least one yarn as disclosed herein disposed in the polymeric resin. In yet other embodiments, the composites of the present invention comprise a polymeric resin and at least one fabric as disclosed herein disposed in the polymeric resin. In some embodiments, the composites of the present invention comprise at least one weft yarn comprising at least one fiberglass strand as disclosed herein and at least one warp yarn comprising at least one fiberglass strand as disclosed herein.

[0056] The composites of the present invention can include a variety of polymeric resins depending on the desired properties and application. In some composite embodiments of the present invention, the polymeric resin includes an epoxy resin. In other composite embodiments of the present invention, the polymeric resin can include polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, polydicyclopentadiene, polyphenylene sulfide, polyether ether ketone, cyanate ester, bismaleimide, and thermoset polyurethane resin. The present invention is illustrated through the following series of specific embodiments. However, those skilled in the art will recognize that many other embodiments are contemplated by the principles of the present invention. [Example]

[0057] Table 1 provides data on several fiberizable glass compositions according to various embodiments of the present invention and various properties of such compositions.

[0058] The glasses in these examples were made by melting a mixture of powdered commercial chemicals and reagent-grade chemicals (reagent-grade chemicals were used only for the rare earth oxides) in 10% Rh / Pt crucibles at temperatures between 1500°C and 1600°C (2732°F and 2822°F) for 4 hours. Each batch was approximately 1000 grams. After the 4-hour melting period, the molten glass was poured onto a steel plate for quenching. Volatile species, boron and fluoride, were adjusted in the batch for their emission losses. The compositions in the examples represent the as-batched compositions with the above adjustments. Commercially available raw material components were used in preparing the glasses. Batch calculations took into account special material retention factors to calculate the oxides in each glass. The retention factors are based on years of glass batch melting and measured oxide yields in the glasses. Therefore, the as-batched compositions illustrated in the examples are considered to be close to the measured compositions. can be done.

[0059] [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5] [Table 1-6]

[0060] Melting Properties The melt viscosity and liquidus temperature as a function of temperature were measured according to ASTM test methods C965, "Standard Practice for Measuring Viscosity of Glass Above the Softening Point," and C829, "Standard Practices for Measurement of Liquidus The softening of glass was determined using the "Temperature of Glass by the Gradient Furnace Method." The softening of glass was determined using ASTM C338-93 (2008) "Standard Test Method for Softening Point of Glass" was used to determine this.

[0061] Table 1 shows the measured liquidus temperatures (T L ), the reference molding temperature (T F ), and the reference melting temperature (T MThe difference between the forming temperature and the liquidus temperature (ΔT) is also shown.

[0062] Thermal Properties The coefficient of linear thermal expansion of glass was measured according to ASTM test method E228-11 "Standard Test Method The glass transition temperature, T, of glass was determined using the "For Linear Thermal Expansion of Solid Materials With a Push-Rod Dilatometer." g Decide It was determined.

[0063] Electrical characteristics The dielectric constant of each glass (D k ) and dielectric loss tangent (D f ) at a frequency of 1 GHz, according to ASTM test method D150 "Standard Test Methods for AC Loss Characteristics and The dielectric constant of solid electrical insulating materials was determined using the "Permittivity (Dielectric Constant) of Solid Electrical Insulating Materials" at a frequency of 1 GHz using an Agilent E4991A RF Impedance / Material Analyzer. k and D f For the measurement of the abrasive discs of each glass sample with a diameter of 40 mm and a thickness of 1 to 1.5 mm were used.

[0064] Mechanical properties The Young's modulus was also measured for certain glass compositions in Table 1 using the following technique. Approximately 50 grams of glass cullet having a composition corresponding to the appropriate example in Table 1 was remelted in a 90Pt / 10Rh crucible at a melting temperature defined as 100 poise for two hours. The crucible was then transferred to a vertical, electrically heated furnace. The furnace temperature was preset to a fiber drawing temperature close to or equal to a 1000 poise melt viscosity. The glass was allowed to equilibrate at that temperature for one hour before fiber drawing. The top of the fiber drawing furnace contained a cover with a center hole, on which a water-cooled copper coil was placed to control fiber cooling. A silica rod was then manually immersed in the melt through the cooling coil, and fibers were drawn and collected to lengths of approximately 1 to 1.5 meters. Fiber diameters ranged from 100 μm at one end to 1000 μm at the other end.

[0065] For fibers drawn from glass melts, the elastic modulus was determined using an ultrasonic acoustic pulse technique (Panatherm 5010 unit manufactured by Panametrics, Inc., Waltham, Massachusetts). The wave reflection time was obtained using a 200 kHz pulse with a duration of 20 microseconds. The length of the sample was measured and the respective stretching wave velocity (V E ) was calculated. Fiber density (ρ) was measured using a Micromeritics AccuPyc 1330 hydrometer. Approximately 20 measurements were taken for each composition, and the average Young's modulus (E) was calculated using the following formula: E=V E 2 ×ρ The elastic modulus tester used a waveguide with a diameter of 1 mm, so that the fiber diameter on the contact side with the waveguide was approximately the same as the diameter of the waveguide. In other words, the end of a fiber with a diameter of 1000 μm was connected to the contact side of the waveguide. Fibers with various diameters were tested for Young's modulus. The results show that fiber diameters from 100 to 1000 μm do not affect the elastic modulus of the fiber. The specific modulus value was calculated by dividing the Young's modulus value by the corresponding density.

