WO2012037219A1 - Low density and high strength fiber glass for reinforcement applications - Google Patents
Low density and high strength fiber glass for reinforcement applications Download PDFInfo
- Publication number
- WO2012037219A1 WO2012037219A1 PCT/US2011/051555 US2011051555W WO2012037219A1 WO 2012037219 A1 WO2012037219 A1 WO 2012037219A1 US 2011051555 W US2011051555 W US 2011051555W WO 2012037219 A1 WO2012037219 A1 WO 2012037219A1
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- WO
- WIPO (PCT)
- Prior art keywords
- weight percent
- glass
- fiber
- fabric
- present
- Prior art date
Links
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
- D02G3/16—Yarns or threads made from mineral substances
- D02G3/18—Yarns or threads made from mineral substances from glass or the like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
Definitions
- the present invention relates to low density and high strength glass fibers and yarns, fabrics, and composites comprising low density and high strength glass fibers adapted for use in reinforcement applications.
- Glass fibers have been used to reinforce various polymeric resins for many years.
- Some commonly used glass compositions for use in reinforcement applications include the “E-glass” and “D-glass” families of compositions.
- Another commonly used glass composition is commercially available from AGY (Aiken, South Carolina) under the trade name "S-2 Glass.”
- Glass fibers have been arranged to form fabrics for many years.
- a glass fabric is woven by interweaving weft yarns (also referred to as "fill yarns") into a plurality of warp yarns.
- weft yarns also referred to as "fill yarns”
- this is accomplished by positioning the warp yarns in a generally parallel, planar array on a loom, and thereafter weaving the weft yarns into the warp yarns by passing the weft yarns over and under the warp yarns in a predetermined repetitive pattern.
- the pattern used will depend upon the desired fabric style.
- Warp yarns are typically formed by attenuating a plurality of molten glass streams from a bushing or spinner. Thereafter, a coating (or primary sizing composition) is applied to the individual glass fibers and the fibers are gathered together to form a strand. The strands are subsequently processed into yarns by transferring the strands to a bobbin via a twist frame. During this transfer, the strands can be given a twist to aid in holding the bundle of fibers together. These twisted strands are then wound about the bobbin and the bobbins are used in the weaving processes.
- a coating or primary sizing composition
- a loom beam comprises a specified number of warp yarns (also referred to as "ends") wound in an essentially parallel arrangement (also referred to as "warp sheet”) about a cylindrical core.
- Loom beam preparation typically requires combining multiple yarn packages, each package comprising a fraction of the number of ends required for the loom beam, into a single package or loom beam. For example and although not limiting herein, a 50 inch (127 cm) wide, 7781 style fabric which utilizes a DE75 yarn input typically require 2868 ends. However, conventional equipment for forming a loom beam does not allow for all of these ends to be transferred from bobbins to a single beam in one operation.
- a section beam typically includes a cylindrical core comprising a plurality of essentially parallel warp yarns wound thereabout. While it will be recognized by one skilled in the art that the section beam can comprise any number of warp yarns required to form the final loom beam, generally the number of ends contained on a section beam is limited by the capacity of the warping creel. For a 7781 style fabric, four section beams of 717 ends each of DE75 are typically provided and when combined offer the required 2868 ends for the warp sheet, as discussed above.
- a primary sizing composition is applied to the glass fibers, typically immediately after forming.
- the filaments forming the continuous glass fiber strands used in weaving fabric are treated with an aqueous starch- oil sizing, which typically includes partially or fully dextrinized starch or amylose, hydrogenated vegetable oil, a cationic wetting agent, emulsifying agent, and water, as is well known to those skilled in the art.
- an aqueous starch- oil sizing typically includes partially or fully dextrinized starch or amylose, hydrogenated vegetable oil, a cationic wetting agent, emulsifying agent, and water, as is well known to those skilled in the art.
- sizing compositions are generally robust enough to provide protection to the fibers during fiber forming and loom beam manufacturing processes, they normally are unable to protect the glass fibers, and in particular the warp yarn fibers, from abrasion and wear during high speed weaving.
- the slashing size includes either fully or partially hydrolyzed polyvinyl alcohol (PVA) materials and is a mixture in the 6-8% solids range with a viscosity of 15 to 20 centipoise (CPS).
- PVA polyvinyl alcohol
- CPS centipoise
- the slashing size is typically applied by submerging the warp yarn sheet in a vessel containing the slashing size via a series of submersion rollers and then passing it through a squeeze roll system, which typically exerts 15 to 20 pounds per square inch of squeezing pressure on the coated yarn in addition to the dead weight of the squeeze roller (the squeeze pressure can vary due to yarn diameter), to remove the excess slashing size.
- the slashing size can be applied at an elevated temperature, e.g., in the range of 130 to 150 °F (54 to 66 °C) or at room temperature, depending upon the recommendations of the PVA producer.
- the slashing sized sheet is dried in any convenient manner known in the art, such as but not limited to passing the sheet over heated rollers and/or through a hot air drying oven.
- the surface temperature of the cans is typically in the range of 240 to 280 °F (1 16 to 138 °C).
- the actual temperature profile of the drying cans depends in part on the can arrangement, number of cans, and yarn speed.
- the air temperature within the oven typically ranges from 275 to 300 °F (135 to 149 °C).
- the warp yarn sheet passes through a series of split rods to separate the warp sheets and through a hook reed assembly and comb to combine the warp sheets and assure that no ends are adhered to each other.
- the yarn sheet is then wound onto the loom beam.
- Both the primary starch-oil coating and slashing size are not compatible with polymeric resin matrix materials used to impregnate woven fabric incorporating the coated yams. As a result, these coatings must be removed from the fabric, e.g., by heat cleaning and/or scrubbing, prior to incorporation of a fabric woven from these yarns into the matrix material.
- a typical one-step heat cleaning process can entail heating the fabric at 600 to 800 °F (316 to 427 °C) for 70-80 hours to remove the starch- oil primary sizing composition and slashing size.
- the fabric is unrolled through an oven where it is exposed to a flame that burns off a portion of the sizes, and then heated at 600 to 800 °F (316 to 427 °C) for 50 to 60 hours.
- the first step of this two-step operation is sometimes referred to as caramelizing and is typically used to heat clean fabrics woven from coarse yarns, i.e., 7628 style fabric.
- Rolled ends which is a condition wherein adjacent glass strands roll on top of each other and are twisted together, are particularly troublesome as they can lead to end breaks during weaving, which in turn are associated with fabric quality issues such as ends out, fuzzy ends, chaffed ends, and undesirable yarn splices.
- Various embodiments of the present invention relate generally to low density and high strength glass fibers, and to fiber glass strands, yarns, fabrics, and composites comprising low density and high strength glass fibers adapted for use in reinforcement applications. Some embodiments of the present invention relate to fiber glass strands.
- a number of fiberizable glass compositions are disclosed herein as part of the present invention, and it should be understand that various embodiments of the present invention can comprise glass fibers, fiber glass strands, yarns, and other products incorporating glass fibers formed from such compositions.
- a fiber glass strand of the present invention comprises a plurality of glass fibers comprising a glass composition that comprises the following components:
- the (Li20 + Na20 + 20) content is less than 2 weight percent and wherein the MgO content is at least twice the content of CaO on a weight percent basis.
- a fiber glass strand of the present invention comprises a plurality of glass fibers comprising a glass composition that comprises the following components:
- the plurality of glass fibers can have a diameter between about 5 microns and about 13 microns.
- the fiber glass strand is at least partially coated with a sizing composition.
- Some embodiments of the present invention relate to yarns formed from at least one fiber glass strand formed from a glass composition described herein. Some embodiments of the present invention relate to fabrics incorporating at least one fiber glass strand formed from a glass composition described herein.
- a fill yarn used in the fabric can comprise the at least one fiber glass strand.
- a warp yarn in some embodiments, can comprise the at least one fiber glass strand.
- fiber glass strands can be used in both fill yarns and warp yarns used to form fabrics according to the present invention.
- fabrics of the present invention can comprise a plain weave fabric, a twill fabric, a crowfoot fabric, a satin weave fabric, a stitch bonded fabric, or a 3D woven fabric.
- Some embodiments of the present invention relate to composites comprising a polymeric resin and glass fibers formed from one of the various glass compositions described herein.
- the glass fibers can be from a fiber glass strand according to some embodiments of the present invention.
- the glass fibers can be incorporated into a fabric, such as a woven fabric.
- the glass fibers can be in a fill yarn and/or a warp yarn that are woven to form a fabric.
- the composite comprises a fabric
- the fabric can comprise a plain weave fabric, a twill fabric, a crowfoot fabric, a satin weave fabric, a stitch bonded fabric, or a 3D woven fabric.
- the glass fibers can be incorporated into the composite in other forms as well as discussed in more detail below.
- composites of the present invention can comprise one or more of a variety of polymeric resins.
- the polymeric resin comprises at least one of polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, polydicyclopentadiene, polyphenylene sulfide, polyether ether ketone, cyanate esters, bis-maleimides, and thermoset polyurethane resins.
- the polymeric resin can comprise an epoxy resin in some embodiments.
- Composites of the present invention can be in a variety of forms and can be used in a variety of applications.
- the composites can include aerospace composites, aviation composites, radomes, laminates, fiber-metal laminates, and others.
- a fiber-metal laminate can comprise various layers of glass reinforced composites and metal sheets.
