JP2013542904A - Low density, high strength fiber glass for reinforcement applications - Google Patents

Abstract

The present invention relates to fiber glass strands, yarns, fabrics, composites, prepregs, laminates, fiber-metal laminates and other articles incorporating glass fibers formed of a glass composition. Glass fibers, in some embodiments, are incorporated into composites that can be used for reinforcing applications. The glass fibers formed in some embodiments of the glass composition may have certain desirable properties, such as, for example, desirable electrical properties (eg, low D _k ) or desirable mechanical properties. Properties (eg, specific strength) may be mentioned.

Description

This application claims priority to US Provisional Patent Application No. 61 / 382,738, filed Sep. 14, 2010, the entire disclosure of which is incorporated herein by reference. Is incorporated by reference in the This application is a continuation-in-part of US patent application Ser. No. 13 / 229,012, filed Sep. 9, 2011, and claims priority thereto. The U.S. patent application Ser. No. 13 / 229,012 is a continuation-in-part of U.S. patent application Ser. No. 12 / 940,764, filed Nov. 5, 2010, which is incorporated herein by reference. No. 764 is a U.S. patent application Ser. No. 11 / 610,761 filed Dec. 14, 2006, which is currently one of U.S. Pat. No. 7,829,490 issued Nov. 9, 2010. The contents of which are incorporated herein by reference in their entirety.

FIELD OF THE INVENTION The present invention relates to low density, high strength glass fibers and yarns, fabrics, and composites comprising low density, high strength glass fibers adapted for use in reinforcement applications.

BACKGROUND Glass fibers have been used for many years to strengthen various polymeric resins. One example of a commonly used glass composition for use in toughening applications is the composition of the "E-glass" and "D-glass" groups. Another glass composition commonly used is that commercially available from AGY (Aiken, South Carolina) under the trade name "S-2 Glass".

  Glass fibers have been arranged to form fabrics for many years. In conventional glass fiber weaving operations, glass cloth is a woven fabric by interweaving "weft yarn" (also referred to as "fill yarn") with a plurality of warp yarns. Generally, this is done by arranging the warp yarns in a generally parallel planar array on the loom and then interweaving the weft yarns with the warp yarns and the weft yarns over and under the warp yarns in a predetermined repeating pattern . The pattern used depends on the desired cloth style.

  Warp yarns are typically formed by tapering a plurality of molten glass streams from a bushing or spinning machine. The coating (or primary sizing composition) is then applied to the individual glass fibers and the fibers are gathered together to form a strand. Subsequently, the strands are processed into yarns by transferring the strands to a bobbin by means of a twist frame. During this transfer, the strands may be twisted to help hold the bundle of fibers together. The twisted strand is then wound on a bobbin, which is used in the weaving process.

  The placement of the warp threads on the weaving machine is typically performed by a warp beam. The warp beam comprises a specified number of warp yarns (also referred to as "ends") wound in a configuration essentially parallel to the cylindrical core (also referred to as "warp sheet"). Warp beam preparation typically includes multiple yarn packages (each package includes a portion of the number of ends required for the warp beam), a single package or warp beam It is necessary to adjust to For example, but not limiting herein, a 50 inch (127 cm) wide 7781 style fabric (which uses a DE 75 input yarn) typically requires 2868 ends. Ru. However, conventional equipment for forming a warp beam does not allow all such ends to be transferred from the bobbin into a single beam in one operation. Thus, a plurality of beams (typically referred to as "section beams") composed of the required number of end portions are produced and then combined to form a warp beam. Similar to the warp beam, the section beam is typically one that includes a cylindrical core with a plurality of essentially parallel warp yarns wrapped around it. One skilled in the art will recognize that the section beam may be any number of warp threads needed to form the final warp beam, but generally the number of ends included in the section beam Is limited by the capacity of the warping reel. For the 7781 style fabric, combining the 717 end four section beams (each typically supplied with DE 75) provides the 2868 ends required for the warp sheet (see above As stated).

  As discussed above, the primary sizing composition is applied to the glass fibers, typically immediately after formation. Traditionally, the filaments forming the continuous glass fiber strands used in textile weaving are treated with aqueous starch oil sizing, which typically includes partially or fully dextrinated starch or amylose, water Vegetable oils, cationic wetting agents, emulsifiers and water are included and are well known to those skilled in the art. For additional information on such sizing compositions, see Non-Patent Document 1 (which is specifically incorporated herein by reference). Such sizing compositions are generally sufficiently robust to provide protection to the fibers during fiber formation and during the warp beam manufacturing process, but usually during high speed weaving of glass fibers, especially warp fibers. Can not be protected from wear and tear. As a result, in the textile weaving industry, the warp is threaded through the slasher, which applies the slashing size to the warp during warp beam manufacturing, in the manner discussed in more detail later, and provides the additional protection needed. It is customary to obtain. More specifically, the slashing operation provides a vehicle for adding additional film forming chemistry to the fibers forming the warp sheet. Typically, thrashing sizing agents include either fully hydrolyzed or partially hydrolyzed hydrolyzed polyvinyl alcohol (PVA) materials, with a solids range of 6-8%, 15-20 It is a mixture having a viscosity of centipoise (CP). The thrashing size is typically applied by immersing the warp sheet in a bath containing the thrashing size via a series of dip rollers and then passing it through a squeeze roll system, which is And typically apply a squeeze pressure of 15 to 20 pounds per square inch to the coated yarn in addition to the dead load of the squeeze roller (the squeeze pressure may vary depending on the diameter of the yarn) and excess thrashing sizing It is something to remove. The slashing size may be applied at elevated temperatures (e.g., in the range of 130-150 <0> F (54-66 <0> C)) or room temperature, depending on the PVA manufacturer's recommendations. After squeezing out excess sizing agent from the yarn sheet, passing the slashed sized sheet in any convenient manner known in the art, including, but not limited to, passing the sheet over a heated roller and / or in a hot air drying oven Let dry). In slashers that incorporate a heated roller or can, the surface temperature of the can is typically in the range of 240-280 ° F. (116-138 ° C.). The actual temperature profile of the drying can depends, in part, on the can configuration, the number of cans and the speed of the yarn. In a hot air drying oven, the temperature of the air in the oven is typically in the range of 275-300 ° F (135-149 ° C). After drying, the warp sheet is passed through a series of split rods to separate the warp sheet, and the hook lead assembly and comb to align the warp sheet and ensure that there are no ends adhering to one another. The yarn sheet is then wound around the warp beam.

  Both primary starch oil coatings and slashing sizes are not compatible with the polymeric resin matrix material used to impregnate the fabric in which the coated yarn is incorporated. As a result, such coatings must be removed from the fabric, for example by heat cleaning and / or scrubbing, before incorporating the fabric woven with such yarns into the matrix material. For example, a typical one-step heat cleaning process involves heating the fabric at 600-800 ° F. (316-427 ° C.) for 70-80 hours to remove the primary sizing composition of the starch oil and the slashing size It can be In an alternative two-step operation, the fabric is deployed in a furnace where it is exposed to flames to burn off a portion of the sizing agent and then heated at 600-800 ° F. (316-427 ° C.) for 50-60 hours Do. The first step of this two-step operation, sometimes referred to as caramelization, is typically used to heat heavy fabrics woven clean fabrics (i.e., 7628 style fabrics).

  It has been found that applying a primary sizing composition that is compatible with the resin matrix material to the individual glass fibers during formation eliminates the need for the application of additional slashing sizes to protect the glass fibers. As a result, the need for additional fiber protection by the application of thrashing size is eliminated. However, passing such a warp with a resin compatible coating to a warp beam of multiple section beams, for example, passing the warp through a slasher without addition of a slashing size, heating and drying (or in some cases "dry slashing") It has been observed that when simply winding to form a warp beam, the number of warp beam defects (such as end breakage due to end winding and twisting) becomes excessive. The winding of the end is such that adjacent glass strands are wound together and twisted together on top of one another, which may result in breakage of the end during weaving, which is also an issue of fabric quality ( Particularly troublesome because it relates to end-outs, fuzzy ends, frayed ends and unwanted yarn splices.

  Nevertheless, as the primary method of forming the warp beam in the textile weaving industry is through the use of thrashers, and because most weaving operations already have this type of equipment, thrashers without the use of thrashing sizing agents It is important to be able to make a warp beam with a warp having a resin compatible coating thereon.

K. Loewenstein, The Manufacturing Technology of Continuous Glass Fibers, (Third Edition. 1993), pages 237-244.

SUMMARY Various embodiments of the present invention generally comprise low density, high strength glass fibers, and low density, high strength glass fibers adapted for use in fiber glass strands, yarns, fabrics, and reinforcement applications. Related to composites.

  Some embodiments of the present invention relate to fiber glass strands. Although some fiberizable glass compositions are disclosed herein as part of the present invention, various embodiments of the present invention include glass fibers, fiber glass strands, yarns, and such compositions. It is to be understood that the formed glass fiber may encompass other products incorporating it.

In one aspect, the fiber glass strand of the present invention comprises the following components:
60-68 weight percent SiO2;
B2O3 7 to 12 weight percent;
Al2O3 9-15 weight percent;
MgO 8 to 15 weight percent;
CaO 0-4 weight percent;
Li2O 0-2% by weight;
Na2O 0-1 weight percent;
K2O 0-1 weight percent;
0 to 1 weight percent of Fe2O3;
F2 0-1 weight percent;
0 to 2 weight percent TiO 2; and 0 to 5 weight percent in total of the other constituents;
A plurality of glass fibers including a glass composition having a (Li2O + Na2O + K2O) content of less than 2 weight percent and a MgO content of at least twice the content of CaO on a weight percent basis are included.

In another aspect, the fiber glass strand of the present invention comprises the following components:
SiO 2 53.5-77 weight percent;
B2O3 4.5 to 14.5 weight percent;
Al2O3 4.5 to 18.5% by weight;
MgO 4 to 12.5 weight percent;
CaO 0-0.5% by weight;
Li2O 0-4 weight percent;
0 to 2 weight percent Na2O;
K2O 0-1 weight percent;
0 to 1 weight percent of Fe2O3;
F2 0-2 weight percent;
And a plurality of glass fibers including a glass composition containing 0 to 2 weight percent of TiO2; and 0 to 5 weight percent in total.

  In some embodiments, the plurality of glass fibers can have a diameter of about 5 microns to about 13 microns. In some embodiments, the fiber glass strands are at least partially coated with a sizing composition.

  Some embodiments of the present invention relate to yarns formed of at least one fiber glass strand formed of a glass composition as described herein. Some embodiments of the present invention relate to fabrics incorporating at least one fiber glass strand formed of a glass composition as described herein. In some embodiments, weft yarns used in the fabric may include the at least one fiber glass strand. The warp, in some embodiments, may be comprised of the at least one fiber glass strand. In some embodiments, fiber glass strands may be used for both weft and warp yarns used to form a fabric according to the present invention. In some embodiments, the fabrics of the present invention may include plain, twill, crowfoot, satin, stitch bonded, or 3D fabrics.

  Some embodiments of the present invention relate to composites comprising a polymeric resin and glass fibers formed of one of the various glass compositions described herein. The glass fibers may be from fiber glass strands according to some embodiments of the present invention. In some embodiments, glass fibers can be incorporated into fabrics, such as textiles. For example, glass fibers may be present in the weft and / or warp yarns woven to form a fabric. In embodiments where the composite comprises a fabric, the fabric may comprise plain weave, twill weave, twill weave, satin weave, stitch bonded weave, or 3D weave. Glass fibers may be incorporated into the composite in other forms, as well as as discussed in more detail below.

  With respect to polymeric resins, the composites of the present invention may be comprised of one or more different polymeric resins. In some embodiments, the polymeric resin is polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, polydicyclopentadiene, polyphenylene sulfide, polyetheretherketone, It contains at least one of cyanate ester, bis-maleimide, and thermosetting polyurethane resin. The polymeric resin may, in some embodiments, comprise an epoxy resin.

  The composites of the present invention may be in various forms and may be used in various applications. For example, without limitation, composites may include aerospace composites, aerospace composites, radomes, laminates, fiber-metal laminates, and the like. As an example, a fiber-metal laminate may be provided with various layers of glass reinforced composites and metal sheets. In one embodiment, a fiber-metal laminate is a prepreg comprising a fabric comprising a polymeric resin and glass fibers formed of one of a plurality of various glass compositions described herein. A first metal sheet adhesively fixed to one surface of the prepreg (pregreg), and a second metal sheet adhesively fixed to the second surface of the prepreg (prereg); A prepreg may be provided to be disposed between the two metal sheets. In another embodiment, a second prepreg is disposed between the second metal sheet and the third metal sheet. In one embodiment, the metal sheet may contain aluminum, and the polymer resin may contain epoxy.

  These and other embodiments are discussed in further detail in the detailed description below.

DETAILED DESCRIPTION For the purpose of the present description, unless otherwise stated, all numbers indicating the amounts of components, reaction conditions etc used herein are in all cases modified by the term "about" Please understand. Thus, unless stated otherwise, the numerical parameters set forth herein below are approximations that may differ depending on the desired properties sought to be obtained in the present invention. At the very least, in order to ensure that the application of the doctrine of equivalents to the scope of the claims is not restricted, each numerical parameter should at least be applied to the usual rounding method in view of the fact that the figures are significant figures. Please interpret that it is due to.

  Notwithstanding that the numerical ranges and parameters set forth in the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains errors necessarily resulting from the standard deviation found in applicable test measurements.

  Furthermore, as used herein, the singular forms "a", "an" and "the" include plural referents unless the invention is explicitly and explicitly limited to a single referent. It should be noted that

  Reinforcing some materials, such as polymeric resins, with glass fibers can result in composites with improved impact resistance and / or other desirable mechanical properties. For some glass fiber reinforced applications, it may be desirable to use stronger, lighter, more cost effective glass fibers. The combination of high strength and / or high modulus and low density may be particularly important for some aerospace and transportation applications where weight is often an important design parameter. As compared to glass fibers containing E-glass, the glass fibers useful in some embodiments of the present invention exhibit high strain to failure, high strength and / or low fiber density. Obtained and having them together may result in a glass fiber reinforced composite having a lower fiber density for a given fiber volume fraction or for a given composite performance. In some embodiments, the glass fibers may be first arranged in the fabric. In some embodiments, the glass fibers of the present invention may be supplied in other forms, such as, but not limited to, chopped strands (dry or wet), yarns, woving, prepregs, and the like. In short, the various embodiments of the glass composition (and any fibers formed of the composition) can be used for various applications.