[0066] It should be understood that this description illustrates aspects of the present invention that are relevant for a clear understanding of the present invention. Certain aspects of the present invention that are believed to be obvious to those skilled in the art and are therefore unlikely to facilitate a better understanding of the present invention have not been presented in order to simplify the description. While the present invention has been described in connection with certain specific embodiments, it is not intended that the present invention be limited to the specific embodiments disclosed, but rather that it is intended to cover modifications within the spirit and scope of the present invention.

[0067] According to a preferred embodiment of the present invention, for example, the following is provided: (Section 1) 1. A glass composition suitable for fiber formation, comprising: SiO2 in an amount of about 50 to about 55 weight percent; B2O3 in an amount of about 17 to about 26 weight percent; Al2O3 in an amount of about 13 to about 19 weight percent; MgO in an amount of about 0 to about 8.5 weight percent; ZnO in an amount of about 0 to about 7.5 weight percent; CaO in an amount of about 0 to about 6 weight percent; LiO in an amount of about 0 to about 1.5 weight percent; F2 in an amount of about 0 to about 1.5 weight percent; NaO in an amount of about 0 to about 1 weight percent; Fe2O3 in an amount of about 0 to about 1 weight percent; TiO2 in an amount of about 0 to about 1 weight percent, and A composition comprising one or more rare earth oxides (RE2O3) in a total amount of 0 to about 8 weight percent. (Section 2) Item 1, wherein the SiO2 content is about 51 to about 54 weight percent. (Section 3) 3. The composition according to any one of items 1 to 2, wherein the B2O3 content is about 17.5 to about 25 weight percent. (Section 4) 4. The composition according to any one of items 1 to 3, wherein the B2O3 content is about 19 to about 24 weight percent. (Section 5) 5. The composition according to any one of items 1 to 4, wherein the Al2O3 content is about 14 to about 18 weight percent. (Section 6) 6. The composition according to any one of items 1 to 5, wherein the content of MgO is from greater than 0 to about 7.5 weight percent. (Section 7) 6. The composition according to any one of items 1 to 5, wherein the MgO content is from about 2 to about 8.5 weight percent. (Section 8) 8. The composition according to any one of items 1 to 7, wherein the content of Al2O3 + MgO is from about 14 to about 26.5 weight percent. (Section 9) 9. The composition according to any one of items 1 to 8, wherein the content of Al2O3 + MgO is about 14 to about 26 weight percent. (Section 10) 10. The composition according to any one of items 1 to 9, wherein the ZnO content is from greater than 0 to about 5 weight percent. (Section 11) 11. The composition according to any one of items 1 to 10, wherein the content of Al2O3 + ZnO is about 14 to about 22 weight percent. (Section 12) 12. The composition according to any one of items 1 to 11, wherein the CaO content is from greater than 0 to about 5.5 weight percent. (Section 13) 13. The composition of any one of items 1 to 12, wherein the MgO+CaO content is about 9 weight percent or less. (Section 14) 13. The composition according to any one of items 1 to 12, wherein the content of MgO+CaO is from greater than 0 to about 9 weight percent. (Section 15) 15. The composition according to any one of items 1 to 14, wherein the Na2O content is from greater than 0 to about 0.5 weight percent. (Section 16) 16. The composition according to any one of items 1 to 15, wherein the Li2O content is about 0.8 weight percent or less. (Section 17) 16. The composition according to any one of items 1 to 15, wherein the content of Li2O is from greater than 0 to about 0.8 weight percent. (Section 18) 18. The composition of any one of items 1 to 17, wherein the total content of Na2O+Li2O is about 1.5 weight percent or less. (Section 19) 19. The composition according to any one of items 1 to 18, wherein the content of F2 is from more than 0 to about 1.5 weight percent. (Section 20) 20. The composition according to any one of items 1 to 19, wherein the content of Fe2O3 is from greater than 0 to about 0.5 weight percent. (Section 21) 21. The composition according to any one of items 1 to 20, wherein the TiO2 content is from greater than 0 to about 0.7 weight percent. (Section 22) 22. The composition according to any one of items 1 to 21, wherein the TiO2 content is from greater than 0 to about 0.6 weight percent. (Section 23) 23. The composition of any of paragraphs 1 to 22, wherein the glass composition comprises one or more rare earth oxides in an amount greater than about 0.01 weight percent. (Section 24) 23. The composition according to any one of paragraphs 1 to 22, wherein the content of one or more rare earth oxides is from greater than 0 to about 8 weight percent. (Section 25) 23. The composition of any one of paragraphs 1 to 22, wherein the content of one or more rare earth oxides is from greater than 0 to about 7.5 weight percent. (Section 26) 26. The composition according to any one of paragraphs 1 to 25, wherein the content of one or more rare earth oxides is from greater than 0 to about 7 weight percent. (Section 27) 27. The composition according to any one of paragraphs 1 to 26, wherein the content of RE2O3 + Al2O3 is about 13 to about 22 weight percent. (Section 28) 28. The composition according to any one of items 1 to 27, wherein the one or more rare earth oxides include at least one of La2O3, CeO2, Y2O3, and Sc2O3. (Section 29) 29. The composition according to any one of items 1 to 28, wherein the composition is substantially free of BaO. (Section 30) 30. The composition according to any one of items 1 to 29, wherein the composition is substantially free of SrO. (Section 31) 31. A fiber formed from the composition according to any one of items 1 to 30. (Section 32) 32. An article of manufacture comprising the fiber according to claim 31. (Section 33) 33. The article of manufacture according to claim 32, wherein the article of manufacture is a printed circuit board.