- a fiber-metal laminate can comprise a prepreg comprising a polymeric resin and a fabric comprising a plurality of glass fibers formed from one of the various glass compositions described herein, a first metal sheet adhesively secured to one surface of the pregreg, and a second metal sheet adhesively secured to a second surface of the prereg, such that the prepreg is positioned between the two metal sheets.
- a second prepreg and be positioned between the second metal sheet and a third metal sheet.
- the metal sheets can comprise aluminum and the polymeric resin can comprise epoxy.
- Glass fibers useful in some embodiments of the present invention can exhibit high strain-to-failure, high strength, and/or low fiber density, which combination can result in glass fiber-reinforced composites having a lower areal density for a given fiber volume fraction or a given composite performance.
- the glass fibers may be first arranged into a fabric.
- glass fibers of the present invention can be provided in other forms including, for example and without limitation, as chopped strands (dry or wet), yarns, wovings, prepregs, etc.
- various embodiments of the glass compositions (and any fibers formed therefrom) can be used in a variety of applications.
- Fiberizable glass compositions have been developed which provide improved electrical performance (i.e., low dielectric constant, D k , and/or low dissipation factor, D f ) relative to standard E-glass, while providing temperature- viscosity relationships that are more conducive to commercially practical fiber forming than previous low D k glass proposals.
- Such glass compositions are described in U.S. Pat. No. 7,829,490 and U.S. Patent Application Serial No. 13/229,012, filed September 9, 2011 , both of which are incorporated herein by reference in their entireties.
- Another optional aspect of the glass compositions described in U.S. Patent No. 7,829,490 and U.S. Patent Application Serial No. 13/229,012 is that at least some of the compositions can be made commercially with relatively low raw material batch cost.
- 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 present invention are particularly suitable for weaving applications. In addition, some embodiments of the present invention relate to glass fiber fabrics. Some embodiments of glass fiber fabrics of the present invention are particularly suitable for use in reinforcement applications, especially reinforcement applications in which low density and high modulus, high strength, and/or high strain-to-failure are important. Further, some embodiments of the present invention relate to composites that incorporate fiber glass strands, glass fiber yarns, and glass fiber fabrics, such as fiber reinforced polymer composites.
- Some composites of the present invention are particularly suitable for use in reinforcement applications, especially reinforcement applications in which low density and high modulus, high strength, and/or high strain-to- failure are important, such as aerospace, aviation, wind energy, radome, and other applications. Some composites of the present invention may be especially suitable for use in any application in which high impact resistance and low density are desirable.
- Exemplary applications include, among others, aerospace applications, aviation applications, automobile applications, shipping applications, wind energy applications, bridge construction, and radomes.
- Some embodiments of the present invention relate to aerospace composites.
- Other embodiments of the present application relate to aviation composites.
- Still other embodiments of the present invention relate to composites suitable for use in wind energy applications.
- Some embodiments of the present invention relate to prepregs.
- Other embodiments of the present invention relate to laminates.
- Some embodiments of the present invention relate to fiber-metal laminates (e.g., fiber glass prepregs positioned between metal sheets) that can be used, for example, in secondary aircraft structures.
- Other embodiments of the present invention relate to radomes.
- a fiber glass strand of the present invention comprises a plurality of glass fibers comprising a glass composition that comprises the following components:
- the (Li 2 0 + Na 2 0 + K 2 0) content can be less than 2 weight percent and the MgO content can be at least twice the content of CaO on a weight percent basis.
- a fiber glass strand of the present invention comprises a plurality of glass fibers comprising a glass composition that comprises the following components:
- a fiber glass strand of the present invention comprises a glass composition comprising:
- Li 2 0 content is greater than either the Na 2 0 content or the K 2 0 content.
- a number of other glass compositions are disclosed herein as part of the present invention, and other embodiments of the present invention relate to fiber glass strands formed from such compositions.
- fiber glass strands formed from glass compositions described herein can exhibit desirable properties, such as improved fiber strength, Young's modulus, failure strain, and/or linear coefficient of thermal expansion, while also exhibiting relatively low density. Fiber glass strands comprising other glass compositions as disclosed herein may also exhibit one or more such desirable properties.
- Fiber glass strands can comprise glass fibers of various diameters, depending on the desired application.
- a fiber glass strand of the present invention comprises at least one glass fiber having a diameter between about 5 and about 13 ⁇ . In other embodiments, the at least one glass fiber has a diameter between about 5 and about 7 ⁇ .
- fiber glass strands of the present invention can be formed into rovings.
- Rovings can comprise assembled, multi-end, or single-end direct draw rovings.
- Rovings comprising fiber glass strands of the present invention can comprise direct draw single-end rovings having various diameters and densities, depending on the desired application.
- a roving comprising fiber glass strands of the present invention exhibits a density up to about 1 12 yds/lb.
- a yarn of the present invention comprises at least one fiber glass strand comprising a glass composition that comprises 60-68 weight percent Si0 2 , 7-12 weight percent B 2 0 3 , 9-15 weight percent A1 2 0 3 , 8-15 weight percent MgO, 0-4 weight percent CaO, 0-2 weight percent Li 2 0, 0-1 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-1 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- a yarn in some embodiments, comprises at least one fiber glass strand comprising a glass composition that comprises 53.5-77 weight percent Si0 2 , 4.5-14.5 weight percent B 2 0 3 , 4.5-18.5 weight percent A1 2 0 3 , 4-12.5 weight percent MgO, 0-10.5 weight percent CaO, 0-4 weight percent Li 2 0, 0-2 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-2 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- a yarn of the present invention can comprise at least one fiber glass strand comprising one of the other glass compositions disclosed herein as part of the present invention.
- a yarn of the present invention comprises at least one fiber glass strand as disclosed herein, wherein the at least one fiber glass strand is at least partially coated with a sizing composition.
- the sizing composition is compatible with a thermosetting polymeric resin.
- the sizing composition can comprise a starch-oil sizing composition.
- Yarns can have various linear mass densities, depending on the desired
- a yarn of the present invention has a linear mass density from of 5,000 yds/lb to about 10,000 yds/lb.
- Yarns can have various twist levels and directions, depending on the desired application.
- a yarn of the present invention has a twist in the z direction of about 0.5 to about 2 turns per inch. In other embodiments, a yarn of the present invention has a twist in the z direction of about 0.7 turns per inch.
- Yarns can be made from one or more strands that are twisted together and/or plied, depending on the desired application. Yarns can be made from one or more strands that are twisted together but not plied; such yarns are known as "singles.” Yarns of the present invention can be made from one or more strands that are twisted together but not plied. In some embodiments, yarns of the present invention comprise 1-4 strands twisted together. In other embodiments, yarns of the present invention comprise 1 twisted strand.
- Some embodiments of yarns comprising glass compositions of the present invention can demonstrate improved break load retention following heat cleaning and finishing as compared to yarns made from conventional glass compositions.
- a fabric comprises at least one fiber glass strand comprising a glass composition that comprises 60-68 weight percent Si0 2 , 7-12 weight percent B 2 0 3 , 9-15 weight percent A1 2 0 3 , 8-15 weight percent MgO, 0-4 weight percent CaO, 0-2 weight percent Li 2 0, 0-1 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-1 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- a fabric in some embodiments, comprises at least one fiber glass strand comprising a glass composition that comprises 53.5-77 weight percent Si0 2 , 4.5-14.5 weight percent B 2 0 3 , 4.5-18.5 weight percent A1 2 0 3 , 4-12.5 weight percent MgO, 0-10.5 weight percent CaO, 0-4 weight percent Li 2 0, 0-2 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-2 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- a fabric of the present invention can comprise at least one fiber glass strand comprising one of the other glass compositions disclosed herein as part of the present invention.
- a fabric of the present invention comprises a yarn as disclosed herein. Fabrics of the present invention, in some embodiments, can comprise at least one fill yarn comprising at least one fiber glass strand as disclosed herein. Fabrics of the present invention, in some embodiments, can comprise at least one warp yarn comprising at least one fiber glass strand as disclosed herein. In some embodiments, a fabric of the present invention comprises at least one fill yarn comprising at least one fiber glass strand as disclosed herein and at least one warp yarn comprising at least one fiber glass strand as disclosed herein.
- the glass fiber fabric is a fabric woven in accordance with industrial fabric style no. 7781.
- the fabric comprises a plain weave fabric, a twill fabric, a crowfoot fabric, a satin weave fabric, a stitch bonded fabric (also known as a non crimp fabric), or a "three-dimensional" woven fabric.
- a composite of the present invention comprises a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein at least one of the plurality of glass fibers comprises a glass composition that comprises the following components: 60-68 weight percent Si0 2 , 7-12 weight percent B 2 0 3 , 9-15 weight percent A1 2 0 3 , 8-15 weight percent MgO, 0-4 weight percent CaO, 0-2 weight percent Li 2 0, 0-1 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-1 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- a composite of the present invention in some embodiments, comprises a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein at least one of the plurality of glass fibers comprises a glass composition that comprises the following components: 53.5-77 weight percent Si0 2 , 4.5-14.5 weight percent B 2 0 3 , 4.5-18.5 weight percent A1 2 0 3 , 4-12.5 weight percent MgO, 0-10.5 weight percent CaO, 0-4 weight percent Li 2 0, 0-2 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-2 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- a composite of the present invention can comprise a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein at least one of the plurality of glass fibers was formed from one of the other glass compositions disclosed herein as part of the present invention.
- a composite of the present invention comprises a polymeric resin and at least one fiber glass strand as disclosed herein disposed in the polymeric resin.