While providing improved electrical performance (ie, low dielectric constant (D _k ) and / or low dissipation factor (D _f )) as compared to standard E-glass, previous low D _k glass proposals A fiberizable glass composition has been developed which provides a more conductive temperature-viscosity relationship to commercially available commercial fiber formers. Such glass compositions are described in U.S. Patent No. 7,829,490 and U.S. Patent Application No. 13 / 229,012 (filed September 9, 2011), both of which are incorporated herein by reference in their entirety. (Incorporated). Another optional aspect of the glass composition described in U.S. Patent No. 7,829,490 and U.S. Patent Application No. 13 / 229,012 is that the raw material batch cost is relatively low, at least in part of the composition Can be made commercially.

  Some embodiments of the present invention relate to fiber glass strands. Some embodiments of the present invention relate to yarns comprising fiber glass strands. Some embodiments of yarns of the invention are particularly suitable for weaving applications. Also, some embodiments of the present invention relate to fiberglass fabrics. Some embodiments of the glass fiber cloth of the present invention are particularly suitable for use in reinforcement applications, in particular low density, high modulus, high strength and / or high break strain is important where high strain is important. Furthermore, some embodiments of the present invention relate to fiber glass strands, fiber glass yarns and composites (such as fiber reinforced polymer composites) incorporating glass fiber cloth. Some of the composites of the present invention may be used in reinforcement applications, particularly in low density, high modulus, high strength and / or high fracture strain critical applications (aerospace, aerospace, wind energy, radomes, etc., and others) Particularly suitable for use in the Some composites of the invention may be particularly suitable for use in any application where high impact resistance and low density are desired. Exemplary applications include aerospace applications, aerospace applications, automotive applications, marine transport applications, wind energy applications, bridge construction, and radomes, among others. Some embodiments of the present invention relate to aerospace composites. Another embodiment of the present application relates to a composite for the aircraft industry. Yet another embodiment of the present invention relates to a composite suitable for use in wind energy applications. Some embodiments of the present invention relate to a prepreg. Another embodiment of the invention relates to a laminate. Some embodiments of the present invention relate to fiber-metal laminates (eg, fiber glass prepregs disposed between metal sheets) that may be used, for example, in aircraft secondary structures. Another embodiment of the invention relates to a radome.

Some embodiments of the present invention relate to fiber glass strands. In some embodiments, the fiber glass strand of the present invention comprises the following components:
SiO ₂ 60-68 weight percent;
B ₂ O ₃ 7 to 12 weight percent;
Al ₂ O ₃ 9-15% by weight;
MgO 8 to 15 weight percent;
CaO 0-4 weight percent;
Li ₂ O 0-2% by weight;
Na ₂ O 0 to 1% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
F ₂ 0 to 1 weight percent;
In which a plurality of glass fibers contains glass composition containing 0 to 5 weight percent, and other constituents total included; TiO 2 _{0 to 2} percent by weight. In some embodiments, the (Li ₂ O + Na ₂ O + K ₂ O) content may be less than 2 weight percent, and the MgO content may be at least twice the content of CaO on a weight percent basis.

In some embodiments, the fiber glass strand of the present invention comprises the following components:
SiO ₂ 53.5 to 77 weight percent;
B ₂ O ₃ 4.5 to 14.5 weight percent;
Al ₂ O ₃ 4.5 to 18.5% by weight;
MgO 4 to 12.5 weight percent;
CaO 0-0.5% by weight;
Li ₂ O 0-4% by weight;
Na ₂ O 0 to 2% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
F ₂ 0-2% by weight;
In which a plurality of glass fibers contains glass composition containing 0 to 5 weight percent, and other constituents total included; TiO 2 _{0 to 2} percent by weight.

In some embodiments, the fiber glass strands of the present invention are:
SiO ₂ 60-68 weight percent;
B ₂ O ₃ 7 to 12 weight percent;
Al ₂ O ₃ 9-15% by weight;
MgO 8 to 15 weight percent;
CaO 0-4 weight percent;
Li ₂ O> 0~2 wt%;
Na ₂ O 0 to 1% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
F ₂ 0 to 1 weight percent;
0 to 2 weight percent of TiO ₂ ; and 0 to 5 weight percent in total of other components,
A glass composition is included which has a Li ₂ O content greater than either Na ₂ O content or K ₂ O content.

  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 with such compositions.

  In some embodiments, fiber glass strands formed with the glass compositions described herein have desirable properties (such as improved fiber strength, Young's modulus, breaking strain, and / or linear thermal expansion coefficient). As shown, it may also exhibit relatively low density. Also, fiber glass strands, including other glass compositions disclosed herein, may also exhibit one or more such desirable properties.

  Fiber glass strands may include glass fibers of various diameters depending on the desired application. In some embodiments, the fiber glass strands of the present invention comprise at least one glass fiber having a diameter of about 5 to about 13 μm. In another embodiment, the at least one glass fiber has a diameter of about 5 to about 7 μm.

  In some embodiments, the fiber glass strands of the present invention may be formed into rovings. Roving may include focusing, multi-end or single-ended direct draw roving. Rovings containing fiber glass strands of the present invention may include direct drawn single ended rovings having various diameters and densities depending on the desired application. In some embodiments, rovings comprising the fiber glass strands of the present invention exhibit a density of up to about 112 yd / lb.

Some embodiments of the present invention relate to a yarn comprising at least one fiber glass strand as disclosed herein. In some embodiments, the yarn of the present invention comprises 60 to 68 weight percent SiO ₂ , 7 to 12 weight percent B ₂ O ₃ , 9 to 15 weight percent Al ₂ O ₃ , 8 to 15 weight percent MgO, 0 to 4 weight percent CaO, 0 to 2 weight percent Li ₂ O, 0 to 1 weight percent Na ₂ O, 0 to 1 weight percent K ₂ O, 0 to 1 weight percent F ₂ O ₃ , 0-1 wt% of F _2, composed of at least one fiberglass strand that contains glass composition comprising other constituents of 0-5 weight percent TiO _2, and the sum of 0-2% by weight It is done. The yarns, in some embodiments, from 53.5 to 77 percent by weight of _SiO 2, 4.5-14.5% by weight of _B 2 _O 3, from 4.5 to 18.5% by weight of _Al 2 O ₃ , 4 to 12.5 weight percent of MgO, 0 to 0.55 weight percent of CaO, 0 to 4 weight percent of Li ₂ O, 0 to 2 weight percent of Na ₂ O, 0 to 1 weight percent of K ₂ A glass composition comprising O, 0 to 1 weight percent F ₂ O ₃ , 0 to 2 weight percent F ₂ , 0 to 2 weight percent TiO ₂ , and a total of 0 to 5 weight percent other constituents It consists of at least one fiber glass strand included. In another embodiment, the yarn of the present invention comprised at least one fiber glass strand comprising one of the other glass compositions disclosed herein as part of the present invention. It can be

  In some embodiments, the yarn of the present invention is comprised of at least one fiber glass strand disclosed herein, wherein the at least one fiber glass strand is at least partially coated with a sizing composition. It is done. In some embodiments, the sizing composition is compatible with the thermosetting polymer resin. In other embodiments, the sizing composition may comprise a starch oil sizing composition.

  The yarns can be of various linear mass densities depending on the desired application. In some embodiments, the yarns of the present invention have a linear mass density of 5,000 yd / lb to about 10,000 yd / lb.

  The yarns can be of various twist levels and orientations 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 turns per inch. In another embodiment, the yarn of the present invention has a twist in the z-direction of about 0.7 revolutions per inch.

  The yarn may be made of one or more strands twisted and / or crimped together depending on the desired application. The yarns may be made of one or more strands that are twisted together but not retwisted; such yarns are known as "singles". The yarns of the present invention may be made of one or more strands that are twisted together but not retwisted. In some embodiments, the yarn of the present invention is comprised of 1 to 4 strands twisted together. In another embodiment, the yarn of the present invention comprises a single stranded strand.

  In some embodiments of yarns that include the glass composition of the present invention, improved heat load retention can be exhibited after heat cleaning and finishing as compared to yarns made with conventional glass compositions.

Some embodiments of the present invention relate to a fabric comprising at least one fiber glass strand. In some embodiments, the fabric comprises 60 to 68 weight percent SiO ₂ , 7 to 12 weight percent B ₂ O ₃ , 9 to 15 weight percent Al ₂ O ₃ , 8 to 15 weight percent MgO, 0 to 4 weight percent CaO, 0 to 2 weight percent Li ₂ O, 0 to 1 weight percent Na ₂ O, 0 to 1 weight percent K ₂ O, 0 to 1 weight percent F ₂ O ₃ , 0 At least one fiber glass strand comprised of a glass composition comprising ̃1 weight percent F ₂ , 0 ̃2 weight percent TiO ₂ , and a total of 0 ̃5 weight percent other constituents It is a thing. The fabric, in some embodiments, from 53.5 to 77 percent by weight of _SiO 2, 4.5 to 14.5% by weight of _B 2 _O 3, _4.5~18.5 wt% of _Al 2 O ₃ , 4 to 12.5 weight percent of MgO, 0 to 0.55 weight percent of CaO, 0 to 4 weight percent of Li ₂ O, 0 to 2 weight percent of Na ₂ O, 0 to 1 weight percent of K ₂ A glass composition comprising O, 0 to 1 weight percent F ₂ O ₃ , 0 to 2 weight percent F ₂ , 0 to 2 weight percent TiO ₂ , and a total of 0 to 5 weight percent other constituents Included is at least one fiber glass strand included. In another embodiment, a fabric of the present invention comprises at least one fiber glass strand comprising one of the other glass compositions disclosed herein as part of the present invention. possible. In some embodiments, the fabrics of the present invention include the yarns disclosed herein. The fabric of the present invention may, in some embodiments, include at least one weft comprising at least one fiber glass strand as disclosed herein. The fabric of the present invention may, in some embodiments, include at least one warp comprising at least one fiber glass strand as disclosed herein. In some embodiments, the inventive fabric comprises at least one weft yarn comprising at least one fiber glass strand as disclosed herein and at least one fiber glass strand as disclosed herein And at least one warp yarn is included.

  In some embodiments of the invention that make up a fabric, the glass fiber fabric is a fabric according to industrial fabric style number 7781. In other embodiments, the fabric comprises plain weave, twill weave, twill weave, satin weave, stitch bonded weave (also known as non-crimp weave), or "three-dimensional" weave.

Some embodiments of the present invention relate to composites. In some embodiments, the composite of the present invention comprises a polymer resin and a plurality of glass fibers disposed in the polymer resin, wherein at least one of the plurality of glass fibers is included. One kind of the following components: 60 to 68 weight percent SiO ₂ , 7 to 12 weight percent B ₂ O ₃ , 9 to 15 weight percent Al ₂ O ₃ , 8 to 15 weight percent MgO, 0 to 4 weight percent CaO, 0 to 2 wt% of _Li 2 O, 0 to 1% by weight of _Na 2 O, 0 to 1% by weight of _K 2 O, 0 to 1% by weight of _F 2 _O 3, 0~1 wt A glass composition comprising percent F ₂ , 0-2 weight percent TiO ₂ , and a total of 0-5 weight percent other constituents is included. The composite material of the present invention, in some embodiments, comprises a polymer resin and a plurality of glass fibers disposed in the polymer resin, and at least one of the plurality of glass fibers. One of the following components: 53.5 to 77 weight percent SiO ₂ , 4.5 to 14.5 weight percent B ₂ O ₃ , 4.5 to 18.5 weight percent Al ₂ O ₃ , 4 12.5 wt% of MgO, 0-10.5 wt% of CaO, 0-4 wt% _Li 2 O, 0 to 2 wt% of _Na 2 O, 0-1% by weight _K 2 O, 0 Glass compositions comprising 1 wt.% F ₂ O ₃ , 0 2 wt.% F ₂ , 0 2 wt.% TiO ₂ , and a total of 0 5 wt.% Other constituents It is a thing. In another embodiment, the composite of the present invention comprises a polymer resin and a plurality of glass fibers disposed in the polymer resin, wherein at least one of the plurality of glass fibers is included. The type may be formed of one of the other glass compositions disclosed herein as part of the present invention. In some embodiments, the composite of the present invention comprises a polymeric resin and at least one fiber glass strand disclosed herein disposed in the polymeric resin. In some embodiments, the composite of the present invention comprises at least a portion of a roving comprising a polymer resin and at least one fiber glass strand disclosed herein disposed in the polymer resin. Have. In another embodiment, the composite of the present invention comprises a polymeric resin and at least one yarn disclosed herein disposed in the polymeric resin. In yet another embodiment, the composite of the present invention comprises a polymeric resin and at least one fabric disclosed herein disposed in the polymeric resin. In some embodiments, the inventive composite comprises at least one weft comprising at least one fiber glass strand as disclosed herein and at least one fiber glass as disclosed herein And at least one warp comprising strands.

  The composites of the present invention may be provided with various polymeric resins depending on the desired properties and applications. In some embodiments of the present invention that constitute composites, the polymeric resin comprises an epoxy resin. In another embodiment of the invention comprising the composite, the polymeric resin is polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, polydicyclopentadiene, polyphenylene It may include sulfides, polyetheretherketones, cyanates, bis-maleimides, and thermosetting polyurethane resins.

  Some embodiments of the present invention relate to aerospace composites. In some embodiments, the aerospace composites of the present invention have desirable properties (such as high modulus, high failure-to-strain, and / or low density) for use in aerospace applications. It is shown. The low density of some aerospace composites of the present invention may make such composites particularly desirable for use in aerospace applications where weight reduction is important. Also, the aerospace composites of the present invention may be less expensive than other composites used in aerospace applications.