Claims

1. 1. A glass composition suitable for fiber formation, comprising: SiO in an amount of 50 to 55 weight percent ２ , B in an amount of 17 to 26 weight percent ２ O ３ , Al in an amount of 13 to 19 weight percent ２ O ３ , MgO in an amount of 4.15 to 8.5 weight percent; ZnO in an amount of 0 to 7.5 weight percent; CaO in an amount of 0 to 6 weight percent, Li in an amount of 0 to 1.5 weight percent ２ O. F2 in an amount of 0 to 1.5 weight percent, Na 2 O in an amount of 0 to 1 weight percent; Fe in an amount of greater than 0 to 1 weight percent ２ O ３ , and TiO in an amount of greater than 0 to 1 weight percent ２ , and one or more rare earth oxides (RE) in an amount of 0 to 8 weight percent in total; ２ O ３ ), wherein the composition does not contain P 2 O 5 ; composition.

2. SiO ２ The composition of claim 1, wherein the content of is from 51 to 54 weight percent.

3. B ２ O ３ 3. The composition according to claim 1, wherein the content of is from 17.5 to 25 weight percent.

4. B ２ O ３ 4. The composition of claim 1, wherein the content of is from 19 to 24 weight percent.

5. Al ２ O ３ 5. The composition of claim 1, wherein the content of is from 14 to 18 weight percent.

6. 6. The composition of claim 1, wherein the MgO content is from 4.15 to 7.5 weight percent.

7. 6. The composition of claim 1, wherein the MgO content is from 7 to 8.5 weight percent.

8. Al ２ O ３ 8. The composition according to claim 1, wherein the content of MgO is from 20 to 26.5 percent by weight.

9. Al ２ O ３ 8. The composition of claim 1, wherein the MgO content is from 20 to 26 percent by weight.

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

11. Al ２ O ３ 11. The composition of claim 1, wherein the ZnO content is from 14 to 22 percent by weight.

12. 12. The composition of any one of claims 1 to 11, wherein the CaO content is from greater than 0 to 5.5 weight percent.

13. 13. The composition of any of claims 1 to 6 and 8 to 12, wherein the MgO + CaO content is 9 weight percent or less.

14. Na in an amount of greater than 0 to 0.5 weight percent ２ 14. The composition of claim 1, further comprising O.

15. Li ２ 15. The composition of claim 1, wherein the O content is 0.8 weight percent or less.

16. Li ２ 15. The composition of claim 1, wherein the O content is from greater than 0 to 0.8 weight percent.

17. Na ２ O + Li ２ 17. The composition of any of claims 1 to 16, wherein the total O content is 1.5 weight percent or less. Claim 18: F in an amount of greater than 1.0 to 1.5 weight percent ２ 18. The composition of any of claims 1 to 17, further comprising:

19. Fe ２ O ３ 19. The composition of claim 1, wherein the content of is greater than 0.2 to 0.5 weight percent.

20. TiO ２ 20. The composition of claim 1, wherein the content of is from greater than 0 to 0.7 weight percent.

21. TiO ２ 21. The composition of claim 1, wherein the content of is from greater than 0 to 0.6 weight percent.

22. 22. The composition of any of claims 1 to 21, wherein the content of the one or more rare earth oxides is greater than 0.01 weight percent to 8 weight percent.

23. 22. The composition of any one of claims 1 to 21, wherein the content of the one or more rare earth oxides is from greater than 0 to 8 weight percent.

24. 22. The composition of any one of claims 1 to 21, wherein the content of the one or more rare earth oxides is from greater than 0 to 7.5 weight percent.

25. 25. The composition of any one of claims 1 to 24, wherein the content of the one or more rare earth oxides is from greater than 0 to 7 weight percent.

26. RE ２ O ３ +Al ２ O ３ 26. The composition of claim 1, wherein the content of is from 13 to 22 weight percent.

27. The one or more rare earth oxides are La ２ O ３ , CeO ２ , Y ２ O ３ , and Sc ２ O ３ 27. The composition of claim 1, comprising at least one of:

28. 28. The composition of any of claims 1 to 27, wherein the composition is substantially free of BaO.

29. 29. A glass fiber formed from the composition of any one of claims 1 to 28.

30. 30. An article of manufacture comprising the glass fiber of claim 29.

31. 31. The article of manufacture of claim 30, wherein the article of manufacture is a printed circuit board.

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