- a composite of the present invention comprises a polymeric resin and at least a portion of a roving comprising at least one fiber glass strand as disclosed herein disposed in the polymeric resin.
- a composite of the present invention comprises a polymeric resin and at least one yarn as disclosed herein disposed in the polymeric resin. In still other embodiments, a composite of the present invention comprises a polymeric resin and at least one fabric as disclosed herein disposed in the polymeric resin. In some embodiments, a composite of the present invention comprises at least one fill yarn comprising at least one fiber glass strand as disclosed herein and at least one warp yarn comprising at least one fiber glass strand as disclosed herein.
- Composites of the present invention can comprise various polymeric resins, depending on the desired properties and applications.
- the polymeric resin comprises an epoxy resin.
- the polymeric resin can comprise polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, polydicyclopentadiene, polyphenylene sulfide, polyether ether ketone, cyanate esters, bis- maleimides, and thermoset polyurethane resins.
- Some embodiments of the present invention relate to aerospace composites.
- an aerospace composite of the present invention exhibits properties desirable for use in aerospace applications, such as high modulus, high failure-to-strain, and/or low density.
- the low density of some aerospace composites of the present invention can make such composites especially desirable for use in aerospace applications in which reducing weight is important. Aerospace composites of the present invention can also cost less than other composites used in aerospace applications.
- an aerospace composite of the present invention comprises a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein at least one of the plurality of glass fibers comprises a glass composition that comprises the following components: 60-68 weight percent Si0 2 , 7-12 weight percent B 2 0 3 , 9-15 weight percent A1 2 0 3 , 8-15 weight percent MgO, 0-4 weight percent CaO, 0-2 weight percent Li 2 0, 0-1 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-1 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- An 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 at least one of the plurality of glass fibers comprises a glass composition that comprises the following components: 53.5-77 weight percent Si0 2 , 4.5-14.5 weight percent B 2 0 3 , 4.5-18.5 weight percent A1 2 0 3 , 4-12.5 weight percent MgO, 0-10.5 weight percent CaO, 0-4 weight percent Li 2 0, 0-2 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-2 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- an aerospace composite of the present invention can comprise a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein at least one of the plurality of glass fibers was formed from one of the other glass compositions disclosed herein as part of the present invention.
- an aerospace composite of the present invention comprises a polymeric resin and at least one fiber glass strand as disclosed herein disposed in the polymeric resin.
- an aerospace composite of the present invention comprises a polymeric resin and at least a portion of a roving comprising at least one fiber glass strand as disclosed herein disposed in the polymeric resin.
- an aerospace composite of the present invention comprises a polymeric resin and at least one yarn as disclosed herein disposed in the polymeric resin.
- an aerospace composite of the present invention comprises a polymeric resin and at least one fabric as disclosed herein disposed in the polymeric resin.
- an aerospace composite of the present invention comprises at least one fill yarn comprising at least one fiber glass strand as disclosed herein and at least one warp yarn comprising at least one fiber glass strand as disclosed herein.
- Aerospace composites of the present invention can comprise various polymeric resins, depending on the desired properties and applications.
- the polymeric resin comprises an epoxy resin.
- the polymeric resin can comprise polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, polydicyclopentadiene, polyphenylene sulfide, polyether ether ketone, cyanate esters, bis-maleimides, and thermoset polyurethane resins.
- aerospace composites of the present invention can include, but are not limited to floor panels, overhead bins, galleys, seat back, and other internal compartments that are potentially prone to impact, as well as external components such as helicopter rotor blades.
- an aviation composite of the present invention exhibits properties desirable for use in aviation applications, such as high modulus, high failure-to-strain, and/or low density.
- the high failure-to-strain of some aviation composites of the present invention can make such composites especially desirable for use in aviation applications in which high impact resistance is important, such as aircraft interior applications.
- aviation composites of the present invention can demonstrate increased impact performance as compared to composites formed from E-glass fabrics.
- Aviation composites of the present invention can also cost less than other composites used in aviation applications.
- Aviation composites of the present invention can be suitable for use in aircraft interiors (including, among other things, luggage storage bins, seats, and floors).
- an aviation composite of the present invention comprises a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein at least one of the plurality of glass fibers comprises a glass composition that comprises the following components: 60-68 weight percent Si0 2 , 7-12 weight percent B 2 0 3 , 9-15 weight percent A1 2 0 3 , 8-15 weight percent MgO, 0-4 weight percent CaO, 0-2 weight percent Li 2 0, 0-1 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-1 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- An aviation composite of the present invention in some embodiments, comprises a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein at least one of the plurality of glass fibers comprises a glass composition that comprises the following components: 53.5-77 weight percent Si0 2 , 4.5-14.5 weight percent B 2 0 3 , 4.5-18.5 weight percent A1 2 0 3 , 4-12.5 weight percent MgO, 0-10.5 weight percent CaO, 0-4 weight percent Li 2 0, 0-2 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-2 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- an aviation composite of the present invention can comprise a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein at least one of the plurality of glass fibers was formed from one of the other glass compositions disclosed herein as part of the present invention.
- an aviation composite of the present invention comprises a polymeric resin and at least one fiber glass strand as disclosed herein disposed in the polymeric resin. In some embodiments, an aviation composite of the present invention comprises a polymeric resin and at least a portion of a roving comprising at least one fiber glass strand as disclosed herein disposed in the polymeric resin. In other embodiments, an aviation composite of the present invention comprises a polymeric resin and at least one yarn as disclosed herein disposed in the polymeric resin. In still other embodiments, an aviation composite of the present invention comprises a polymeric resin and at least one fabric as disclosed herein disposed in the polymeric resin. In some embodiments, an aviation composite of the present invention comprises at least one fill yarn comprising at least one fiber glass strand as disclosed herein and at least one warp yarn comprising at least one fiber glass strand as disclosed herein.
- Aviation composites of the present invention can comprise various polymeric resins, depending on the desired properties and applications.
- the polymeric resin comprises a phenolic resin.
- the polymeric resin can comprise epoxy, polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, polydicyclopentadiene, polyphenylene sulfide, polyether ether ketone, cyanate esters, bis-maleimides, and thermoset
- aerospace composites of the present invention can include, but are not limited to floor panels, overhead bins, galleys, seat back, and other internal compartments that are potentially prone to impact, as well as external components such as helicopter rotor blades.
- Some embodiments of the present invention relate to composites that can be used in wind energy applications.
- a composite of the present invention suitable for use in wind energy applications exhibits properties desirable for use in wind energy applications, such as high modulus/high failure-to-strain and low density.
- Composites of the present invention suitable for use in wind energy applications can also cost less than other composites used in wind energy applications.
- Composites of the present invention can be suitable for use in wind turbine blades, particularly long wind turbine blades that are lighter weight but still strong compared to other long wind turbine blades.
- 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, wherein at least one of the plurality of glass fibers comprises a glass composition that comprises the following components: 60-68 weight percent Si0 2 , 7-12 weight percent B 2 0 3 , 9-15 weight percent A1 2 0 3 , 8-15 weight percent MgO, 0-4 weight percent CaO, 0-2 weight percent Li 2 0, 0-1 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-1 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- 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, wherein at least one of the plurality of glass fibers comprises a glass composition that comprises the following components: 53.5-77 weight percent Si0 2 , 4.5-14.5 weight percent B 2 0 3 , 4.5- 18.5 weight percent A1 2 0 3 , 4-12.5 weight percent MgO, 0-10.5 weight percent CaO, 0-4 weight percent Li 2 0, 0-2 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-2 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- an aviation composite of the present invention can comprise a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein at least one of the plurality of glass fibers was formed from one of the other glass compositions disclosed herein as part of the present invention.
- a composite of the present invention suitable for use in wind energy applications comprises a polymeric resin and at least one fiber glass strand as disclosed herein disposed in the polymeric resin.
- a composite of the present invention suitable for use in wind energy applications comprises a polymeric resin and at least a portion of a roving comprising at least one fiber glass strand as disclosed herein disposed in the polymeric resin.
- a composite of the present invention suitable for use in wind energy applications comprises a polymeric resin and at least one yarn as disclosed herein disposed in the polymeric resin.
- a composite of the present invention suitable for use in wind energy applications comprises a polymeric resin and at least one fabric as disclosed herein disposed in the polymeric resin.
- a composite of the present invention suitable for use in wind energy applications comprises at least one fill yarn comprising at least one fiber glass strand as disclosed herein and at least one warp yarn comprising at least one fiber glass strand as disclosed herein.
- Composites of the present invention suitable for use in wind energy applications can comprise various polymeric resins, depending on the desired properties and applications.
- the polymeric resin comprises an epoxy resin.
- the polymeric resin can comprise polyester resins, vinyl esters, thermoset polyurethanes, or polydicyclopentadiene resins.
- Laminates of the present invention can comprise a plurality of sheet-like layers combined to form a laminate.
- a laminate of the present invention comprises at least one layer comprising a composite as described herein.
- a laminate of the present invention comprises at least one layer comprising a composite comprising a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein at least one of the plurality of glass fibers comprises a glass composition that comprises the following components: 60-68 weight percent Si0 2 , 7-12 weight percent B 2 0 3 , 9-15 weight percent A1 2 0 3 , 8-15 weight percent MgO, 0-4 weight percent CaO, 0-2 weight percent Li 2 0, 0-1 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-1 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- a laminate of the present invention comprises at least one layer comprising a composite comprising a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein at least one of the plurality of glass fibers comprises a glass composition that comprises the following components: 53.5-77 weight percent Si0 2 , 4.5-14.5 weight percent B 2 0 3 , 4.5-18.5 weight percent A1 2 0 3 , 4-12.5 weight percent MgO, 0-10.5 weight percent CaO, 0-4 weight percent Li 2 0, 0-2 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-2 weight percent F 2 , 0- 2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- a laminate of the present invention can comprise at least one layer comprising a composite comprising a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein at least one of the plurality of glass fibers was formed from one of the other glass compositions disclosed herein as part of the present invention.