In some embodiments, the aerospace composite of the present invention comprises a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, the plurality of glass fibers comprising At least one of the following components: 60 to 68 weight percent SiO ₂ , 7 to 12 weight percent B ₂ O ₃ , 9 to 15 weight percent Al ₂ O ₃ , 8 to 15 weight percent MgO, 0 to 4 weight percent CaO, 0 to 2 weight percent Li ₂ O, 0 to 1 weight percent Na ₂ O, 0 to 1 weight percent K ₂ O, 0 to 1 weight percent F ₂ O ₃ , 0 1 weight percent _F 2, those containing the glass composition comprising other constituents of 0-5 weight percent TiO _2, and the sum of 0-2% by weight. The aerospace composite of the present invention, in some embodiments, comprises a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein the plurality of glass fibers At least one of the following components: 53.5 to 77 weight percent SiO ₂ , 4.5 to 14.5 weight percent B ₂ O ₃ , 4.5 to 18.5 weight percent Al ₂ O ₃ , 4 to 12.5 weight percent of MgO, 0 to 0.55 weight percent of CaO, 0 to 4 weight percent of Li ₂ O, 0 to 2 weight percent of Na ₂ O, 0 to 1 weight percent of K ₂ A glass composition comprising O, 0 to 1 weight percent F ₂ O ₃ , 0 to 2 weight percent F ₂ , 0 to 2 weight percent TiO ₂ , and a total of 0 to 5 weight percent other constituents Also included It is. In another embodiment, the aerospace composite material of the present invention comprises a polymer resin and a plurality of glass fibers disposed in the polymer resin, and among the plurality of glass fibers, Or at least one of the other glass compositions may be formed of one of the other glass compositions disclosed herein as part of the present invention.

  In some embodiments, the aerospace composite of the present invention comprises a polymeric resin and at least one fiber glass strand disclosed herein disposed in the polymeric resin. In some embodiments, the aerospace composite of the present invention is a roving comprising a polymeric resin and at least one fiber glass strand disclosed herein disposed in the polymeric resin. It has at least a part. In another embodiment, the aerospace composite of the present invention comprises a polymeric resin and at least one yarn disclosed herein disposed in the polymeric resin. In yet another embodiment, the aerospace composite of the present invention comprises a polymeric resin and at least one fabric disclosed herein disposed in the polymeric resin. In some embodiments, the aerospace composite of the present invention comprises at least one weft comprising at least one fiber glass strand as disclosed herein and at least one weft disclosed herein. And at least one warp comprising a fiber glass strand of

  The aerospace composites of the present invention may be provided with various polymeric resins depending on the desired properties and applications. In some embodiments of the invention comprising an aerospace composite, the polymeric resin comprises an epoxy resin. In another embodiment of the present invention, which constitutes an aerospace composite, the polymeric resin is polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, polydicyclo It may include pentadiene, polyphenylene sulfide, polyetheretherketone, cyanate ester, bis-maleimide, and thermosetting polyurethane resin. Examples of parts in which the aerospace composites of the present invention may be used include, but are not limited to, floorboards, in-flight overhead storage bins, kitchens, seatbacks, and possibly other interior compartments susceptible to impact, and External components such as helicopter blades may be mentioned.

  Some embodiments of the present invention relate to composites for the aircraft industry. In some embodiments, the composites for aircraft industry of the present invention exhibit desirable properties (such as high modulus, high strain at break, and / or low density) for use in aircraft industry applications. The high fracture strain of some aircraft industry composites of the present invention may make such composites particularly desirable for use in aircraft industry applications where high impact resistance is important, such as aircraft interior applications. . In some embodiments, the composite for aircraft industry of the present invention may exhibit increased impact performance as compared to a composite formed of E-glass cloth. Also, the composites for the aircraft industry of the present invention may be less expensive than other composites used in aircraft industry applications. The composite for the aircraft industry of the present invention may be suitable for use in the interior of an aircraft, such as, for example, luggage storage, seating and floors.

In some embodiments, the composite for the aircraft industry of the present invention comprises a polymer resin and a plurality of glass fibers disposed in the polymer resin, wherein the plurality of glass fibers is At least one of the following components: 60 to 68 weight percent SiO ₂ , 7 to 12 weight percent B ₂ O ₃ , 9 to 15 weight percent Al ₂ O ₃ , 8 to 15 weight percent MgO, 0 to 4 weight percent CaO, 0 to 2 weight percent Li ₂ O, 0 to 1 weight percent Na ₂ O, 0 to 1 weight percent K ₂ O, 0 to 1 weight percent F ₂ O ₃ , 0 1 weight percent _F 2, those containing the glass composition comprising other constituents of 0-5 weight percent TiO _2, and the sum of 0-2% by weight. The composite for aircraft industry of the present invention, in some embodiments, comprises a polymer resin and a plurality of glass fibers disposed in the polymer resin, wherein the plurality of glass fibers At least one of the following components: 53.5 to 77 weight percent SiO ₂ , 4.5 to 14.5 weight percent B ₂ O ₃ , 4.5 to 18.5 weight percent Al ₂ O ₃ , 4 to 12.5 weight percent of MgO, 0 to 0.55 weight percent of CaO, 0 to 4 weight percent of Li ₂ O, 0 to 2 weight percent of Na ₂ O, 0 to 1 weight percent of K ₂ A glass composition comprising O, 0 to 1 weight percent F ₂ O ₃ , 0 to 2 weight percent F ₂ , 0 to 2 weight percent TiO ₂ , and a total of 0 to 5 weight percent other constituents Included Than is. In another embodiment, the composite for aircraft industry of the present invention comprises a polymer resin and a plurality of glass fibers disposed in the polymer resin, wherein the plurality of glass fibers are included in the plurality of glass fibers. Or at least one of the other glass compositions may be formed of one of the other glass compositions disclosed herein as part of the present invention.

  In some embodiments, the composite for the aircraft industry of the present invention comprises a polymeric resin and at least one fiber glass strand disclosed herein disposed in the polymeric resin. In some embodiments, the composite for the aircraft industry of the present invention is a roving comprising a polymer resin and at least one fiber glass strand disclosed herein disposed in the polymer resin. It has at least a part. In another embodiment, the composite for the aircraft industry of the present invention comprises a polymeric resin and at least one yarn disclosed herein disposed in the polymeric resin. In yet another embodiment, the composite for the aircraft industry of the present invention comprises a polymeric resin and at least one fabric disclosed herein disposed in the polymeric resin. In some embodiments, the composite for the aircraft industry of the present invention comprises at least one weft comprising at least one fiber glass strand as disclosed herein and at least one weft disclosed herein. And at least one warp comprising a fiber glass strand of

  The composite for the aircraft industry of the present invention may be provided with various polymer resins depending on the desired properties and applications. In some embodiments of the present invention that make up composites for the aircraft industry, the polymeric resin comprises a phenolic resin. In another embodiment of the present invention, which constitutes a composite for the aircraft industry, the polymeric resin is epoxy, polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, It may include polydicyclopentadiene, polyphenylene sulfide, polyetheretherketone, cyanate ester, bis-maleimide, and thermosetting polyurethane resins. Examples of parts in which the aerospace composites of the present invention may be used include, but are not limited to, floorboards, in-flight overhead storage bins, kitchens, seatbacks, and possibly other interior compartments susceptible to impact, and External components such as helicopter blades may be mentioned.

  Some embodiments of the present invention relate to composites that may be used in wind energy applications. In some embodiments, inventive composites suitable for use in wind energy applications are those that exhibit desirable properties (such as high modulus / high rupture strain and low density) for use in wind energy applications. Also, the composites of the present invention suitable for use in wind energy applications may be less expensive than other composites used in wind energy applications. The composites of the present invention may be suitable for use in wind turbine blades, in particular lighter but still powerful long wind turbine blades as compared to other long wind turbine blades.

In some embodiments, a composite of the present invention suitable for use in wind energy applications comprises a polymeric resin and a plurality of glass fibers disposed in the polymeric resin. At least one of the plurality of glass fibers comprises the following components: 60 to 68 weight percent SiO ₂ , 7 to 12 weight percent B ₂ O ₃ , 9 to 15 weight percent Al ₂ O ₃ , 8 to 15 Weight percent MgO, 0-4 weight percent CaO, 0-2 weight percent Li ₂ O, 0-1 weight percent Na ₂ O, 0-1 weight percent K ₂ O, 0-1 weight percent F ₂ O _3, 0 to 1% by weight of _F 2, 0 to 2% by weight of TiO _2, and the glass composition comprising other constituents of 0-5% by weight in total were included Than is. Composites of the invention suitable for use in wind energy applications, in some embodiments, comprise a polymeric resin and a plurality of glass fibers disposed in the polymeric resin at least one of the plurality of glass fibers, the following components: 53.5 to 77% by weight of _SiO 2, 4.5-14.5% by weight of _B 2 _O 3, from 4.5 to 18.5 wt Percent Al ₂ O ₃ , 4 to 12.5 weight percent MgO, 0 to 0.55 weight percent CaO, 0 to 4 weight percent Li ₂ O, 0 to 2 weight percent Na ₂ O, 0 to 1 weight percent _K 2 O, 0 to 1% by weight of _F 2 _O 3, _0~2 wt% of _F 2, 0 to 2% by weight of TiO _2, and the other constituents of 0-5 wt% in total In which free glass composition is included. In another embodiment, the composite for aircraft industry of the present invention comprises a polymer resin and a plurality of glass fibers disposed in the polymer resin, wherein the plurality of glass fibers are included in the plurality of glass fibers. Or at least one of the other glass compositions may be formed of one of the other glass compositions disclosed herein as part of the present invention.

  In some embodiments, inventive composites suitable for use in wind energy applications comprise a polymeric resin and at least one fiber glass strand disclosed herein disposed in the polymeric resin. Have. In some embodiments, inventive composites suitable for use in wind energy applications comprise a polymeric resin and at least one fiber glass strand disclosed herein disposed in the polymeric resin. At least a portion of the included rovings. In another embodiment, a composite of the present invention suitable for use in wind energy applications comprises a polymeric resin and at least one yarn disclosed herein disposed in the polymeric resin. . In yet another embodiment, a composite of the present invention suitable for use in wind energy applications comprises a polymeric resin and at least one fabric disclosed herein disposed in the polymeric resin. . In some embodiments, inventive composites suitable for use in wind energy applications comprise at least one weft comprising at least one fiber glass strand disclosed herein; And at least one warp comprising at least one fiber glass strand disclosed.

  Composites of the present invention suitable for use in wind energy applications may be provided with various polymeric resins depending on the desired properties and applications. In some embodiments of the present invention that constitute composites suitable for use in wind energy applications, the polymeric resin comprises an epoxy resin. In another embodiment of the present invention, which constitutes a composite suitable for use in wind energy applications, the polymeric resin may comprise a polyester resin, a vinyl ester, a thermosetting polyurethane, or a polydicyclopentadiene resin.

Some embodiments of the present invention relate to laminates. The laminate of the present invention may comprise a plurality of sheet-like layers which are combined to form a laminate. In some embodiments, the laminate of the present invention comprises at least one layer comprising the composite described herein. In some embodiments, the laminate of the present invention is a composite comprising a polymer resin and a plurality of glass fibers disposed in the polymer resin, wherein the composite is one of the plurality of glass fibers. At least one of the following components: 60 to 68 weight percent SiO ₂ , 7 to 12 weight percent B ₂ O ₃ , 9 to 15 weight percent Al ₂ O ₃ , 8 to 15 weight percent MgO, 0 to 0 4 weight percent CaO, 0 to 2 weight percent Li ₂ O, 0 to 1 weight percent Na ₂ O, 0 to 1 weight percent K ₂ O, 0 to 1 weight percent F ₂ O ₃ , 0 to 1 weight percent F _2, Bei at least one layer containing the composite material comprises a glass composition comprising other constituents of 0-5 weight percent TiO _2, and the sum of 0-2% by weight To have. The laminate of the present invention, in some embodiments, is a composite material comprising a polymer resin and a plurality of glass fibers disposed in the polymer resin, wherein the composite material is one of the plurality of glass fibers. At least one of the following components: 53.5 to 77 weight percent SiO ₂ , 4.5 to 14.5 weight percent B ₂ O ₃ , 4.5 to 18.5 weight percent Al ₂ O ₃ , 4 to 12.5 weight percent MgO, 0 to 0.55 weight percent CaO, 0 to 4 weight percent Li ₂ O, 0 to 2 weight percent Na ₂ O, 0 to 1 weight percent K ₂ O, A glass composition comprising 0-1 weight percent F ₂ O ₃ , 0-2 weight percent F ₂ , 0-2 weight percent TiO ₂ , and a total of 0-5 weight percent other constituents The composite material is Or a comprises at least one layer. In another embodiment, the laminate of the present invention is a composite comprising a polymer resin and a plurality of glass fibers disposed in the polymer resin, wherein at least one of the plurality of glass fibers is a composite material. One may comprise at least one layer including a composite formed of one of the other glass compositions disclosed herein as part of the present invention.

  In some embodiments, the laminate of the present invention comprises a polymer resin and a composite comprising at least one fiber glass strand disclosed herein disposed in the polymer resin. It is In some embodiments, the laminate of the present invention comprises at least a portion of a roving comprising a polymer resin and at least one fiber glass strand disclosed herein disposed in the polymer resin. Have. In another embodiment, the laminate of the present invention comprises a composite comprising a polymeric resin and at least one yarn disclosed herein disposed in the polymeric resin. In yet another embodiment, the laminate of the present invention comprises a composite comprising a polymeric resin and at least one fabric disclosed herein disposed in the polymeric resin. In some embodiments, the laminate of the present invention comprises at least one weft comprising at least one fiber glass strand as disclosed herein and at least one fiber glass as disclosed herein And at least one warp comprising strands.

  The laminate of the present invention may be provided with various polymer resins depending on the desired properties and applications. In some embodiments of the invention comprising a laminate, the polymeric resin comprises an epoxy resin. In another embodiment of the invention comprising the composite, the polymeric resin is polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, polydicyclopentadiene, polyphenylene It may include sulfides, polyetheretherketones, cyanates, bis-maleimides, and thermosetting polyurethane resins.

Some embodiments of the present invention relate to a prepreg. The prepreg of the present invention may comprise a polymeric resin and at least one fiber glass strand as disclosed herein. In some embodiments, the prepreg of the present invention comprises a polymer resin and a plurality of glass fibers in contact with the polymer resin, wherein at least one of the plurality of glass fibers is but the following components: 60 to 68% by weight of _SiO 2, 7 to 12% by weight of _B 2 _O 3, 9 to 15% by weight of _Al 2 _O 3, 8 to 15% by weight of MgO, 0 to 4% by weight CaO, 0-2 weight percent Li ₂ O, 0-1 weight percent Na ₂ O, 0-1 weight percent K ₂ O, 0-1 weight percent F ₂ O ₃ , 0-1 weight percent A glass composition comprising F ₂ , 0 to 2 weight percent TiO ₂ , and a total of 0 to 5 weight percent other constituents is included. The prepreg of the present invention, in some embodiments, comprises a polymer resin and a plurality of glass fibers in contact with the polymer resin, wherein at least one of the plurality of glass fibers is used. The following components: 53.5 to 77 weight percent SiO ₂ , 4.5 to 14.5 weight percent B ₂ O ₃ , 4.5 to 18.5 weight percent Al ₂ O ₃ , 4 to 12 .5% by weight of MgO, from 0 to 10.5% by weight of CaO, 0 to 4 weight percent _Li 2 O, 0 to 2 wt% of _Na 2 O, 0-1% by weight _K 2 O, 0-1 A glass composition comprising weight percent F ₂ O ₃ , 0 to 2 weight percent F ₂ , 0 to 2 weight percent TiO ₂ , and a total of 0 to 5 weight percent other constituents Ah . In another embodiment, the prepreg of the present invention comprises a polymer resin and a plurality of glass fibers in contact with the polymer resin, wherein at least one of the plurality of glass fibers is It may be formed of one of the other glass compositions disclosed herein as part of the present invention.

  In some embodiments, the prepreg of the present invention comprises a polymeric resin and at least one fiber glass strand as disclosed herein in contact with the polymeric resin. In some embodiments, the prepreg of the present invention comprises at least a portion of a roving comprising a polymer resin and at least one fiber glass strand disclosed herein disposed in the polymer resin. ing. In another embodiment, the prepreg of the present invention comprises a polymeric resin and at least one yarn disclosed herein in contact with the polymeric resin. In yet another embodiment, the prepreg of the present invention comprises a polymeric resin and at least one fabric disclosed herein in contact with the polymeric resin. In some embodiments, a prepreg of the present invention comprises at least one weft yarn comprising at least one fiber glass strand as disclosed herein and at least one fiber glass strand as disclosed herein And at least one warp yarn.

  The prepreg of the present invention may be provided with various polymer resins depending on the desired properties and applications. In some embodiments of the invention comprising a prepreg, the polymeric resin comprises an epoxy resin. In another embodiment of the present invention constituting a prepreg, the polymer resin is polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenol type, polyester, vinyl ester, polydicyclopentadiene, polyphenylene sulfide , Polyether ether ketone, cyanate ester, bis-maleimide, and thermosetting polyurethane resin.

  Prepregs may be incorporated into other products in some embodiments of the invention. For example, in some embodiments, the prepreg of the present invention may be incorporated into a fiber-metal laminate. Incorporating the prepregs of the present invention into fiber-metal laminates is, in some embodiments, superior crack arrest properties and specific gravity compared to metal sheets (eg, aluminum alloy sheets) in which the prepreg will be used. It can be advantageous because it can be Several fiber-metal laminates, such as GLARE and ARALL, are well known, and the prepregs of the present invention can be easily incorporated into the structure. Fiber-metal laminates such as GLARE ("Glass Laminated Aluminum Reinforced Epoxy") and ARALL (Aramid fiber-based fiber-metal laminates) are used as lightweight aircraft materials for aerospace applications As developed, GLARE is generally for airframe applications and ARALL is generally for wing applications. GLARE fiber-metal laminates conventionally consist of a fiberglass / epoxy prepreg (unidirectional or biaxial) and a pretreated aluminum foil (ie 0.224 mm thick 2024 T3 foil, composite layer It has been constructed with alternating layers of what has been etched using a proprietary process to improve adhesion. Such laminated structures are widely used in aircraft structures due to their excellent fatigue performance, low corrosion rates, and slow crack propagation properties in the presence of stress risers (eg, perforations, rivets, edges). Application possibilities. Such laminates are typically molded under heat and pressure in autoclaves and presses. An example of a GLARE fiber-metal laminate may be one incorporating three layers of aluminum and two layers of biaxial composite, sometimes referred to as a GLARE 3/2 laminate. There may also be embodiments that incorporate four layers of aluminum and three layers of composites, or five layers of aluminum and four layers of composites.

  The prepregs of the present invention can be replaced in such GLARE and ARALL fiber-metal laminates (or other fiber-metal laminates) as a substitute for current fiber glass prepregs used in such products. Thus, the fiber-metal laminate is adhesively attached to the prepreg according to some embodiments of the present invention, the first metal sheet adhesively fixed to one surface of the prepreg, and the second surface of the prepreg. It may be provided with a fixed second metal sheet, such that the prepreg is to be disposed between the two metal sheets. In some embodiments, multiple layers of prepregs have, for example, a 3/2 configuration (a metal / prepreg / metal / prepreg / metal configuration of two prepreg layers between three metal sheets), a 4/3 configuration ( Three prepreg layers of metal / prepreg / metal / prepreg / metal / prepreg / metal configuration between four metal sheets, 5/4 configuration (four prepreg layers of metal / prepreg / metal / between five metal sheets) Prepregs / metals / prepregs / metals / prepregs / metals configurations) or may be incorporated into other configurations. In some embodiments, the metal sheet may be comprised of aluminum or other metals typically used in fiber-metal laminates. In some embodiments, the polymeric resin used for the prepreg comprises epoxy. In some embodiments, the prepreg is adhesively secured to the metal sheet using a film adhesive known to those skilled in the art for bondline thickness control. In some embodiments, a separate adhesive is not required because the prepreg can be adhered to the metal sheet by the polymeric resin (eg, epoxy) used for the prepreg.

  Some embodiments of the present invention relate to a radome. A radome is a radar enclosure or structural shell and is typically constructed using materials that provide a low dielectric constant to minimize signal reflections into and out of the radar. High cost fibers (such as quartz and aramid) and high strength fiberglass are successfully used in combination with various resin systems in the preparation of radomes. In addition to the permeability requirements of the radar, the materials for the radome preferably have high stiffness / strength and excellent durability properties to withstand environmental loads (wind, snow, rain, rain, temperature fluctuations and UV degradation) It is obtained. Glass fibers according to some embodiments of the present invention may have a dielectric constant of 5.3 at 1 MHz, which is greater than quartz (about 3.5) but E-glass (6.3 to 1 MHz) 6.6) Smaller and equivalent to S-2 glass (5 to 5.4 at 1 MHz), making it a suitable glass fiber for use in radome applications.

In some embodiments, the radome of the present invention comprises a polymer resin and a plurality of glass fibers disposed in the polymer resin, wherein at least one of the plurality of glass fibers is types, the following components: 60 to 68% by weight of _SiO 2, 7 to 12% by weight of _B 2 _O 3, 9 to 15% by weight of _Al 2 _O 3, 8 to 15% by weight of MgO, 0 to 4 wt % of CaO, 0 to 2 wt% of _Li 2 O, 0 to 1% by weight of _Na 2 O, 0 to 1% by weight of _K 2 O, 0 to 1% by weight of _F 2 _O 3, 0~1 wt% of _F 2, those containing the glass composition comprising other constituents of 0-5 weight percent TiO _2, and the sum of 0-2% by weight. The radome of the present invention, in some embodiments, comprises a polymer resin and a plurality of glass fibers disposed in the polymer resin, wherein at least one of the plurality of glass fibers is Types are as follows: 53.5 to 77 weight percent SiO ₂ , 4.5 to 14.5 weight percent B ₂ O ₃ , 4.5 to 18.5 weight percent Al ₂ O ₃ , 4 to 4 12.5 wt% of MgO, 0 to 10.5% by weight of CaO, 0 to 4 weight percent _Li 2 O, 0 to 2 wt% of _Na 2 O, 0-1% by weight _K 2 O, 0 to Glass compositions comprising 1 weight percent F ₂ O ₃ , 0-2 weight percent F ₂ , 0-2 weight percent TiO ₂ , and a total of 0-5 weight percent other constituents Is . In another embodiment, the radome of the present invention comprises a polymer resin and a plurality of glass fibers disposed in the polymer resin, wherein at least one of the plurality of glass fibers is used. May be formed of one of the other glass compositions disclosed herein as part of the present invention.

  In some embodiments, the radome of the present invention comprises a polymeric resin and a radar enclosure or structural shell comprising at least one fiber glass strand disclosed herein disposed in the polymeric resin. including. In some embodiments, a radome of the invention comprises at least a portion of a roving comprising a polymer resin and at least one fiber glass strand disclosed herein disposed in the polymer resin. ing. In another embodiment, the radome of the present invention comprises a polymeric resin and at least one yarn disclosed herein disposed in the polymeric resin. In yet another embodiment, the radome of the present invention comprises a polymeric resin and at least one fabric disclosed herein disposed in the polymeric resin. In some embodiments, the radome of the invention comprises at least one weft comprising at least one fiber glass strand as disclosed herein and at least one fiber glass strand as disclosed herein And at least one warp yarn.

  The radome of the present invention may be equipped with various polymeric resins depending on the desired properties and applications. In some embodiments of the invention relating to a radome, the polymeric resin is epoxy, phenolic, polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, polydicyclo It may include pentadiene, polyphenylene sulfide, polyetheretherketone, cyanate ester, bis-maleimide, and thermosetting polyurethane resin.

  Glass fibers useful in the present invention may be made by any suitable method known to one skilled in the art, including but not limited to the methods described herein above. Additionally, the primary sizing composition may be applied to the glass fibers using any suitable method known to those skilled in the art. In some embodiments, the sizing composition may be applied immediately after the formation of the glass fibers. The sizing composition may comprise any suitable sizing composition known to those skilled in the art for reinforcing applications. In some embodiments, the sizing composition does not include a starch oil sizing composition. In some embodiments of the present invention that constitute a sizing composition that does not include a starch oil sizing composition, sized glass fibers or glass fiber strands are thrashing compositions prior to using the fibers or strands in a weaving application. There is no need for further processing. In other embodiments that constitute a sizing composition that does not include a starch oil sizing composition, sized glass fibers or glass fiber strands optionally thrashing compositions prior to using the fibers or strands in a weaving application Can be further processed. In some embodiments of the present invention that constitute a primary sizing composition, the sizing composition may comprise a starch oil sizing composition. In some embodiments of the present invention that constitute a starch oil sizing composition, the starch oil sizing composition is later removed from the fabric formed of at least one sized glass fiber or fiber glass strand obtain. In some embodiments, the starch oil sizing may be removed from the fabric using any suitable method known to one skilled in the art, including but not limited to heat cleaning. In embodiments of the present invention which constitute a fabric from which a starch oil sizing composition has been removed, the fabric of the present invention may be further treated with a finish coating.

  The fiber glass strands of the present invention may be prepared by any suitable method known to those skilled in the art. The fiberglass cloth of the present invention is generally, for example, but not limited to, by any suitable method known to the person skilled in the art, also referred to as "weft yarn" (also referred to as "fill yarn") Can be made by interweaving a plurality of warp yarns. Such interlacing may be accomplished by arranging the warp yarns in a generally parallel planar array on a loom and then weaving the weft yarns into the warp yarns and the weft yarns over and under the warp yarns in a predetermined repeating pattern. The pattern used depends on the desired cloth style.

  The warp can generally be prepared using techniques known to those skilled in the art. The warp can be formed by tapering multiple molten glass streams from a bushing or spinning machine. The sizing composition can then be applied to the individual glass fibers and the fibers can be gathered together to form a strand. Subsequently, the strands can be processed into yarns by transferring the strands to a bobbin by means of a twist frame. During this transfer, the strands may be twisted to help hold the bundle of fibers together. The twisted strand may then be wound on a bobbin, which may be used in the weaving process.

  The placement of the warp on the weaving machine can generally be performed using techniques known to those skilled in the art. Placement of the warp yarns on the weaving machine can be done by a warp beam. The warp beam comprises a specified number of warp yarns (also referred to as "ends") wound in a configuration essentially parallel to the cylindrical core (also referred to as "warp sheet"). Warp beam preparation involves combining multiple yarn packages (each package contains a portion of the number of ends required for the warp beam) into a single package or warp beam It can be. For example, but not limiting herein, a 50 inch (127 cm) wide 7781 style fabric (which uses a DE 75 input yarn) typically requires 2868 ends. Ru. However, conventional equipment for forming a warp beam does not allow all such ends to be transferred from the bobbin into a single beam in one operation. Thus, a plurality of beams (typically referred to as "section beams") composed of the required number of end portions may be produced and then combined to form a warp beam. Similar to the warp beam, the section beam may include a cylindrical core with a plurality of essentially parallel warp yarns wrapped around it. One skilled in the art will recognize that the section beam may be any number of warp threads needed to form the final warp beam, but generally the number of ends included in the section beam Is limited by the capacity of the warping reel. For the 7781 style fabric, combining the 717 end four section beams (each typically supplied with DE 75) provides the 2868 ends required for the warp sheet (see above As stated).

  The composites of the present invention may be any suitable method known to those skilled in the art, including but not limited to vacuum assisted resin injection molding, extrusion compounding, compression molding, resin transfer molding, filament winding, prepreg / autoclave curing, and extrusion molding Etc.). The composites of the present invention may be prepared using molding techniques such as those known to those skilled in the art. In particular, embodiments of composites of the present invention incorporating woven fiberglass cloth may be prepared using techniques known to those skilled in the art for the preparation of such composites.

  As an example, some composites of the present invention can be made using vacuum assisted compression molding, which procedure is well known to those skilled in the art and is briefly described below. As known to those skilled in the art, in vacuum assisted compression molding, a stack of preimpregnated glass cloths is placed in a platen. In some embodiments of the present invention, the pre-impregnated glass cloth stack may comprise one or more cloths of the present invention described herein cut to the desired size and shape. . When the stacking operation of the corresponding number of layers is finished, the press is closed and the platen is connected to the vacuum pump in such a way that the stacked cloth is compressed by the upper platen until the desired pressure is reached. The vacuum assists in the evacuation of air trapped within the stacked fabric and results in low void content in the formed laminate. After connecting the platen to the vacuum pump, the temperature of the platen is then increased to a specific predetermined temperature setting for the resin used to accelerate the rate of conversion of the resin (eg, a thermosetting resin), and the temperature and pressure settings Until the laminate reaches sufficient cure. At this point, the heat is turned off and the platen is cooled by water circulation to room temperature. The platen can then be opened and the shaped laminate can be removed from the press.