- a laminate of the present invention comprises a composite comprising a polymeric resin and at least one fiber glass strand as disclosed herein disposed in the polymeric resin.
- a laminate of the present invention comprises a polymeric resin and at least a portion of a roving comprising at least one fiber glass strand as disclosed herein disposed in the polymeric resin.
- a laminate of the present invention comprises a composite comprising a polymeric resin and at least one yarn as disclosed herein disposed in the polymeric resin.
- a laminate of the present invention comprises a composite comprising a polymeric resin and at least one fabric as disclosed herein disposed in the polymeric resin.
- a laminate of the present invention comprises at least one fill yarn comprising at least one fiber glass strand as disclosed herein and at least one warp yarn comprising at least one fiber glass strand as disclosed herein.
- Laminates of the present invention can comprise various polymeric resins, depending on the desired properties and applications.
- the polymeric resin comprises an epoxy resin.
- the polymeric resin can comprise polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, polydicyclopentadiene, polyphenylene sulfide, polyether ether ketone, cyanate esters, bis- maleimides, and thermoset polyurethane resins.
- Prepregs of the present invention can comprise a polymeric resin and at least one fiber glass strand as disclosed herein.
- a prepreg of the present invention comprises a polymeric resin and a plurality of glass fibers in contact with the polymeric resin, wherein at least one of the plurality of glass fibers comprises a glass composition that comprises the following components: 60-68 weight percent Si0 2 , 7-12 weight percent B 2 0 3 , 9-15 weight percent A1 2 0 3 , 8-15 weight percent MgO, 0-4 weight percent CaO, 0-2 weight percent Li 2 0, 0-1 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-1 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- a prepreg of the present invention in some embodiments, comprises a polymeric resin and a plurality of glass fibers in contact with the polymeric resin, wherein at least one of the plurality of glass fibers comprises a glass composition that comprises the following components: 53.5-77 weight percent Si0 2 , 4.5-14.5 weight percent B 2 0 3 , 4.5-18.5 weight percent A1 2 0 3 , 4-12.5 weight percent MgO, 0-10.5 weight percent CaO, 0-4 weight percent Li 2 0, 0-2 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-2 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- a prepreg of the present invention can comprise a polymeric resin and a plurality of glass fibers in contact with the polymeric resin, wherein at least one of the plurality of glass fibers was formed from one of the other glass compositions disclosed herein as part of the present invention.
- a 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.
- a prepreg of the present invention comprises a polymeric resin and at least a portion of a roving comprising at least one fiber glass strand as disclosed herein disposed in the polymeric resin.
- a prepreg of the present invention comprises a polymeric resin and at least one yarn as disclosed herein in contact with the polymeric resin.
- a prepreg of the present invention comprises a polymeric resin and at least one fabric as disclosed herein in contact with the polymeric resin.
- a prepreg of the present invention comprises at least one fill yarn comprising at least one fiber glass strand as disclosed herein and at least one warp yarn comprising at least one fiber glass strand as disclosed herein.
- Prepregs of the present invention can comprise various polymeric resins, depending on the desired properties and applications.
- the polymeric resin comprises an epoxy resin.
- the polymeric resin can comprise polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester,
- polydicyclopentadiene polyphenylene sulfide
- polyether ether ketone polyether ether ketone
- cyanate esters polyether ether ketone
- bis- maleimides polystyrene resins
- prepregs of the present invention can be incorporated into other products.
- prepregs of the present invention can be incorporated into a fiber-metal laminate.
- Incorporating a prepreg of the present invention into a fiber-metal laminate can be advantageous because, in some embodiments, the prepreg can have excellent crack arresting properties and specific gravity relative to the metal sheets that might be used (e.g., an aluminum alloy sheet).
- the metal sheets that might be used e.g., an aluminum alloy sheet.
- Several fiber-metal laminates, such as GLARE and ARALL, are well-known, and prepregs of the present invention can readily be incorporated into those structures.
- Fiber- metal laminates such as GLARE ("Glass Laminate Aluminum Reinforced Epoxy") and ARALL (an aramid fiber-based fiber-metal laminate) were developed as lightweight fuselage materials for aerospace applications with GLARE generally directed towards fuselage applications and ARALL generally directed towards wing applications.
- GLARE fiber-metal laminates are traditionally constructed by alternating layers of a fiber glass/epoxy prepreg (unidirectional or biaxial) with pre-treated aluminum foil (i.e., 0.2- 0.4 mm thick 2024 T3 foil, etched using proprietary processes to enhance adhesion to the composite layers).
- GLARE fiber-metal laminate can incorporate 3 layers of aluminum and 2 layers of biaxial composite and is sometimes referred to as a GLARE 3/2 laminates.
- Embodiments may also exist that incorporate 4 layers of aluminum and 3 layers of composite, or 5 layers of aluminum and 4 layers of composite.
- a fiber-metal laminate can comprise a prepreg according to some embodiments of the present invention, a first metal sheet adhesively secured to one surface of the prepreg, and a second metal sheet adhesively secured to a second surface of the prepreg, such that the prepreg is positioned between the two metal sheets.
- multiple layers of prepregs can be incorporated in, for example, a 3/2 arrangement (two prepreg layers between three metal sheets in a metal/prepreg/metal/prepreg/metal arrangement), a 4/3 arrangement (three prepreg layers between four metal sheets in a 3/2 arrangement (two prepreg layers between three metal sheets in a metal/prepreg/metal/prepreg/metal arrangement), a 4/3 arrangement (three prepreg layers between four metal sheets in a
- metal/prepreg/metal/prepreg/metal/prepreg/metal arrangement a 5/4 arrangement (four prepreg layers between five metal sheets in a
- the metal sheets can comprise aluminum or other metals typically used in fiber-metal laminates.
- the polymeric resin used in the prepreg comprises epoxy.
- the prepreg is adhesively secured to the metal sheets using a film adhesive for a controlled bond line thickness as is known to those of skill in the art. In some embodiments, a separate adhesive is not require as the polymeric resin (e.g., an epoxy) used in the prepreg can adhere the prepreg to the metal sheets.
- Radomes are radar enclosures or structural shells that are typically built using materials that provide a low dielectric constant to minimize signal reflections to/from the radar.
- High cost fibers such as quartz and aramid, as well as high strength fiber glass, have been used successfully in the production of radomes in combination with various resin systems.
- materials for radomes preferably provide high stiffness/strength as well as excellent durability characteristics to withstand
- Glass fibers according to some embodiments of the present invention can have a dielectric constant of 5.3 @ 1 MHz which, although higher than quartz ( ⁇ 3.5), is lower than E-glass (6.3-6.6 @ 1 MHz) and comparable to S-2 glass (5-5.4 @ 1 MHz), making it a suitable glass fiber for use in radome applications.
- a radome of the present invention comprises a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein at least one of the plurality of glass fibers comprises a glass composition that comprises the following components: 60-68 weight percent Si0 2 , 7-12 weight percent B 2 0 3 , 9-15 weight percent A1 2 0 3 , 8-15 weight percent MgO, 0-4 weight percent CaO, 0-2 weight percent Li 2 0, 0-1 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-1 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- a radome of the present invention in some embodiments, comprises a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein at least one of the plurality of glass fibers comprises a glass composition that comprises the following components: 53.5-77 weight percent Si0 2 , 4.5-14.5 weight percent B 2 0 3 , 4.5-18.5 weight percent A1 2 0 3 , 4-12.5 weight percent MgO, 0-10.5 weight percent CaO, 0-4 weight percent Li 2 0, 0-2 weight percent Na 2 0, 0-1 weight percent K 2 0, 0-1 weight percent F 2 0 3 , 0-2 weight percent F 2 , 0-2 weight percent Ti0 2 , and 0-5 weight percent total other constituents.
- a radome of the present invention can comprise a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, wherein at least one of the plurality of glass fibers was formed from one of the other glass compositions disclosed herein as part of the present invention.
- a radome of the present invention comprises a radar enclosure or structural shell comprising a polymeric resin and at least one fiber glass strand as disclosed herein disposed in the polymeric resin.
- a radome of the present invention comprises a polymeric resin and at least a portion of a roving comprising at least one fiber glass strand as disclosed herein disposed in the polymeric resin.
- a radome of the present invention comprises a polymeric resin and at least one yarn as disclosed herein disposed in the polymeric resin.
- a radome of the present invention comprises a polymeric resin and at least one fabric as disclosed herein disposed in the polymeric resin.
- a radome of the present invention comprises at least one fill yarn comprising at least one fiber glass strand as disclosed herein and at least one warp yarn comprising at least one fiber glass strand as disclosed herein.
- Radomes of the present invention can comprise various polymeric resins, depending on the desired properties and applications.