  As another example, some composites of the present invention can be made using vacuum assisted resin injection techniques (described further herein). A stack of fiberglass cloth of the present invention may be cut to the desired size and placed on a silicone release agent treated glass table. The stacked fabric can then be covered with a release ply, attached with a flow enhancing medium, and vacuum bagged using a nylon bagging film. Next, a so-called "lay up" can be subjected to a vacuum force of about 27 inches Hg. Alternatively, polymeric resins to be reinforced with fiberglass cloth can be prepared using techniques known to those skilled in the art for specific such resins. For example, for some polymeric resins, a suitable resin (eg, an amine curable epoxy resin) should be recommended by the appropriate curing agent (eg, an amine for an amine curable epoxy resin) and the resin manufacturer Or as known to the person skilled in the art. The combined resin may then be degassed in a vacuum chamber for 30 minutes and poured into the fabric preform until substantially complete wetting of the stacked fabrics is achieved. At this point, the table may be covered with a heating blanket (set to a temperature of about 45-50 ° C.) for 24 hours. The resulting hard composite can then be demolded and postcured for 4 hours at about 250 ° F. in a programmable convection oven. However, as is known to those skilled in the art, various parameters (such as degassing time, heating time, and post curing conditions) may vary based on the particular resin system used, and will be appreciated by those skilled in the art. It is understood how to select such parameters based on the specific resin system.

  The laminates of the present invention may be prepared by any suitable means known to one skilled in the art, including but not limited to injection.

  The prepregs of the present invention may be any suitable means known to those skilled in the art, including but not limited to passing fiber glass strands, rovings or cloths through a resin bath; using solvent-based resins; or using resin membranes Etc.).

  The fiber-metal laminate of the present invention may be prepared by any suitable means known to those skilled in the art using the prepreg of the present invention.

  The radome of the present invention may be prepared by any suitable means known to those skilled in the art.

  As mentioned above, some embodiments of the present invention may include more than one glass fiber. Glass fibers suitable for use in the present invention may be of any suitable diameter known to those skilled in the art depending on the desired application. Glass fibers suitable for use in some embodiments of the present invention are those having a diameter of about 5 to about 13 μm. Glass fibers suitable for use in other embodiments of the invention are those having a diameter of about 5-7 μm.

Also, glass fibers and glass fiber strands suitable for use in the present invention may include various glass compositions that are also embodiments of the present invention. Some embodiments of such glass fibers and fiber glass strands are shown above, others are shown below. As noted above, one example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is
SiO ₂ 60-68 weight percent;
B ₂ O ₃ 7 to 12 weight percent;
Al ₂ O ₃ 9-15% by weight;
MgO 8 to 15 weight percent;
CaO 0-4 weight percent;
Li ₂ O 0-2% by weight;
Na ₂ O 0 to 1% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
F ₂ 0 to 1 weight percent;
And a glass composition containing 0 to 5 weight percent in total of TiO ₂ 0 to 2 weight percent; and other constituents.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is
SiO ₂ 60-68 weight percent;
B ₂ O ₃ 7 to 12 weight percent;
Al ₂ O ₃ 9-15% by weight;
MgO 8 to 15 weight percent;
CaO 0-4 weight percent;
Li ₂ O> 0~2 wt%;
Na ₂ O 0 to 1% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
F ₂ 0 to 1 weight percent;
0 to 2 weight percent TiO ₂ ; and 0 to 5 weight percent in total of the other constituents;
A glass composition is included which has a Li ₂ O content greater than either Na ₂ O content or K ₂ O content. In another embodiment, the CaO content is 0-3 weight percent. In yet another embodiment, the CaO content is 0-2 weight percent. In some embodiments, the CaO content is 0-1 weight percent. In some embodiments of the present invention, the MgO content is 8 to 13 weight percent. In another embodiment, the MgO content is 9 to 12 weight percent. In some embodiments, TiO ₂ content is 0-1 weight percent. In some embodiments, the B ₂ O ₃ content is 10 weight percent or less. In some embodiments of the present invention, the Al ₂ O ₃ content is 9 to 14 weight percent. In another embodiment, the Al ₂ O ₃ content is 10 to 13 weight percent. In some embodiments, the (Li ₂ O + Na ₂ O + K ₂ O) content is less than 2 weight percent. In some embodiments, the composition comprises 0-1 weight percent BaO and 0-2 weight percent ZnO. In another embodiment, the composition is essentially free of BaO and essentially free of ZnO. In some embodiments, the other constituents (if present) are present in a total amount of 0 to 2 weight percent. In other embodiments, the other constituents (if present) are present in a total amount of 0-1 weight percent. In some embodiments, the Li ₂ O content is 0.4 to 2.0 weight percent. In another embodiment comprising a Li ₂ O content of 0.4 to 2.0 weight percent, the Li ₂ O content is greater than the (Na ₂ O + K ₂ O) content.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is
SiO ₂ 60-68 weight percent;
7 to 13 weight percent of B ₂ O ₃ ;
Al ₂ O ₃ 9-15% by weight;
MgO 8 to 15 weight percent;
CaO 0-4 weight percent;
Li ₂ O 0-2% by weight;
Na ₂ O 0 to 1% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
And a glass composition comprising F ₂ 0 to 1 weight percent; and TiO ₂ 0 to 2 weight percent. In some embodiments, the glass composition is characterized by a relatively low content, such as on the order of about 0 to 4 weight percent CaO. In still other embodiments, the CaO content may be on the order of about 0-3 weight percent. In some embodiments, the MgO content is twice the CaO content (by weight percent). Some embodiments of the present invention may have a MgO content greater than about 6.0 weight percent, and in other embodiments the MgO content may be greater than about 7.0 weight percent. Some glass compositions suitable for use in some embodiments of the present invention may be characterized by the presence of less than 1.0 weight percent BaO. In embodiments where BaO is present in only minor amounts, the BaO content may be characterized as being less than 0.05 weight percent.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is
SiO ₂ 60-68 weight percent;
B ₂ O ₃ 7 to 12 weight percent;
Al ₂ O ₃ 9-15% by weight;
MgO 8 to 15 weight percent;
CaO 0-4 weight percent;
Li ₂ O> 0~2 wt%;
Na ₂ O 0 to 1% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
F ₂ 0 to 1 weight percent;
0 to 2 weight percent TiO ₂ ; and 0 to 5 weight percent in total of the other constituents;
Selected so that a glass with a Li ₂ O content greater than either the Na ₂ O content or the K ₂ O content and the constituent material has a dielectric constant (D _k ) less than 6.7 at a frequency of 1 MHz Glass composition is included. In another embodiment, the constituents are chosen such that a glass having a dielectric constant (D _k ) of less than 6 at a frequency of 1 MHz is obtained. In yet another embodiment, the constituents are selected such that a glass having a dielectric constant (D _k ) of less than 5.8 at a frequency of 1 MHz is obtained. In some embodiments, the constituents are selected to provide a glass having a dielectric constant (D _k ) of less than 5.6 at a frequency of 1 MHz.

The constituents of the glass composition suitable for use in some embodiments of the present invention have the desired forming temperature (defined as the temperature at which the viscosity is 1000 poise) and / or the desired liquidus line It can be selected based on the temperature. In some embodiments, glass fibers or fiber glass strands suitable for use in the present invention are:
SiO ₂ 60-68 weight percent;
B ₂ O ₃ 7 to 12 weight percent;
Al ₂ O ₃ 9-15% by weight;
MgO 8 to 15 weight percent;
CaO 0-4 weight percent;
Li ₂ O> 0~2 wt%;
Na ₂ O 0 to 1% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
F ₂ 0 to 1 weight percent;
0 to 2 weight percent TiO ₂ ; and 0 to 5 weight percent in total of the other constituents;
A glass composition selected such that the Li ₂ O content is greater than either the Na ₂ O content or the K ₂ O content and the constituent has a viscosity of 1000 poise with a forming temperature T _F of 1370 ° C. or less It is included. In another embodiment, the constituents are chosen such that a viscosity of 1000 poise results in a molding temperature T _F of 1320 ° C. or less. In yet another embodiment, the constituents are selected such that a viscosity of 1000 poise results in a molding temperature T _F of 1300 ° C. or less. In some embodiments, the components are selected to provide a molding temperature T _F of 1290 ° C. or less at a viscosity of 1000 poise. In some embodiments, the constituents are selected such that a viscosity of 1000 poise results in a molding temperature _TF less than or equal to 1370 ° C. and a liquidus temperature T _L at least 55 ° C. less than the molding temperature. In another embodiment, the constituents are selected such that a viscosity of 1000 poise results in a molding temperature _TF of 1320 ° C. or less and a liquidus temperature T _L at least 55 ° C. less than the molding temperature. In yet another embodiment, the constituents are selected such that a viscosity of 1000 poise results in a molding temperature _TF less than or equal to 1300 ° C. and a liquidus temperature T _L at least 55 ° C. less than the molding temperature. In some embodiments, the constituents are selected such that a viscosity of 1000 poise results in a molding temperature T _F of 1290 ° C. or less and a liquidus temperature T _L at least 55 ° C. less than the molding temperature.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is
B ₂ O ₃ less than 12% by weight;
Al ₂ O ₃ 9-15% by weight;
MgO 8 to 15 weight percent;
CaO 0-4 weight percent;
SiO ₂ 60-68 weight percent;
Li ₂ O> 0~2 wt%;
Na ₂ O 0 to 1% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
A glass composition comprising F ₂ 0 to 1 weight percent; and TiO ₂ 0 to 2 weight percent;
The glass exhibits a dielectric constant (D _k ) less than 6.7 and a forming temperature (T _F ) less than 1370 ° C. with a viscosity of 1000 poise, and the Li ₂ O content is either Na ₂ O or K ₂ O content More glass compositions are included. In some embodiments, the CaO content is 0-1 weight percent.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is
SiO ₂ 60-68 weight percent;
B ₂ O ₃ 7 to 12 weight percent;
Al ₂ O ₃ 9-15% by weight;
MgO 8 to 15 weight percent;
CaO 0-3% by weight;
Li ₂ O 0.4 to ₂ % by weight;
Na ₂ O 0 to 1% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
A glass composition comprising F ₂ 0 to 1 weight percent; and TiO ₂ 0 to 2 weight percent;
The glass exhibits a dielectric constant (D _k ) of less than 5.9 and a forming temperature (T _F ) of less than 1300 ° C. with a viscosity of 1000 poise, and the Li ₂ O content is either Na ₂ O or K ₂ O content More glass compositions are included.

Another example of glass fibers or fiber glass strands suitable for use in some embodiments of the present invention are essentially SiO ₂ 60 to 68% by weight;
7 to 11 weight percent of B ₂ O ₃ ;
Al ₂ O ₃ 9-13% by weight;
MgO 8 to 13 weight percent;
CaO 0-3% by weight;
Li ₂ O 0.4 to ₂ % by weight;
Na ₂ O 0 to 1% by weight;
K ₂ O 0 to 1% by weight;
_{(Na 2 O + K 2 O} + Li 2 O) 0~2 % by weight;
Fe ₂ O ₃ 0-1% by weight;
F ₂ 0 to 1 weight percent; and TiO ₂ 0 to 2 weight percent;
A glass composition is included which has a Li ₂ O content greater than either Na ₂ O content or K ₂ O content. In some embodiments, the CaO content is 0-1 weight percent. In some embodiments that include a 0 to 1 weight percent CaO content, the B ₂ O ₃ content is 10 weight percent or less.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is
SiO ₂ 60-68 weight percent;
B ₂ O ₃ 7 to 10 weight percent;
Al ₂ O ₃ 9-15% by weight;
MgO 8 to 15 weight percent;
CaO 0-4 weight percent;
Li ₂ O> 0~2 wt%;
Na ₂ O 0 to 1% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
F ₂ 0 to 1 weight percent;
0 to 2 weight percent TiO ₂ ; and 0 to 5 weight percent other constituents.
A glass composition is included which has a Li ₂ O content greater than either Na ₂ O content or K ₂ O content. In some embodiments, the components are selected to provide a glass having a dielectric constant (D _k ) of less than 6.7 at a frequency of 1 MHz. In another embodiment, the constituents are chosen such that a glass having a dielectric constant (D _k ) of less than 6 at a frequency of 1 MHz is obtained. In yet another embodiment, the constituents are selected such that a glass having a dielectric constant (D _k ) of less than 5.8 at a frequency of 1 MHz is obtained. In some embodiments, the constituents are selected to provide a glass having a dielectric constant (D _k ) of less than 5.6 at a frequency of 1 MHz.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is:
SiO ₂ 53.5 to 77 weight percent;
B ₂ O ₃ 4.5 to 14.5 weight percent;
Al ₂ O ₃ 4.5 to 18.5% by weight;
MgO 4 to 12.5 weight percent;
CaO 0-0.5% by weight;
Li ₂ O 0-4% by weight;
Na ₂ O 0 to 2% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
F ₂ 0-2% by weight;
Glass compositions comprising 0 to 2 weight percent TiO ₂ ; and 0 to 5 weight percent in total of the other constituents.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is:
SiO ₂ 60-77% by weight;
B ₂ O ₃ 4.5 to 14.5 weight percent;
Al ₂ O ₃ 4.5 to 18.5% by weight;
MgO 8 to 12.5 weight percent;
CaO 0-4 weight percent;
Li ₂ O 0-3% by weight;
Na ₂ O 0 to 2% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
F ₂ 0-2% by weight;
And a glass composition containing 0 to 5 weight percent in total of TiO ₂ 0 to 2 weight percent; and other constituents.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is:
SiO ₂ at least 60 weight percent;
B ₂ O ₃ 5 to 11% by weight;
Al ₂ O ₃ 5-18 weight percent;
MgO 5 to 12 weight percent;
CaO 0 to 10% by weight;
Li ₂ O 0-3% by weight;
Na ₂ O 0 to 2% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
F ₂ 0-2% by weight;
Glass compositions comprising 0 to 2 weight percent TiO ₂ ; and 0 to 5 weight percent in total of the other constituents.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is:
SiO ₂ 60-68 weight percent;
5 to 10 weight percent of B ₂ O ₃ ;
Al ₂ O ₃ 10 to 18% by weight;
MgO 8 to 12 weight percent;
CaO 0-4 weight percent;
Li ₂ O 0-3% by weight;
Na ₂ O 0 to 2% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
F ₂ 0-2% by weight;
Glass compositions comprising 0 to 2 weight percent TiO ₂ ; and 0 to 5 weight percent in total of the other constituents.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is:
SiO ₂ 62-68% by weight;
B ₂ O ₃ 7 to 9% by weight;
Al ₂ O ₃ 11-18% by weight;
MgO 8-11 weight percent;
CaO 1-2 weight percent;
Li ₂ O 1 to 2% by weight;
Na ₂ O 0 to 0.5% by weight;
K ₂ O 0 to 0.5% by weight;
Fe ₂ O ₃ 0 to 0.5% by weight;
F ₂ 0.5-1% by weight;
Glass compositions comprising 0 to 1 weight percent TiO ₂ ; and 0 to 5 weight percent in total of the other constituents.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is:
SiO ₂ 62-68% by weight;
Less than about 9 weight percent B ₂ O ₃ ;
Al ₂ O ₃ 10 to 18% by weight;
A glass composition comprising 8 to 12 weight percent MgO; and 0 to 4 weight percent CaO;
A glass composition is included whose glass exhibits a dielectric constant (D _k ) less than 6.7 and a forming temperature (T _F ) less than 1370 ° C. with a viscosity of 1000 poise.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is:
B ₂ O ₃ less than 14% by weight;
Al ₂ O ₃ 9-15% by weight;
MgO 8 to 15 weight percent;
A glass composition comprising 0 to 4 weight percent of CaO; and 60 to 68 weight percent of SiO ₂ ;
A glass composition is included whose glass exhibits a dielectric constant (D _k ) less than 6.7 and a forming temperature (T _F ) less than 1370 ° C. with a viscosity of 1000 poise.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is:
B ₂ O ₃ less than 9% by weight;
Al ₂ O ₃ 11-18% by weight;
MgO 8-11 weight percent;
A glass composition comprising 1 to 2 weight percent of CaO; and 62 to 68 weight percent of SiO ₂ ;
A glass composition is included whose glass exhibits a dielectric constant (D _k ) less than 6.7 and a forming temperature (T _F ) less than 1370 ° C. with a viscosity of 1000 poise.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is:
SiO ₂ 60-68 weight percent;
7 to 13 weight percent of B ₂ O ₃ ;
Al ₂ O ₃ 9-15% by weight;
MgO 8 to 15 weight percent;
CaO 0-3% by weight;
Li ₂ O 0.4 to ₂ % by weight;
Na ₂ O 0 to 1% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
A glass composition comprising F ₂ 0 to 1 weight percent; and TiO ₂ 0 to 2 weight percent;
A glass composition is included, the glass exhibiting a dielectric constant (D _k ) of less than 5.9 and a forming temperature (T _F ) of less than 1300 ° C. with a viscosity of 1000 poise.

Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention is:
SiO ₂ 60-68 weight percent;
7 to 11 weight percent of B ₂ O ₃ ;
Al ₂ O ₃ 9-13% by weight;
MgO 8 to 13 weight percent;
CaO 0-3% by weight;
Li ₂ O 0.4 to ₂ % by weight;
Na ₂ O 0 to 1% by weight;
K ₂ O 0 to 1% by weight;
_{(Na 2 O + K 2 O} + Li 2 O) 0~2 % by weight;
Fe ₂ O ₃ 0-1% by weight;
And a glass composition comprising F ₂ 0 to 1 weight percent; and TiO ₂ 0 to 2 weight percent.

In addition to, or instead of, the features of the invention described above, some embodiments of the glass composition of the invention have a dissipation factor (D _f ) that is less than that of a standard electronics E-glass It can be used to obtain glass. In some embodiments, D _F may be 0.0150 or less at 1 GHz, and 0.0100 or less at 1 GHz in other embodiments.

In some embodiments of the glass composition, D _F is less than or equal to 0.007 at 1 GHz, in other embodiments less than or equal to 0.003 at 1 GHz, and in other embodiments less than or equal to 0.002 at 1 GHz.

  In some embodiments, glass compositions that can be used in the glass fibers or fiber glass strands of the present invention are characterized by relatively low CaO content, such as on the order of about 0 to 4 weight percent. In still other embodiments, the CaO content may be on the order of about 0-3 weight percent. In still other embodiments, the CaO content may be on the order of about 0-2 weight percent. In general, minimizing the CaO content resulted in improved electrical properties, and in some embodiments, the CaO content was reduced to such low levels that it could be considered as an optional constituent. In some other embodiments, the CaO content may be on the order of about 1 to 2 weight percent.

  On the other hand, the MgO content is relatively high in this type of glass, and in some embodiments, the MgO content is twice the CaO content (by weight percent). Some embodiments of the present invention may have a MgO content greater than about 5.0 weight percent, and in other embodiments the MgO content may be greater than 8.0 weight percent. In some embodiments, the composition is characterized by a content of MgO, for example, on the order of about 8 to 13 weight percent. In still other embodiments, the MgO content may be on the order of about 9 to 12 weight percent. In some other embodiments, the MgO content may be on the order of about 8 to 12 weight percent. In some other embodiments, the MgO content may be on the order of about 8 to 10 weight percent.

  In some embodiments, the composition that can be used for the glass fibers or fiber glass strands of the present invention is characterized by a (MgO + CaO) content that is, for example, less than 16 weight percent. In yet another embodiment, the (MgO + CaO) content is less than 13 weight percent. In some other embodiments, the (MgO + CaO) content is 7 to 16 weight percent. In still other embodiments, the (MgO + CaO) content may be on the order of about 10 to 13 weight percent.

In some other embodiments, the composition may be one characterized by the order of about _{9.0 (MgO + CaO) / (} Li 2 O + Na 2 O + K 2 O) content ratio. In certain embodiments, the Li ₂ O / (MgO + CaO) content ratio may be on the order of about 0-2.0. In some other embodiments, the Li ₂ O / (MgO + CaO) content ratio may be on the order of about 1 to 2.0. In certain embodiments, the Li ₂ O / (MgO + CaO) content ratio may be on the order of about 1.0.

In some other embodiments, the (SiO ₂ + B ₂ O ₃ ) content may be as high as 70-76 weight percent. In yet another embodiment, the (SiO ₂ + B ₂ O ₃ ) content may be as high as 70 weight percent. In another embodiment, the (SiO ₂ + B ₂ O ₃ ) content may be as high as 73 weight percent. In yet another embodiment, the ratio of the weight percent of Al ₂ O _{3 to} the weight percent of B ₂ O ₃ is in the order of 1-3. In some other embodiments, the ratio of the weight percent of Al ₂ O _{3 to} the weight percent of B ₂ O ₃ is on the order of 1.5 to 2.5. In certain embodiments, the SiO ₂ content is on the order of 65 to 68 weight percent.

As noted above, some low D _k compositions of the prior art have the disadvantage of requiring the inclusion of substantial amounts of BaO, but in some embodiments of the glass composition of the present invention It can be seen that BaO is not required. While the advantageous electrical and manufacturing properties of the present invention do not exclude the presence of BaO, the absence of intentional inclusion of BaO can be regarded as a further advantage of some embodiments of the present invention . Thus, embodiments of the present invention may be characterized by the presence of less than 1.0 weight percent BaO. In embodiments where only trace amounts of impurities are present, the BaO content may be characterized as being less than or equal to 0.05 weight percent.

The compositions that can be used glass fibers or fiber glass strands of the present invention, B ₂ O ₃ is in an amount of less than the prior art approaches that rely on high B ₂ O ₃ in order to achieve low D _k include. This results in considerable cost savings. In some embodiments, the required B ₂ O ₃ content is 13 weight percent or less, or 12 weight percent or less. Further, some embodiments of the present invention are those included in the definition of ASTM electronics for E- glass, i.e. _B 2 _{O 3} is 10 wt% or less.

In some embodiments, the composition is characterized by, for example, a B ₂ O ₃ content on the order of about 5 to 11 weight percent. In some embodiments, the B ₂ O ₃ content may be 6 to 11 weight percent. The B ₂ O ₃ content may be 6 to 9 weight percent in some embodiments. In some embodiments, the B ₂ O ₃ content may be 5 to 10 weight percent. In some other embodiments, the B ₂ O ₃ content is not greater than 9 weight percent. In still other some embodiments, the B ₂ O ₃ content is not greater than 8 weight percent.

In some embodiments, compositions that can be used for the glass fibers or fiber glass strands of the present invention are characterized by, for example, an Al ₂ O ₃ content on the order of about 5 to 18 weight percent. The Al ₂ O ₃ content may be 9 to 18 weight percent in some embodiments. In yet another embodiment, the Al ₂ O ₃ content is on the order of about 10 to 18 weight percent. In some other embodiments, the Al ₂ O ₃ content is on the order of about 10 to 16 weight percent. In still other some embodiments, the Al ₂ O ₃ content is on the order of about 10 to 14 weight percent. In certain embodiments, the Al ₂ O ₃ content is on the order of about 11 to 14 weight percent.

In some embodiments, Li ₂ O is an optional constituent. In some embodiments, the composition is characterized by, for example, a Li ₂ O content on the order of about 0.4 to 2.0 weight percent. In some embodiments, the Li ₂ O content is greater than the (Na ₂ O + K ₂ O) content. In some embodiments, the (Li ₂ O + Na ₂ O + K ₂ O) content is not more than 2 weight percent. In some embodiments, the (Li ₂ O + Na ₂ O + K ₂ O) content is on the order of about 1 to 2 weight percent.

In certain embodiments, the compositions of the present invention are characterized by, for example, a TiO ₂ content on the order of about 0 to 1 weight percent.

In some embodiments of the compositions set forth above, the constituents are balanced so as to obtain a glass having a dielectric constant less than that of standard E-glass. For a standard electronics E-glass for comparison, this may be less than about 6.7 at a frequency of 1 MHz. In another embodiment, the dielectric constant (D _k ) may be less than 6 at a frequency of 1 MHz. In other embodiments, the dielectric constant (D _k ) may be less than 5.8 at a frequency of 1 MHz. A further embodiment is one which exhibits a dielectric constant (D _k ) of less than 5.6 or even smaller at a frequency of 1 MHz. In another embodiment, the dielectric constant (D _k ) may be less than 5.4 at a frequency of 1 MHz. In still other embodiments, the dielectric constant (D _k ) may be less than 5.2 at a frequency of 1 MHz. In still other embodiments, the dielectric constant (D _k ) may be less than 5.0 at a frequency of 1 MHz.

Also, the compositions set forth above may have desirable temperature-viscosity relationships that lead to the practical commercial manufacture of glass fibers. In general, lower temperatures are required for the production of the fibers as compared to the D-glass type of prior art compositions. The desired properties may be displayed in several ways, which may be obtained alone or in combination according to some embodiments of the compositions described herein. For example, some specific glass compositions within the ranges indicated above can be made that exhibit a molding temperature (T _F ) of 1370 ° C. or less at a viscosity of 1000 poise. In some embodiments, the T _F is 1320 ° C. or less, or 1300 ° C. or less, or 1290 ° C. or less, or 1260 ° C. or less, or 1250 ° C. or less. Such compositions may also include glasses where the difference between the forming temperature and the liquidus temperature ( _TL ) is a positive value, and in some embodiments the forming temperature is greater than the liquidus temperature. It is at least 55 ° C. high, which favors the commercial production of fibers from such glass compositions.

In general, lowering the D _k can be aided by minimizing the alkali oxide content of the glass composition used to form the glass fibers or fiber glass strands. In embodiments where it is desired to optimize D _k reduction, the total alkali oxide may be up to 2 weight percent of the glass composition. In some embodiments, minimizing Na ₂ O and K ₂ O has been found to be more effective than Li ₂ O in this context. The presence of alkali oxides generally results in low molding temperatures. Thus, in embodiments of the present invention where obtaining a relatively low molding temperature is a priority, Li ₂ O is included in significant amounts, eg at least 0.4 weight percent. To this end, in some embodiments, the Li ₂ O content is greater than the content of either Na ₂ O or K ₂ O, and in other embodiments, the Li ₂ O content is Na ₂ O and K ₂ More than the sum of the content of O, and in some embodiments more than twice as much.

An advantageous aspect of some embodiments is that the conventional constituents in the fiberglass industry and their raw material sources rely on the avoidance of significant amounts of constituents that are expensive. In this aspect, constituents added to those specified in the definition of composition of the glass of the present invention may be contained in a total amount which is not necessary but not more than 5 weight percent. Such optional constituents include melting aids, fining aids, coloring agents, trace impurities and other additives known to those skilled in the art of glass making. Compared to some prior art low D _k glasses, the compositions of the present invention do not require BaO, but the inclusion of small amounts of BaO (e.g., up to about 1 weight percent) can not be excluded. Similarly, although large amounts of ZnO are not required in the present invention, in some embodiments small amounts (eg, up to about 2.0 weight percent) may be included. In embodiments of the present invention where the optional constituents are minimal, the total amount of optional constituents is 2 weight percent or less, or 1 weight percent or less. Alternatively, some embodiments of the invention may be said to consist essentially of the named components.

The choice of batch components and their cost depend significantly on their purity requirements. For example, typical commercially available components for the preparation of E-glass include impurities such as Na ₂ O, K ₂ O, Fe ₂ O ₃ or FeO, SrO, F ₂ , TiO ₂ , SO ₃ etc. Contained in the form. Most of the cations derived from such impurities can increase the D _k of the glass by forming non-crosslinked oxygen with the SiO ₂ and / or B ₂ O ₃ of the glass.

Also, sulfate (denoted as SO ₃ ) may be present as a fining agent. Also, small amounts of impurities derived from raw materials or mixed in the melt process, such as SrO, BaO, Cl ₂ , P ₂ O ₅ , Cr ₂ O ₃ or NiO (not limited to these specific chemical forms) It is also possible to do. Also, other fining and / or processing aids may be present, such as, but not limited to, As ₂ O ₃ , MnO, MnO ₂ , Sb ₂ O ₃ or SnO ₂ . Such impurities and fining agents, if present, are each typically present in an amount of less than 0.5% by weight of the total glass composition. Optionally, an element of the rare earth group of the periodic table of the elements, for example, atomic numbers 21 (Sc), 39 (Y) and 57 (La) to 71 (Lu) may be added to the composition of the invention . These can serve either as processing aids or to improve the electrical, physical (thermal or optical), mechanical and chemical properties of the glass. Rare earth additives may be included in view of the original chemical form and oxidation state. The addition of rare earth elements is considered optional in the embodiments of the present invention with the purpose of minimizing raw material costs, in particular, since even low concentrations can increase batch costs. In any case, typically, depending on the cost, a rare earth component (measured as an oxide), if contained, in an amount of about 0.1 to 1.0% by weight or less of the total amount of the glass composition It can be determined to exist.