- the polymeric resin can comprise epoxy, phenolic, polyethylene, polypropylene, polyamide, polyimide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester,
- polydicyclopentadiene polyphenylene sulfide
- polyether ether ketone polyether ether ketone
- cyanate esters polyether ether ketone
- bis- maleimides polystyrene resins
- Glass fibers useful in the present invention can be made by any suitable method known to one of ordinary skill in the art, such as but not limited to the method described above herein. Further, a primary sizing composition can be applied to the glass fibers using any suitable method known to one of ordinary skill in the art. In some
- the sizing composition can be applied immediately after forming the glass fibers.
- the sizing composition can comprise any suitable sizing composition known to one of ordinary skill in the art for reinforcement applications.
- the sizing composition does not comprise a starch-oil sizing composition.
- a sized glass fiber or glass fiber strand need not be further treated with a slashing composition prior to using the fiber or strand in weaving applications.
- a sized glass fiber or glass fiber strand may optionally be further treated with a slashing composition prior to using the fiber or strand in weaving applications.
- the sizing composition can comprise a starch-oil sizing composition.
- the starch-oil sizing composition may later be removed from a fabric formed from at least one sized glass fiber or fiber glass strand.
- the starch-oil sizing may be removed from a fabric using any suitable method known to one of ordinary skill in the art, such as but not limited to heat cleaning.
- a fabric of the present invention may further be treated with a finish coating.
- Fiber glass strands of the present invention can be prepared by any suitable method known to one of ordinary skill in the art.
- Glass fiber fabrics of the present invention can generally be made by any suitable method known to one of ordinary skill in the art, such as but not limited to interweaving weft yarns (also referred to as "fill yarns") into a plurality of warp yarns.
- interweaving can be accomplished by positioning the warp yarns in a generally parallel, planar array on a loom, and thereafter weaving the weft yarns into the warp yarns by passing the weft yarns over and under the warp yarns in a predetermined repetitive pattern. The pattern used depends upon the desired fabric style.
- Warp yarns can generally be prepared using techniques known to those of skill in the art. Warp yarns can be formed by attenuating a plurality of molten glass streams from a bushing or spinner. Thereafter, a sizing composition can be applied to the individual glass fibers and the fibers can be gathered together to form a strand. The strands can be subsequently processed into yarns by transferring the strands to a bobbin via a twist frame. During this transfer, the strands can be given a twist to aid in holding the bundle of fibers together. These twisted strands can then be wound about the bobbin, and the bobbins can be used in the weaving processes.
- Positioning of the warp yarns on the loom can generally be done using techniques known to those of ordinary skill in the art. Positioning of the warp yarns on the loom can be done by way of a loom beam.
- a loom beam comprises a specified number of warp yarns (also referred to as "ends") wound in an essentially parallel arrangement (also referred to as "warp sheet”) about a cylindrical core.
- Loom beam preparation can comprise combining multiple yarn packages, each package comprising a fraction of the number of ends required for the loom beam, into a single package or loom beam. For example and although not limiting herein, a 50 inch (127 cm) wide, a 7781 style fabric which utilizes a DE75 yarn input typically requires 2868 ends.
- a section beam can include a cylindrical core comprising a plurality of essentially parallel warp yarns wound thereabout. While it will be recognized by one skilled in the art that the section beam can comprise any number of warp yarns required to form the final loom beam, generally the number of ends contained on a section beam is limited by the capacity of the warping creel. For a 7781 style fabric, four section beams of 717 ends each of DE75 yarn are typically provided and when combined offer the required 2868 ends for the warp sheet, as discussed above.
- Composites of the present invention can be prepared by any suitable method known to one of ordinary skill in the art, such as but not limited to vacuum assisted resin infusion molding, extrusion compounding, compression molding, resin transfer molding, filament winding, prepreg/autoclave curing, and pultrusion.
- Composites of the present invention can be prepared using such molding techniques as known to those of ordinary skill in the art.
- embodiments of composites of the present invention that incorporate woven fiber glass fabrics can be prepared using techniques known to those of skill in the art for preparation of such composites.
- some composites of the present invention can be made using vacuum assisted compression molding, which technique is well-known to those of skill in the art and described briefly below.
- vacuum assisted compression molding a stack of pre-impregnated glass fabrics is placed within a press platen.
- the stack of pre-impregnated glass fabrics can include one or more fabrics of the present invention as described herein that have been cut to a desired size and shape.
- the press is closed and the platens are connected to a vacuum pump so that the upper platen compresses on the stack of fabrics until the desired pressure is achieved.
- the vacuum aids in the evacuation of entrapped air within the stack and provides for a reduced void content in the molded laminate.
- the temperature of the platens is then increased to accelerate the conversion rate of the resin (e.g., a thermosetting resin) to a predetermined temperature setting particular to the resin utilized, and kept at that temperature and pressure setting until the laminate reaches full cure.
- the heat is turned off and the platens are cooled by water circulation until they reach room temperature.
- the platens can then be opened, and the molded laminate can be removed from the press.
- some composites of the present invention can be made using vacuum assisted resin infusion technology, as further described herein.
- a stack of glass fiber fabrics of the present invention may be cut to a desired size and placed on a silicone release treated glass table. The stack may then be covered with a peel ply, fitted with a flow enhancing media, and vacuum bagged using nylon bagging film. Next, the so-called “lay up” may be subjected to a vacuum pressure of about 27 inches Hg.
- the polymeric resin that is to be reinforced with the fiber glass fabrics can be prepared using techniques known to those of skill in the art for that particular resin.
- an appropriate resin e.g., an amine-curable epoxy resin
- an appropriate curing agent e.g., an amine for an amine-curable epoxy resin
- the combined resin may then be degassed in a vacuum chamber for 30 minutes and infused through the fabric preform until substantially complete wet out of the fabric stack is achieved.
- the table may be covered with heated blankets (set to a temperature of about 45 - 50 °C) for 24 hours.
- the resulting rigid composites may then be de-molded and post cured at about 250 °F for 4 hours in a programmable convection oven.
- Laminates of the present invention can be prepared by any suitable means known to one of ordinary skill in the art, such as but not limited to infusion.
- Prepregs of the present invention can be prepared by any suitable means known to one of ordinary skill in the art, such as but not limited to passing fiber glass strands, rovings, or fabrics through a resin bath; using a solvent-based resin; or using a resin film.
- Fiber-metal laminates of the present invention can be prepared by any suitable means known to one of ordinary skill in the art using prepregs of the present invention.
- Radomes of the present invention can be prepared by any suitable means known to one of ordinary skill in the art.
- some embodiments of the present invention can comprise a plurality of glass fibers.
- Glass fibers suitable for use in the present invention can have any appropriate diameter known to one of ordinary skill in the art, depending on the desired application.
- Glass fibers suitable for use in some embodiments of the present invention have a diameter of about 5 to about 13 ⁇ .
- Glass fibers suitable for use in other embodiments of the present invention have a diameter of about 5-7 ⁇ .
- glass fibers and glass fiber strands suitable for use in the present invention can comprise a variety of glass compositions that also represent embodiments of the present invention. Some embodiments of such glass fibers and fiber glass strands are set forth above and others are described below. As noted above, one example of glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising
- the Li 2 0 content is greater than either the Na 2 0 content or the K 2 0 content.
- the CaO content is 0-3 weight percent. In still other embodiments, the CaO content is 0-2 weight percent. In some embodiments, the CaO content is 0-1 weight percent.
- the MgO content is 8-13 weight percent. In other embodiments, the MgO content is 9-12 weight percent.
- the Ti0 2 content is 0-1 weight percent.
- the B 2 0 3 content is no more than 10 weight percent.
- the A1 2 0 3 content is 9-14 weight percent. In other embodiments, the A1 2 0 3 content is 10-13 weight percent.
- the (Li 2 0 + Na 2 0 + K 2 0) content is less than 2 weight percent.
- the composition contains 0-1 weight percent of BaO and 0-2 weight percent ZnO. In other embodiments, the composition contains essentially no BaO and essentially no ZnO.
- other constituents, if any, are present in a total amount of 0-2 weight percent. In other embodiments, other constituents, if any, are present in a total amount of 0-1 weight percent.
- the Li 2 0 content is 0.4-2.0 weight percent. In other embodiments comprising a Li 2 0 content of 0.4-2.0 weight percent, the Li 2 0 content is greater than the (Na 2 0 + K 2 0) content.
- the glass compositions are characterized by relatively low content of CaO, for example on the order of about 0 - 4 weight percent.
- the CaO content can be on the order of about 0 - 3 weight percent. In some embodiments, the MgO content is double that of the CaO content (on a weight percent basis). Some embodiments of the invention can have a MgO content greater than about 6.0 weight percent, and in other embodiments the MgO content can be greater than about 7.0 weight percent.
- embodiments of the present invention can be characterized by the presence of less than 1.0 weight percent BaO.
- the BaO content can be characterized as being no more than 0.05 weight percent.
- the constituents are selected to provide a glass having a dielectric constant (D k ) less than 6.7 at 1 MHz frequency.
- the constituents are selected to provide a glass having a dielectric constant (D k ) less than 6 at 1 MHz frequency.
- the constituents are selected to provide a glass having a dielectric constant (D k ) less than 5.8 at 1 MHz frequency.
- the constituents are selected to provide a glass having a dielectric constant (D k ) less than 5.6 at 1 MHz frequency.
- a glass fiber or fiber glass strand suitable for use in the present invention comprises a glass composition comprising
- the constituents are selected to provide a forming temperature T F at 1000 poise viscosity no greater than 1370 °C.
- the constituents are selected to provide a forming temperature T F at 1000 poise viscosity no greater than 1320 °C.
- the constituents are selected to provide a forming temperature T F at 1000 poise viscosity no greater than 1300 °C.