Glass fibers, fiber glass strands, and other articles incorporating such fibers or strands, in some embodiments of the present invention, particularly fiber glass strands formed of E-glass fibers, E-glass and related It may exhibit desirable mechanical properties as compared to the product. For example, some embodiments of the glass fibers of the present invention may have relatively high specific strength or relatively high specific modulus, especially when compared to E-glass fibers. Specific strength refers to tensile strength (unit: N / m ² ) divided by unit volume weight (unit: N / m ³ ). The specific elastic modulus refers to Young's modulus (unit: N / m ² ) divided by unit volume weight (unit: N / m ³ ). Glass fibers with relatively high specific strength and / or relatively high specific modulus may be desirable in applications where it is desirable to reduce the overall weight of the composite with increased mechanical properties or product performance. Examples of such composites are given above and include, for example, aerospace or aerospace applications (eg, floor inside aircraft), wind energy applications (eg, wind turbine blades), fiber-metal laminate applications, etc. . As another example of mechanical properties, some embodiments of the fiber glass strands of the present invention in the form of rovings are rovings incorporating E-glass fiber glass strands (eg, on the order of 350-400 ksi according to ASTM D2343) It may exhibit increased tensile strength (e.g., in some embodiments, on the order of 400-430 ksi according to ASTM D 2343).

  After forming, the glass fibers are typically at least partially coated with a sizing composition, as is known in the art. Generally, the glass fiber used to form the fiber glass strands, fabrics, composites, laminates and prepregs of the present invention is at least partially coated with a sizing composition. Those skilled in the art will appreciate that many commercial sizings for glass fibers based on several factors, such as the performance characteristics of the sizing composition, the flexibility desired for the resulting fabric, cost etc, and other factors. One of the compositions may be selected. Non-limiting examples of commercially available sizing compositions that may be used in some embodiments of the present invention include sizing compositions often used for single-ended roving (Hybon 2026, Hybon 2002, Hybon 1383, Hybon 2006, Hybon 2022, Hybon 2032, Hybon 2016, and Hybon 1062), and sizing compositions often used for yarns (such as 1383, 611, 900, 610, 695, and 690) Each of these represents a sizing composition for products commercially available from PPG Industries, Inc.).

  As mentioned above, some embodiments of the present invention may include cloth. Any suitable fabric design known to those skilled in the art for reinforcement applications may be used. Suitable fabrics may include fabrics made using standard textile equipment (eg, rapier, projectile, air jet looms). Non-limiting examples of such fabrics include plain weave, twill weave, zigzag twill weave, and satin weave. Also, stitch bonded or non-crimp fabrics may be used in some embodiments of the present invention. Such fabrics may include, for example, unidirectional, biaxial and triaxial non-crimp fabrics. Also, 3D fabrics may be used in some embodiments of the present invention. Such fabrics can be made with the use of either dobby or a jacquard head, with a multi-layered warp end with shedding.

  As noted above, the composites of the present invention may include warp and weft yarns. Any suitable warp and fill known to those skilled in the art for reinforcing applications may be used. In some embodiments, for example, the warp may include G75 yarns, DE75 yarns, DE150 yarns, and / or G150 yarns.

  As mentioned above, the composite of the present invention may include a polymeric resin in some embodiments. Various polymeric resins may be used. Polymeric resins that are known to be useful for reinforcing applications may be particularly useful in some embodiments. In some embodiments, the polymeric resin can comprise a thermosetting resin. Thermoset resin systems useful in some embodiments of the present invention include, but are not limited to, epoxy resins, phenolic resins, polyesters, vinyl esters, thermosetting polyurethanes, polydicyclopentadiene (pDCPD) resins, cyan Acid esters, and bis-maleimides can be mentioned. In some embodiments, the polymeric resin can include an epoxy resin. In another embodiment, the polymeric resin may comprise a thermoplastic resin. Thermoplastic polymers useful in some embodiments of the present invention include, but are not limited to, polyethylene, polypropylene, polyamide (eg, nylon), polybutylene terephthalate, polycarbonate, thermoplastic polyurethane (TPU), polyphenylene sulfide, and poly Ether ether ketone (keteone) (PEEK) is mentioned. Non-limiting examples of commercially available polymeric resins useful in some embodiments of the present invention include EPIKOTE Resin MGS® RIMR 135 Epoxy and Epikure MGS RIMH 1366 curing agents (Momentive Specialty Chemicals Inc. (Columbus (O.I. Ohio), Applied Polaramic MMFCS 2 epoxy (available from Applied Polaramic, Inc. (Benicia, California)), and EP 255 modified epoxy (available from Barrday Composite Solutions (Millbury, Mass.)).

EXAMPLES Some illustrative embodiments of the present invention will now be illustrated by the following specific non-limiting examples.

Example 1
Several properties of glass compositions useful in some embodiments of the present invention were measured under controlled processing conditions using conventional test methods known to those skilled in the art. Some of the measured characteristics are shown in Table 1. Properties of standard E-glass and commercially available NE-glass are also included for reference. The properties shown for the commercial NE-glass are from the literature. The data in Table 1 show that glass fibers suitable for use in the present invention exhibit improved thermal, chemical and mechanical stability as compared to E-glass. Compared to NE-fibers, glass fibers suitable for use in the present invention have 30% higher strength and 25% higher stiffness. As measured by x-ray fluorescence spectroscopy, the glass fibers of test strip 1 in Table 1
SiO ₂ 63.02 ± 0.25 weight percent;
B ₂ O ₃ 9.39 ± 0.15 weight percent;
Al ₂ O ₃ 11.60 ± 0.10 weight percent;
MgO 11.06 ± 0.15 weight percent;
CaO 2.54 ± 0.10 weight percent;
Na ₂ O 0.38 ± 0.02 weight percent;
K ₂ O 0.12 ± 0.01 weight percent;
Fe ₂ O ₃ 0.25 ± 0.05 weight percent;
F ₂ 0.72 ± 0.15 weight percent;
TiO ₂ 0.10 ± 0.01 weight percent;
A glass composition was included comprising: Li ₂ O 0.81 ± 0.05; and 0.02 weight percent SO ₃ .

Example 2
In this example, the yarn breaking load of yarns formed of the fiber glass strands of the present invention ("test strip yarns") was determined using yarns formed of fiber glass strands formed of the conventional 621 glass composition ("621 Compared to "Yarn"). Each yarn was formed of a single fiber glass strand having approximately 200 filaments with a nominal diameter of 7 microns. After forming, the glass fibers were coated with a conventional starch oil sizing composition. The fiber glass strand is dried and then twisted one turn per inch in the z direction to form a yarn, which is then plain weave with 60 picks per inch in the warp direction and 58 picks per inch in the weft direction. Weaved in style cloth.

The breaking load of the fabric was then measured using ASTM 5053. A paper tab was attached to a 1-inch wide by 6-inch long strip of fabric and loaded at a rate of 12 inches / minute until it broke on the universal test frame. A total of 12 breaking load measurements were made per fabric. The average breaking load of the prepared fabric strip in specimen yarn is 197.5lb _f, the average breaking load of the prepared fabric strip at 621 yarn was 181.7lb _f. The fabric was then heat cleaned and finished using the same conventional procedure. After heat cleaning and finishing, the breaking load of the fabric strips was again measured using ASTM 5035. A total of 12 breaking load measurements were made. The average breaking load of the specimen fabric is 119.5lb _f, the average breaking load of 621 cloth was 85.1lb _f. The breaking load retention of the 621 fabric (the breaking load after heat cleaning / finish divided by the breaking load before heat cleaning / finish multiplied by 100) was 46.8%. The breaking load retention of the specimen cloth (the breaking load after heat cleaning / finish divided by the breaking load before heat cleaning / finishing) was 60.5%, showing improvement in breaking load compared to the 621 cloth .

Example 3
The tensile and impact properties of the laminates of the present invention were compared to those of laminates made of glass fibers containing conventional glass compositions. In this example, the fabric was a woven fabric ("test strip fabric") in which warp and weft yarns made of fiber glass strands having the glass composition of the present invention were used. The comparison fabric was formed of standard E-glass yarn ("E-glass fabric"). Further details regarding the fabric are given in Table 2.

  The pre-impregnated fabric was then incorporated into the laminate using vacuum assisted compression molding. The polymeric resin used was an EP 255 modified epoxy resin from Barrday Composite Solutions (Millbury, Mass.). Ten fabric layers were incorporated into each laminate. The processing conditions in Table 3 were used for vacuum assisted compression molding settings:

Sufficient cure of the resin was confirmed by measurement of the glass transition temperature (T _g ) of the composite (115.03 ° C. for the test strip laminate, 116.57 ° C. for the E-glass laminate). The fiber weight fraction of the test piece laminate was 65.72% glass, and the fiber weight fraction of the E-glass laminate was 67.39% glass.

  The tensile properties of the laminate were measured according to ISO 527-4. Five coupon laminates and five E-glass laminates were analyzed. Initial evaluation of the data showed a slight increase in the average tensile strain to failure of the specimen stack as compared to the E-glass laminate (2.15% vs 1.95%). It was also shown that the test piece laminate had a slightly higher tensile strength and a lower tensile modulus. However, such a trend could not be considered statistically significant after performing analysis of variance (ANOVA).

  The impact properties of the laminates were also measured according to ASTM 3763 on specimens of equivalent thickness using a 3/8 "hemispherical impactor and an instrumented impact tester. Test specimen laminates and E-glass laminates It was observed that the impact properties of the body were significantly different: in all cases, with the test strip laminate a significant increase in impact performance (indicated by the high energy at maximum load and the total energy absorbed by the test strip) The average energy for the maximum load was 30.984 joules for the specimen stack and 14.204 joules for the E-glass laminate.The average total energy absorbed is the specimen laminate. And 35.34 joules for E-glass laminates, and 26.76 joules for E-glass laminates, so for specimen strip laminates E at the same impact rate The average 32% more energy than the glass laminate was absorbed. Moreover, the test strip stack, damage is much less indicated than E- glass laminate, but failed to penetrate.

Example 4
The glass of this example is prepared by melting a mixture of chemicals in powder form in reagent grade for 4 hours in a 10% Rh / Pt crucible at a temperature of 1500 ° C. to 1550 ° C. (2732 ° F. to 2822 ° F.) Made. Each batch was about 1200 grams. After a melting period of 4 hours, the molten glass was poured onto a steel plate and quenched. In order to compensate for the B ₂ O ₃ volatilization loss (typically about 5% of the target total B ₂ O ₃ concentration in laboratory batch melting conditions with a batch size of 1200 grams), the boron retention factor in the batch calculation It was set to 95%. Other volatile species (such as fluoride and alkali oxides) did not adjust their emission loss in batches because of their low concentration in the glass. The compositions of the examples represent as-batched compositions. Because the B ₂ O ₃ was sufficiently adjusted to use reagent chemicals in the preparation of the glass, the indicated batch composition is considered to be close to the measured composition.

  Melt viscosity and liquidus temperature as a function of temperature, ASTM Test Method C965 "Standard Practice for Measuring Viscosity of Glass Above the Softening Point" and C829 "Standard Practice for Measurement of Liquidus Temperature of Glass by the Gradient Furnace Method, respectively. It measured by using ".

An abrasive disc of each glass specimen having a diameter of 40 mm and a thickness of 1 to 1.5 mm was used for the measurement of the electrical and mechanical properties, which was made of annealed glass. The dielectric constant (D _k ) and dissipation factor (D _f ) of each glass are from 1 MHz to 1 GHz. ASTM Test Method D150 “Standard Test Methods for AC Loss Characteristics and Permittivity (Dielectric Constant) of Solid Electrical Insulating Materials” Measured by Following this procedure, all specimens were preconditioned for 40 hours at 25 ° C. and 50% humidity. The glass density was selectively tested using ASTM Test Method C 729 "Standard Test Method for Density of Glass by the Sink-Float Comparator," and all test pieces were annealed for the test.

For selected compositions, using the micro-indentation method, Young's modulus (from the initial slope of the indentation load-indentation curve, in the indenter unloading cycle), and microhardness (maximum indentation load and maximum indentation depth) ) Was measured. The same disc specimens (tested for D _k and D _f ) were used for the test. Five indentation measurements were performed to obtain data on average Young's modulus and microhardness. The microindentation device was calibrated using a commercially available standard reference glass block with the product name BK7. This reference glass has a Young's modulus of 90.1 GPa (one standard deviation of 0.26 GPa) and a microhardness of 4.1 GPa (one standard deviation of 0.02 GPa) (all based on 5 measurements) ).

All compositional values in the examples are given in weight percent. In the following table, "E" indicates Young's modulus; "H" indicates microhardness; σ _f indicates filament strength; "Std" indicates standard deviation.

Table 4 Composition Test pieces 1 to 8 were glass compositions in weight percentage (Table 4): SiO ₂ 62.5 to 67.5%, B ₂ O ₃ 8.4 to 9.4%, Al ₂ O ₃ 10 .3 to 16.0%, MgO 6.5 to 11.1%, CaO 1.5 to 5.2%, Li ₂ O 1.0%, Na ₂ O 0.0%, K ₂ O 0.8 %, Fe ₂ O ₃ 0.2-0.8%, F ₂ 0.0%, TiO ₂ 0.0%, and sulfate (denoted as SO ₃ ) 0.0%.

Glass, of 5.44 to 5.67 at 1 MHz _{D k} and 0.0006 to 0.0031 of Df, _D of 5.47 to 6.67 at 1GHz frequency _k and 0.0048 to 0.0077 of _{D f} It turned out that it is what it has. The electrical properties of the compositions of the series III, standard E- glass (at 1 MHz 7.29 _{D k} and 0.003 of _D f, the _{D k} and 0.0168 of _{D f} of 7.14 in 1GHz Significantly smaller (ie, improved) D _k and D _f are shown as compared to having.

With respect to fiber molding properties, the compositions of Table 4 have a molding temperature (T _F ) of 1300-1372 ° C. and a molding window (T _F -T _L ) of 89-222 ° C. This can be compared to standard E-glass (typically with a T _F in the range of 1170 to 1215 ° C.). A forming window (T _F -T _L ) greater than 55 ° C. is desirable to suppress glass devitrification in fiber forming. The compositions in Table 4 all show satisfactory forming windows. The compositions in Table 4 have higher forming temperatures than E-glass, but have significantly lower forming temperatures than D-glass (typically about 1410 ° C.).

Table 5 Composition Test pieces 9 to 15 are glass compositions: SiO ₂ 60.8 to 68.0%, B ₂ O ₃ 8.6 to 11.0%, Al ₂ O ₃ 8.7 to 12.2%, MgO 9.5 to 12.5%, CaO 1.0 to 3.0%, Li ₂ O 0.5 to 1.5%, Na ₂ O 0.5%, K ₂ O 0.8%, Fe ₂ It shows 0.4% O _3, 0.3% F _2, 0.2% TiO ₂ , and 0.0% sulfate (denoted as SO ₃ ).

Glass, of 5.55 to 5.95 at 1 MHz _{D k} and 0.0002 to 0.0013 of _D f, D of _{D k} and 0.0040 to 0.0058 of 5.54 to 5.94 at 1GHz frequency It turned out that it is what has _f . The electrical characteristics of the composition of Table 5, the standard E- glass (at 1 MHz 7.29 _{D k} and 0.003 of _D f, the _{D k} and 0.0168 of _{D f} of 7.14 in 1GHz Significantly smaller (improved) D _k and D _f are shown compared to having.

  In terms of mechanical properties, the compositions of Table 5 have a Young's modulus of 86.5 to 91.5 GPa and a microhardness of 4.0 to 4.2 GPa, both of which are standard E-glass (85.9 GPa Have a Young's modulus and a microhardness of 3.8 GPa) or higher. Also, the Young's modulus of the compositions in Table 5 is also significantly higher than D-glass (about 55 GPa based on literature data).

In terms of fiber molding properties, the compositions of Table 5 have a molding temperature (T _F ) of 1224 to 1365 ° C. and a molding window (T _F -T _L ) of 6 to 105 ° C., while the standard E- The glass has a T _F in the range of 1170 to 1215 ° C. Some (but not all) of the compositions in Table 5 have molding windows (T _F -T _L ) greater than 55 ° C., which, in some situations, are in commercial fiber molding operations It is considered preferable to avoid devitrification of the glass. The compositions in Table 5 have forming temperatures lower than that of D-glass (1410 ° C.) but higher than E-glass.

Test pieces 29 to 62 were glass compositions in weight percentage (Table 8): SiO ₂ 53.74 to 76.97%, B ₂ O ₃ 4.47 to 14.28%, Al ₂ O ₄ 4.63 15.44%, MgO 4.20 to 12.16%, CaO 1.04 to 10.15%, Li ₂ O 0.0 to 3.2%, Na ₂ O 0.0 to 1.61%, K ₂ O 0.01 to 0.05%, Fe ₂ O ₃ 0.06 to 0.35%, F ₂ 0.49 to 1.48%, TiO ₂ 0.05 to 0.65%, and sulfate (SO 2 ₃ ) from 0.0 to 0.16%.

Test pieces 29-62 show the glass composition in weight percentage (Table 8), where the (MgO + CaO) content is 7.81 to 16.00% and the CaO / MgO ratio is 0.09 to 1. It is 74%, the (SiO ₂ + B ₂ O ₃ ) content is 67.68 to 81.44%, the Al ₂ O ₃ / B ₂ O ₃ ratio is 0.90 to 1.71%, (Li 2 O) content ₂ O ₊ Na ₂ O _{+ K} is _{0.03~3.38%, Li 2 O / (} Li 2 O + Na 2 O + K 2 O) ratio is 0.00 to 0.95 percent.

For mechanical properties, the compositions in Table 8 have an average fiber tensile strength of the fiber density and 3050~3578MPa of 2.331~2.416g / cm ³ (or fiber strength).

  In order to measure fiber tensile strength, fiber specimens made of glass compositions were made with a 10 Rh / 90 Pt single tip fiber draw unit. Approximately 85 grams of cullet of a given composition was fed into a bushing melt unit and conditioned for 2 hours at a temperature close to or equivalent to 100 poise melt viscosity. Subsequently, the melt was lowered to a temperature close to or equivalent to 1000 poise melt viscosity and stabilized for 1 hour, followed by fiber drawing. The fiber diameter was controlled to produce fibers of approximately 10 μm diameter by controlling the speed of the fiber draw-winder. All fiber specimens were captured in air without contact with any foreign material. The drawing of the fibers was completed in a room under controlled humidity of 40-45% RH.

  Fiber tensile strength was measured using a Kawabata KES-G1 (Kato Tech Co., Japan) tensile strength analyzer equipped with a Kawabata C-type load cell. Fiber specimens were loaded with resin adhesive on framing paper strips. Tension was applied to the fiber until it broke, whereby the fiber strength was determined based on the fiber diameter and the breaking stress. The test was performed at room temperature under controlled humidity of 40-45% RH. Mean values and standard deviations were calculated by computer based on the 65-72 fiber specimen size for each composition.

The glass was found to be one having a D _k of 4.83 to 5.67 and a D _f of 0.003 to 0.007 at 1 GHz. The electrical properties of compositions of Table 8, significantly smaller than the standard E- glass (having a _{D k} and 0.0168 of _{D f} of 7.14 in 1 GHz) (i.e., improved) D _k and D _f are shown.

In terms of fiber molding properties, the compositions of Table 8 have molding temperatures (T _F ) of 1247 to 1439 ° C. and molding windows (T _F -T _L ) of 53 to 243 ° C. The compositions in Table 8 have liquidus temperatures (T _L ) of 1058 to 1279 ° C. This can be compared to standard E-glass (typically with a T _F in the range of 1170 to 1215 ° C.). A molding window (T _F -T _L ) greater than 55 ° C. is sometimes desirable to suppress glass devitrification in fiber molding. The compositions in Table 8 all show satisfactory forming windows.

Test pieces 63 to 73 are glass compositions in weight percentage (Table 9): SiO ₂ 62.35 to 68.35%, B ₂ O ₃ 6.72 to 8.67%, Al ₂ O ₃ 10.53 to 18.04%, MgO 8.14 to 11.44%, CaO 1.67 to 2.12%, Li ₂ O 1.07 to 1.38%, Na ₂ O 0.02%, K ₂ O 0. 03 to 0.04%, Fe ₂ O ₃ 0.23 to 0.33%, F ₂ 0.49 to 0.60%, TiO ₂ 0.26 to 0.61%, and sulfate (denoted as SO ₃ ) It shows 0.0%.

Specimens 63-73 show the glass composition in weight percentage (Table 9), where the (MgO + CaO) content is 9.81-13.34% and the CaO / MgO ratio is 0.16-0. 20, the (SiO ₂ + B ₂ O ₃ ) content is 69.59 to 76.02%, the Al ₂ O ₃ / B ₂ O ₃ ratio is 1.37 to 2.69, (Li ₂ O + Na _{The 2} O + K ₂ O) content is 1.09 to 1.40%, and the Li ₂ O / (Li ₂ O + Na ₂ O + K ₂ O) ratio is 0.98.

In terms of mechanical properties, the compositions of Table 9 have a fiber density of 2.371 to 2.407 g / cm ³ and an average fiber tensile strength (or fiber strength) of 3730 to 4076 MPa. The fiber tensile strength of the fibers made with the compositions of Table 9 was measured in the same manner as the fiber tensile strength measured for the compositions of Table 8.

The fibers formed with the composition were found to have Young's modulus (E) values in the range of 73.84 to 81.80 GPa. The value of the Young's modulus (E) of the fiber was measured using the ultrasonic elastic modulus method on the fiber. The values of the modulus of elasticity of the glass melt drawn fibers having the described composition were measured on a Panatherm 5010 instrument (from Panametrics, Inc. (Waltham, Mass.)) Using an acoustic ultrasonic pulse technique. Stretch wave reflection times were obtained using 200 kHz pulses, with a duration of 20 microseconds.
The length of the test piece was measured, and the stretching wave velocity (V _E ) of each was calculated. Fiber density (ρ) was measured using a Micromeritics AccuPyc 1330 pycnometer.
In general, 20 measurements were made for each composition and the average Young's modulus (E) was calculated according to the formula E = _VE ² × ρ. The strain at break of the fiber was calculated using Hooke's law based on known fiber strength and Young's modulus values.

Glass was found to be one having a Df of _{D k} and 0.0010 to 0.0020 of 5.20 to 5.54 at 1 GHz. The electrical characteristics of the composition of Table 9, significantly smaller than the standard E- glass (having a _{D k} and 0.0168 of _{D f} of 7.14 in 1 GHz) (i.e., improved) D _k and D _f are shown.

In terms of fiber molding properties, the compositions of Table 9 have a molding temperature ( _TF ) of 1303-1388C and a molding window ( _TF - _TL ) of 51-144C.

  Desirable properties that may be exhibited by various (but not necessarily all) embodiments of the present invention include, but are not limited to: glass fibers with relatively low density, fiber glass strands, glass fiber cloth, composites And provision of laminates; provision of glass fibers having relatively high elastic modulus, fiber glass strands, fiber glass cloth, composites and laminates; Providing composites and laminates; Providing glass fibers useful for reinforcing applications, fiber glass strands, glass fiber cloths, composites, laminates and prepregs; and other glass fibers for reinforcing applications, fiber glass strands, glass Glass fiber with relatively low cost compared to fiber cloth, composites, laminates and prepregs Scan strands, glass fiber cloth, composites, may be mentioned the provision of laminates and prepregs.

  Various embodiments of the invention have been described in fulfillment of the various objects of the invention. It should be recognized that these embodiments are merely illustrative of the principles of the present invention. Many modifications and adaptations are readily apparent to one skilled in the art without departing from the spirit and scope of the present invention.

Claims (37)

The following ingredients:
SiO ₂ 60-68 weight percent;
B ₂ O ₃ 7 to 12 weight percent;
Al ₂ O ₃ 9-15% by weight;
MgO 8 to 15 weight percent;
CaO 0-4 weight percent;
Li ₂ O 0-2% by weight;
Na ₂ O 0 to 1% by weight;
K ₂ O 0 to 1% by weight;
Fe ₂ O ₃ 0-1% by weight;
F ₂ 0 to 1 weight percent;
TiO ₂ 0-2 weight percent; and other constituents in total 0-5 weight percent;
Including
(Li ₂ O + Na ₂ O + K ₂ O) content is less than 2 weight percent, MgO content is at least twice the content of CaO on a weight percent basis,
A fiber glass strand comprising a plurality of glass fibers comprising a glass composition. A yarn comprising at least one fiber glass strand according to claim 1. The yarn of claim 2, wherein the at least one fiber glass strand is at least partially coated with a sizing composition. The yarn of claim 2, wherein the plurality of glass fibers have a diameter of about 5 to about 13 μm. A fabric formed of at least one fiber glass strand according to claim 1. A fabric comprising at least one weft comprising at least one fiber glass strand according to claim 1. A fabric comprising at least one warp comprising at least one fiber glass strand according to claim 1. At least one weft comprising at least one fiber glass strand according to claim 1;
A fabric comprising at least one warp comprising at least one fiber glass strand according to claim 1. 9. The fabric of claim 8, wherein the fabric comprises plain weave, twill weave, zigzag fabric, satin weave, stitch bonded weave, or 3D weave. A composite material comprising: a polymer resin; and the glass fiber derived from the fiber glass strand according to claim 1 disposed in the polymer resin. A composite comprising a polymeric resin; and at least one fabric formed of at least one fiber glass strand according to claim 1. The composite of claim 11, wherein the polymeric resin comprises an epoxy resin. The polymer resin is polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenol type, polyester, vinyl ester, polydicyclopentadiene, polyphenylene sulfide, polyetheretherketone, cyanate ester, bis- The composite of claim 11, comprising at least one of maleimide and a thermosetting polyurethane resin. The composite of claim 11, wherein the fabric comprises plain weave, twill weave, zigzag fabric, satin weave, stitch bonded weave, or 3D weave. An aerospace composite comprising the composite of claim 11. A composite for the aircraft industry comprising the composite of claim 11. A radome comprising the composite of claim 11. A prepreg comprising a polymeric resin; and at least one fiber glass strand according to claim 1. A prepreg according to claim 20;
A first metal sheet adhesively fixed to one surface of the prepreg; and a second metal sheet adhesively fixed to the second surface of the prepreg,
Said prepreg is arranged between said two metal sheets,
Fiber-metal laminate. Claim 20 further comprising a second prepreg and a third metal sheet according to claim 20, wherein the second prepreg is disposed between the second metal sheet and the third metal sheet. The fiber-metal laminate according to 19. 20. The fiber-metal laminate of claim 19, wherein the metal sheet comprises aluminum. 20. The fiber-metal laminate of claim 19, wherein the polymeric resin comprises epoxy. Polymeric resin; and multiple fiber glass cloth,
At least one fabric is formed of at least one fiber glass strand according to claim 1.
Stack. A polymer resin; and a plurality of glass fibers disposed in the polymer resin,
At least one of the plurality of glass fibers comprises the following components:
SiO 2 53.5-77 weight percent;
B2O3 4.5 to 14.5 weight percent;
Al2O3 4.5 to 18.5% by weight;
MgO 4 to 12.5 weight percent;
CaO 0-0.5% by weight;
Li2O 0-4 weight percent;
0 to 2 weight percent Na2O;
K2O 0-1 weight percent;
0 to 1 weight percent of Fe2O3;
F2 0-2 weight percent;
0-2 weight percent TiO2; and other constituents including a glass composition comprising 0 to 5 weight percent in total
Composite material. 25. The composite of claim 24, wherein the plurality of glass fibers are arranged to form a fabric. 25. The composite of claim 24, wherein the fabric comprises plain weave, twill weave, twill weave, satin weave, stitch bonded weave, or 3D weave. 25. The composite of claim 24, wherein the polymeric resin comprises an epoxy resin. The polymer resin is polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenol type, polyester, vinyl ester, polydicyclopentadiene, polyphenylene sulfide, polyetheretherketone, cyanate ester, bis- 25. The composite of claim 24, comprising at least one of maleimide and a thermosetting polyurethane resin. An aerospace composite comprising the composite of claim 24. An aircraft industry composite comprising the composite of claim 24. A radome comprising the composite of claim 24. A prepreg comprising the composite according to claim 24. The prepreg according to claim 32;
A first metal sheet adhesively fixed to one surface of the prepreg; and a second metal sheet adhesively fixed to the second surface of the prepreg,
Said prepreg is arranged between said two metal sheets,
Fiber-metal laminate. Furthermore, it comprises a second prepreg according to claim 32 and a third metal sheet, and the second prepreg is disposed between the second metal sheet and the third metal sheet. The fiber-metal laminate according to claim 33. 34. The fiber-metal laminate of claim 33, wherein the metal sheet comprises aluminum. 34. The fiber-metal laminate of claim 33, wherein the polymeric resin is epoxy. A laminate comprising the prepreg according to claim 32.