- the constituents are selected to provide a forming temperature T F at 1000 poise viscosity no greater than 1290 °C.
- the constituents are selected to provide a forming temperature T F at 1000 poise viscosity no greater than 1370 °C and a liquidus temperature T L at least 55 °C below the forming temperature. In other embodiments, the constituents are selected to provide a forming temperature T F at 1000 poise viscosity no greater than 1320 °C and a liquidus temperature T L at least 55 °C below the forming temperature. In still other embodiments, the constituents are selected to provide a forming temperature T F at 1000 poise viscosity no greater than 1300 °C and a liquidus temperature T L at least 55 °C below the forming temperature. In some embodiments, the constituents are selected to provide a forming temperature T F at 1000 poise viscosity no greater than 1290 °C and a liquidus temperature T L at least 55 °C below the forming temperature.
- the glass exhibits a dielectric constant (D k ) less than 6.7 and forming temperature (T F ) at 1000 poise viscosity no greater than 1370 °C and wherein the Li 2 0 content is greater than either the Na 2 0 content or the K 2 0 content.
- the CaO content is 0-1 weight percent.
- the glass exhibits a dielectric constant (D k ) less than 5.9 and forming temperature (T F ) at 1000 poise viscosity no greater than 1300 °C and wherein the Li 2 0 content is greater than either the Na 2 0 content or the K 2 0 content.
- D k dielectric constant
- T F forming temperature
- the Li 2 0 content is greater than either the Na 2 0 content or the K 2 0 content.
- the CaO content is 0-1 weight percent.
- the B 2 0 3 content is no more than 10 weight percent.
- the constituents are selected to provide a glass having a dielectric constant (D k ) less than 6.7 at 1 MHz frequency. In other embodiments, the constituents are selected to provide a glass having a dielectric constant (D k ) less than 6 at 1 MHz frequency. In still other embodiments, the constituents are selected to provide a glass having a dielectric constant (D k ) less than 5.8 at 1 MHz frequency. In some embodiments,
- the constituents are selected to provide a glass having a dielectric constant (D k ) less than 5.6 at 1 MHz frequency.
- Si0 2 at least 60 weight percent
- the glass exhibits a dielectric constant (D k ) less than 6.7 and a forming temperature (T F ) at 1000 poise viscosity no greater than 1370°C.
- the glass exhibits a dielectric constant (D k ) less than 6.7 and forming temperature (T F ) at 1000 poise viscosity no greater than 1370°C.
- the glass exhibits a dielectric constant (D k ) less than 6.7 and forming temperature (T F ) at 1000 poise viscosity no greater than 1370°C.
- the glass exhibits a dielectric constant (D k ) less than 5.9 and forming temperature (T F ) at 1000 poise viscosity no greater than 1300°C.
- a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising: Si0 2 60 - 68 weight percent;
- some embodiments of the glass compositions of the present invention can be utilized to provide glasses having dissipation factors (D f ) lower than standard electronic E-glass.
- D F may be no more than 0.0150 at 1 GHz, and in other embodiments no more than 0.0100 at 1 GHz.
- D F is no more than 0.007 at 1 GHz, and in other embodiments no more than 0.003 at 1 GHz, and in yet other embodiments no more than 0.002 at 1 GHz.
- the glass compositions that can be used in glass fibers or fiber glass strands of the invention are characterized by relatively low content of CaO, for example, on the order of about 0 - 4 weight percent.
- the CaO content can be on the order of about 0 - 3 weight percent.
- the CaO content can be on the order of about 0 - 2 weight percent.
- minimizing the CaO content yields improvements in electrical properties, and the CaO content has been reduced to such low levels in some embodiments that it can be considered an optional constituent.
- the CaO content can be on the order of about 1 - 2 weight percent.
- the MgO content is relatively high for glasses of this type, wherein in some embodiments the MgO content is double that of the CaO content (on a weight percent basis).
- Some embodiments of the invention can have MgO content greater than about 5.0 weight percent, and in other embodiments the MgO content can be greater than 8.0 weight percent.
- the compositions are characterized by a MgO content, for example, on the order of about 8 - 13 weight percent.
- the MgO content can be on the order of about 9 - 12 weight percent.
- the MgO content can be on the order of about 8 - 12 weight percent.
- the MgO content can be on the order of about 8
- compositions that can be used in glass fibers or fiber glass strands of the invention are characterized by a (MgO + CaO) content, for example, that is less than 16 weight percent. In yet other embodiments, the (MgO + CaO) content is less than 13 weight percent. In some other embodiments, the (MgO + CaO) content is 7 - 16 weight percent. In yet some other embodiments, the (MgO + CaO) content can be on the order of about 10 - 13 weight percent.
- the compositions can be characterized by a ratio of (MgO + CaO)/(Li 2 0 + Na 2 0 + K 2 0) content on the order of about 9.0.
- the ratio of Li 2 0/(MgO + CaO) content can be on the order of about 0 - 2.0.
- the ratio of Li 2 0/(MgO + CaO) content can be on the order of about 1 - 2.0.
- the ratio of Li 2 0/(MgO + CaO) content can be on the order of about 1.0.
- the (Si0 2 + B 2 0 3 ) content can be on the order of 70
- the (Si0 2 + B 2 0 3 ) content can be on the order of 70 weight percent. In other embodiments, the (Si0 2 + B 2 0 3 ) content can be on the order of 73 weight percent. In still other embodiments, the ratio of the weight percent of A1 2 0 3 to the weigh percent of B 2 0 3 is on the order of 1 - 3. In some other
- the ratio of the weight percent of A1 2 0 3 to the weight percent of B 2 0 3 is on the order of 1.5 - 2.5.
- the Si0 2 content is on the order of 65 - 68 weight percent.
- embodiments of the present invention can be characterized by the presence of less than 1.0 weight percent BaO. In those embodiments in which only trace impurity amounts are present, the BaO content can be characterized as being no more than 0.05 weight percent.
- compositions that can be used in glass fibers or fiber glass strands of the invention include B 2 0 3 in amounts less that the prior art approaches that rely upon high B 2 0 3 to achieve low D k . This results in significant cost savings.
- the B 2 0 3 content need be no more than 13 weight percent, or no more than 12 weight percent.
- Some embodiments of the invention also fall within the ASTM definition of electronic E-glass, i.e., no more than 10 weight percent B 2 0 3 .
- the compositions are characterized by a B 2 0 3 content, for example, on the order of about 5 - 1 1 weight percent.
- the B 2 0 3 content can be 6-11 weight percent.
- the B 2 0 3 content in some embodiments, can be 6-9 weight percent.
- the B 2 0 3 content can be 5-10 weight percent.
- the B 2 0 3 content is not greater than 9 weight percent. In yet some other embodiments, the B 2 0 3 content is not greater than 8 weight percent.
- the compositions that can be used in glass fibers or fiber glass strands of the present invention are characterized by a A1 2 0 3 content, for example on the order of about 5 - 18 weight percent.
- the A1 2 0 3 content in some embodiments, can be 9-18 weight percent.
- the A1 2 0 3 content is on the order of about 10 - 18 weight percent.
- the A1 2 0 3 content is on the order of about 10 - 16 weight percent.
- the A1 2 0 3 content is on the order of about 10 - 14 weight percent.
- the A1 2 0 3 content is on the order of about 1 1 - 14 weight percent.
- Li 2 0 is an optional constituent.
- the compositions are characterized by a Li 2 0 content, for example on the order of about 0.4 - 2.0 weight percent.
- the Li 2 0 content is greater than the (Na 2 0 + K 2 0) content.
- the (Li 2 0 + Na 2 0 + K 2 0) content is not greater than 2 weight percent.
- the (Li 2 0 + Na 2 0 + K 2 0) content is on the order of about 1 - 2 weight percent.
- the compositions of the invention are characterized by a Ti0 2 content for example on the order of about 0 - 1 weight percent.
- the constituents are proportioned so as to yield a glass having a dielectric constant lower than that of standard E-glass. With reference to a standard electronic E-glass for comparison, this may be less than about 6.7 at 1 MHz frequency.
- the dielectric constant (D k ) may be less than 6 at 1 MHz frequency.
- the dielectric constant (D k ) may be less than 5.8 at 1 MHz frequency.
- Further embodiments exhibit dielectric constants (D k ) less than 5.6 or even lower at 1 MHz frequency.
- the dielectric constant (D k ) may be less than 5.4 at 1 MHz frequency.
- the dielectric constant (D k ) may be less than 5.2 at 1 MHz frequency.
- the dielectric constant (D k ) may be less than 5.0 at 1 MHz frequency.
- compositions set forth above can also possess desirable temperature - viscosity relationships conducive to practical commercial manufacture of glass fibers. In general, lower temperatures are required for making fibers compared to the D-glass type of composition in the prior art.
- the desirable characteristics may be expressed in a number of ways, and they may be attained by some embodiments of compositions described herein singly or in combination. For example, certain glass compositions within the ranges set forth above can be made that exhibit forming temperatures (T F ) at
- compositions can also encompass glasses in which the difference between the forming temperature and the liquidus temperature (T L ) is positive, and in some embodiments the forming temperature is at least 55°C greater than the liquidus temperature, which is advantageous for commercial manufacturing of fibers from these glass compositions.
- minimizing alkali oxide content of the glass compositions used to form the glass fibers or fiber glass strands can assist in lowering D k .
- the total alkali oxide content may be no more than 2 weight percent of the glass composition.
- the presence of alkali oxides generally results in lower forming temperatures. Therefore, in those embodiments of the invention in which providing relatively low forming temperatures is a priority, Li 2 0 is included in significant amounts, e.g. at least 0.4 weight percent.
- the Li 2 0 content is greater than either the Na 2 0 or K 2 0 contents, and in other embodiments the Li 2 0 content is greater than the sum of the Na 2 0 and K 2 0 contents, in some embodiments greater by a factor of two or more.
- constituents in addition to those explicitly set forth in the compositional definition of the glasses of the present invention may be included even though not required, but in total amounts no greater than 5 weight percent.
- These optional constituents include melting aids, fining aids, colorants, trace impurities and other additives known to those of skill in glassmaking.
- no BaO is required in the compositions of the present invention, but inclusion of minor amounts of BaO (e.g., up to about 1 weight percent) would not be precluded.
- major amounts of ZnO are not required in the present invention, but in some embodiments minor amounts (e.g., up to about 2.0 weight percent) may be included. In those embodiments of the invention in which optional constituents are minimized, the total of optional constituents is no more than 2 weight percent, or no more than 1 weight percent. Alternatively, some
- embodiments of the invention can be said to consist essentially of the named constituents.
- Typical commercial ingredients such as for E-glass making, contain impurities of Na 2 0, K 2 0, Fe 2 0 3 or FeO, SrO, F 2 , Ti0 2 , S0 3 , etc. in various chemical forms. A majority of the cations from these impurities would increase the D k of the glasses by forming nonbridging oxygens with Si0 2 and/or B 2 0 3 in the glass.
- Sulfate (expressed as S0 3 ) may also be present as a refining agent.
- Small amounts of impurities may also be present from raw materials or from contamination during the melting processes, such as SrO, BaO, Cl 2 , P 2 0 5 , Cr 2 0 3 , or NiO (not limited to these particular chemical forms).
- Other refining agents and/or processing aids may also be present such as As 2 0 3 , MnO, Mn0 2 , Sb 2 0 3 , or Sn0 2 , (not limited to these particular chemical forms).
- These impurities and refining agents, when present, are each typically present in amounts less than 0.5% by weight of the total glass composition.
- elements from rare earth group of the Periodic Table of the Elements may be added to compositions of the present invention, including atomic numbers 21 (Sc), 39 (Y), and 57 (La) through 71 (Lu). These may serve as either processing aids or to improve the electrical, physical (thermal and optical), mechanical, and chemical properties of the glasses.
- the rare earth additives may be included with regard for the original chemical forms and oxidization states. Adding rare earth elements is considered optional, particularly in those embodiments of the present invention having the objective of minimizing raw material cost, because they would increase batch costs even at low concentrations. In any case, their costs would typically dictate that the rare earth components (measured as oxides), when included, be present in amounts no greater than about 0.1 - 1.0 % by weight of the total glass composition.
- Glass fibers, fiber glass strands, and other products incorporating such fibers or strands can exhibit desirable mechanical properties in some embodiments of the present invention, particularly as compared to E-glass fibers, fiber glass strands formed from E- glass, and related products.
- some embodiments of glass fibers of the present invention can have relatively high specific strength or relatively high specific modulus, particularly, when compared to E-glass fibers.
- Specific strength refers to the tensile strength in N/m 2 divided by the specific weight in N/m 3 .
- Specific modulus refers to the Young's modulus in N/m 2 divided by the specific weight in N/m 3 .
- Glass fibers having relatively high specific strength and/or relatively high specific modulus may be desirable in applications where there is a desire to increase mechanical properties or product performance while reducing the overall weight of the composite.
- Examples of such composites are set forth above and include, for example, aerospace or aviation applications (e.g., interior floors of planes), wind energy applications (e.g., windmill blades), fiber-metal laminate applications, and others.
- some embodiments of fiber glass strands of the present invention in the form of rovings can exhibit increased tensile strengths (e.g., on the order of 400-430 ksi in some embodiments per ASTM D2343) as compared to rovings incorporating E- glass fiber glass strands (e.g., on the order of 350-400 ksi per ASTM D2343).
- glass fibers are typically at least partially coated with a sizing composition.
- glass fibers used to form fiber glass strands, fabrics, composites, laminates, and prepregs of the present invention will be at least partially coated with a sizing composition.
- Non- limiting examples of commercially available sizing compositions that can be used in some embodiments of the present invention include sizing compositions often used on single-end rovings, such as Hybon 2026, Hybon 2002, Hybon 1383, Hybon 2006, Hybon 2022, Hybon 2032, Hybon 2016, and Hybon 1062, as well as sizing compositions often used on yarns, such as 1383, 611 , 900, 610, 695, and 690, each of which refer to sizing compositions for products commercially available from PPG Industries, Inc.
- some embodiments of the present invention can comprise a fabric. Any suitable fabric design known to one of ordinary skill in the art for
- Suitable fabrics can include fabrics produced using standard textile equipment (e.g., rapier, projectile, or air jet looms). Non-limiting examples of such fabrics include plain weaves, twill, crowfoot, and satin weaves. Stitch bonded or non-crimp fabrics can also be used in some embodiments of the present invention. Such fabrics can include, for example, unidirectional, biaxial and triaxial non- crimp fabrics. In addition, 3D woven fabrics can also be used in some embodiments of the present invention. Such fabrics can be produced using multi-layer warp ends with shedding, either with the use of a dobby or a jacquard head.
- composites of the present invention can comprise warp and weft yarns. Any suitable warp and weft yarns known to one of ordinary skill in the art for reinforcement applications may be used.
- warp yarns can comprise G75 yarn, DE75 yarn, DE150 yarn, and/or G150 yarn.
- composites of the present invention can comprise a polymeric resin, in some embodiments.
- a variety of polymeric resins can be used. Polymeric resins that are known to be useful in reinforcement applications can be particularly useful in some embodiments.
- the polymeric resin can comprise a thermoset resin.
- Thermoset resin systems useful in some embodiments of the present invention can include but are not limited to epoxy resin systems, phenolic based resins, polyesters, vinyl esters, thermoset polyurethanes, polydicyclopentadiene (pDCPD) resins, cyanate esters, and bis-maleimides.
- the polymeric resin can comprise an epoxy resin.
- the polymeric resin can comprise a thermoplastic resin.
- Thermoplastic polymers useful in some embodiments of the present invention include but are not limited to polyethylene, polypropylene, polyamides (including Nylon), polybutylene terephthalate, polycarbonate, thermoplastic polyurethanes (TPU), polyphenylene sulfides, and polyether ether keteone (PEEK).
- Non-limiting examples of commercially available polymeric resins useful in some embodiments of the present invention include EPIKOTE Resin MGS® RIMR 135 epoxy with Epikure MGS RIMH 1366 curing agent (available from Momentive Specialty Chemicals Inc. of Columbus, Ohio), Applied Poleramic MMFCS2 epoxy (available from Applied Poleramic, Inc., Benicia, California), and EP255 modified epoxy (available from Barrday Composite Solutions, Millbury, MA).
- Some properties of a glass composition useful in some embodiments of the present invention were measured under controlled processing conditions using conventional testing methods known to those of ordinary skill in the art. Some measured properties are listed in Table 1. Properties of standard E-glass and commercial NE-glass are included for reference. The properties listed for commercial NE-glass come from the literature. The data in Table 1 indicate that glass fibers suitable for use in the present invention exhibit improved thermal, chemical, and mechanical stability compared to E-glass.
- glass fibers suitable for use in the present invention are 30% stronger and 25% stiffer.
- the glass fibers of Sample 1 in Table 1 comprised a glass composition comprising
- the yarn break load of a yarn formed from a fiber glass strand of the present invention (“the Sample Yarn”) was compared to a yarn made from a fiber glass strand formed from a conventional 621 glass composition (“the 621 Yarn").
- Each of the Yarns was formed from a single fiber glass strand having approximately 200 filaments with a nominal diameter of 7 microns.
- the glass fibers were coated with a conventional starch-oil sizing compositions.
- the fiber glass strands were dried and then twisted 1 turns per inch in the z direction to form the Yarns which were then woven into a plain weave style fabric with 60 picks per inch in the warp direction and 58 picks per inch in the weft direction.
- the break loads of the fabrics were then measured using ASTM 5053.
- a one inch wide, 6 inch long strip of fabric was fitted with paper tabs and loaded at a speed of 12 inches per minute on a universal test frame until failure.
- a total of 12 break load measurements were taken per fabric.
- the average break load for the fabric strips made from the Sample Yarns was 197.5 lb f
- the average break load for the fabric strips made from the 621 Yarns was 181.7 lb f .
- the fabrics were then heat cleaned and finished using the same conventional technique. Following heat cleaning and finishing the break loads of the fabric strips were again measured using ASTM 5035. A total of 12 break load measurements were taken.
- the average break load for the Sample fabric was 1 19.5 lb f , and the average break load for the 621 fabric was 85.1 lb f .
- the break load retention (break load after heat cleaning/finishing divided by break load prior to heat cleaning finishing X 100) for the 621 fabric was 46.8%.
- the break load retention (break load after heat cleaning/finishing divided by break load prior to heat cleaning finishing) for the Sample fabric was 60.5%, demonstrating an improvement in break load over the 621 fabric.
- the tensile and impact properties of laminates of the present invention were compared to those of laminates made from glass fibers comprising conventional glass compositions.
- a fabric was woven using warp and fill yarns made from fiber glass strands having glass compositions of the present invention ("the Sample Fabric”).
- the comparative fabric was formed from standard E-glass yarns ("E-glass Fabric”). Additional details about the fabrics are provided in Table 2: Table 2
- the pre-impregnated fabrics were then incorporated into laminates using vacuum assisted compression molding.
- the polymeric resin used was EP255 modified epoxy resin from Barrday Composite Solutions, Millbury, MA.
- Ten fabric layers were incorporated into each of the laminates.
- the process conditions in Table 3 were used for the vacuum assisted compression molding setup:
- T g glass transition temperature
- 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 testing machine.
- the impact properties of the Sample Laminate and the E-glass laminate were observed to be significantly different.
- the Sample Laminates resulted in significantly increased impact performance evidenced by high energy at maximum load, and total energy absorbed by the samples.
- the average energy to maximum load was 30.984 Joules for the Sample Laminates and 14.204 Joules for the E-glass Laminates.
- the average total energy absorbed was 35.34 Joules for the Sample Laminates and 26.76 Joules for the E-glass Laminates.
- the Sample Laminates absorbed on average 32% more energy than the E-glass Laminates when subjected to the same impact velocity.
- the Sample Laminates exhibited far less damage than the E-glass Laminates and did not reach penetration.
- the glasses in this Example were made by melting mixtures of reagent grade chemicals in powder form in 10%Rh/Pt crucibles at the temperatures between 1500°C and 1550°C (2732°F - 2822°F) for four hours. Each batch was about 1200 grams. After the 4-hour melting period, the molten glass was poured onto a steel plate for quenching. To compensate volatility loss of B 2 0 3 (typically about 5% of the total target B 2 0 3 concentration in laboratory batch melting condition for the 1200 gram batch size), the boron retention factor in the batch calculation was set at 95%. Other volatile species, such as fluoride and alkali oxides, were not adjusted in the batches for their emission loss because of their low concentrations in the glasses.
- the compositions in the examples represent as-batched compositions. Since reagent chemicals were used in preparing the glasses with an adequate adjustment of B 2 0 3 , the as-batched compositions illustrated are considered to be close to the measured compositions.
- a polished disk of each glass sample with 40 mm diameter and 1 - 1.5 mm thickness was used for electrical property and mechanical property measurements, which were made from annealed glasses.
- Dielectric constant (D k ) and dissipation factor (D f ) of each glass were determined from 1 MHz to 1 GHz by ASTM Test Method D150
- a microindentation method was used to determine Young's modulus (from the initial slope of the curve of indentation loading - indentation depth, in the indenter unloading cycle), and microhardness (from the maximum
- microindentation apparatus was calibrated using a commercial standard reference glass block with a product name BK7.
- the reference glass has Young's modulus 90.1 GPa with one standard deviation of 0.26 GPa and microhardness 4.1 GPa with one standard deviation of 0.02 GPa, all of which were based on five measurements.
- Samples 1 - 8 provide glass compositions (Table 4) by weight percentage: Si0 2 62.5 - 67.5%, B 2 0 3 8.4 - 9.4%, A1 2 0 3 10.3 - 16.0%, MgO 6.5 - 11.1%, CaO 1.5 - 5.2%, Li 2 0 1.0%, Na 2 0 0.0%, K 2 0 0.8%, Fe 2 0 3 0.2 - 0.8%, F 2 0.0%, Ti0 2 0.0%, and sulfate (expressed as S0 3 ) 0.0%.
- the glasses were found to have D k of 5.44 - 5.67 and Df of 0.0006 - 0.0031 at 1 MHz, and D k of 5.47 - 6.67 and D f of 0.0048 - 0.0077 at 1 GHz frequency.
- the electric properties of the compositions in Series III illustrate significantly lower (i.e., improved) D k and D f over standard E-glass with D k of 7.29 and D f of 0.003 at 1 MHz and D k of 7.14 and D f of 0.0168 at lGHz.
- the compositions in Table 4 have forming temperatures (T F ) of 1300 - 1372 °C and forming windows (T F - T L ) of 89 - 222°C. This can be compared to a standard E-glass which has T F typically in the range 1170 - 1215°C. To prevent glass devitrification in fiber forming, a forming window (T F - T L ) greater than 55°C is desirable. All of the compositions in Table 4 exhibit satisfactory forming windows. Although the compositions of Table 4 have higher forming temperatures than E-glass, they have significantly lower forming temperatures than D-glass (typically about 1410°C).
- Samples 9 - 15 provide glass compositions: Si0 2 60.8 - 68.0%, B 2 0 3 8.6 and 11.0%, A1 2 0 3 8.7 - 12.2%, MgO 9.5 - 12.5%, CaO 1.0 - 3.0%, Li 2 0 0.5 - 1.5%, Na 2 0 0.5%, K 2 0 0.8%, Fe 2 0 3 0.4%, F 2 0.3%, Ti0 2 0.2%, and sulfate (expressed as S0 3 ) 0.0%.
- the glasses were found to have D k of 5.55 - 5.95 and D f of 0.0002 - 0.0013 at 1 MHz, and D k of 5.54 - 5.94 and D f of 0.0040 - 0.0058 at 1 GHz frequency.
- the electric properties of the compositions in Table 5 illustrate significantly lower (improved) D k and D f over standard E-glass with D k of 7.29 and D f of 0.003 at 1 MHz, and D k of 7.14 and D f of 0.0168 at 1GHz.
- the compositions of Table 5 have Young's modulus of 86.5 - 91.5 GPa and microhardness of 4.0 - 4.2 GPa, both of which are equal or higher than standard E glass that has Young's modulus of 85.9 GPa and microhardness of 3.8 GPa.
- the Young's moduli of the compositions in the Table 5 are also significantly higher than D-glass which is about 55 GPa based on literature data.
- the compositions of Table 5 have forming temperature (T F ) of 1224 - 1365 °C, and forming windows (T F - T L ) of 6 - 105°C as compared to standard E-glass having T F in the range 1 170 - 1215°C.
- Some, but not all, of the Table 5 compositions have a forming window (T F - T L ) greater than 55°C, which is considered preferable in some circumstances to avoid glass devitrification in commercial fiber forming operations.
- the Table 5 compositions have lower forming temperatures than those of D-glass (1410°C), although higher than E-glass.
- Table 7 Some glass compositions useful in some embodiments of the present invention.
- Samples 29 - 62 provide glass compositions (Table 8) by weight percentage: Si0 2 53.74 - 76.97%, B 2 0 3 4.47 - 14.28%, A1 2 0 3 4.63 - 15.44%, MgO 4.20 - 12.16%, CaO 1.04 - 10.15%, Li 2 0 0.0 - 3.2%, Na 2 0 0.0- 1.61%, K 2 0 0.01 - 0.05%, Fe 2 0 3 0.06 - 0.35%, F 2 0.49- 1.48%, Ti0 2 0.05- 0.65%, and sulfate (expressed as S0 3 ) 0.0- 0.16%.
- Samples 29-62 provide glass compositions (Table 8) by weight percentage wherein the (MgO + CaO) content is 7.81- 16.00%, the ratio CaO/MgO is 0.09 - 1.74%, the (Si0 2 +B 2 0 3 ) content is 67.68 - 81.44%, the ratio A1 2 0 3 /B 2 0 3 is 0.90 - 1.71%, the (Li 2 0+Na 2 0+K 2 0) content is 0.03 - 3.38 %, and the ratio Li 2 0/(Li 2 0+Na 2 0+K 2 0) is 0.00 - 0.95%.
- compositions of Table 8 have a fiber density of 2.331 - 2.416g/cm 3 and an average fiber tensile strength (or fiber strength) of 3050 - 3578 MPa.
- fiber samples from the glass compositions were produced from a 10Rh/90Pt single tip fiber drawing unit. Approximately, 85 grams of cullet of a given composition was fed into the bushing melting unit and conditioned at a temperature close or equal to the 100 Poise melt viscosity for two hours. The melt was subsequently lowered to a temperature close or equal to the 1000 Poise melt viscosity and stabilized for one hour prior to fiber drawing. Fiber diameter was controlled to produce an approximately 10 ⁇ diameter fiber by controlling the speed of the fiber drawing winder. All fiber samples were captured in air without any contact with foreign objects. The fiber drawing was completed in a room with a controlled humidity of between 40 and 45% RH.
- Fiber tensile strength was measured using a Kawabata KES-G1 (Kato Tech Co. Ltd., Japan) tensile strength analyzer equipped with a Kawabata type C load cell. Fiber samples were mounted on paper framing strips using a resin adhesive. A tensile force was applied to the fiber until failure, from which the fiber strength was determined based on the fiber diameter and breaking stress. The test was done at room temperature under the controlled humidity between 40 - 45% RH. The average values and standard deviations were computed based on a sample size of 65 - 72 fibers for each composition.
- the glasses were found to have D k of 4.83 - 5.67 and D f of 0.003 - 0.007 at 1 GHz.
- the electric properties of the compositions in Table 8 illustrate significantly lower (i.e., improved) D k and D f over standard E-glass which has a D k of 7.14 and a D f of 0.0168 at 1GHz.
- the compositions in Table 8 have forming temperatures (T F ) of 1247 - 1439 °C and forming windows (T F - T L ) of 53 - 243°C.
- the compositions in Table 8 have liquidus temperature (T L ) of 1058 - 1279 °C. This can be compared to a standard E-glass which has T F typically in the range 1170 - 1215°C. To prevent glass devitrification in fiber forming, a forming window (T F - T L ) greater than 55°C is sometimes desirable. All of the compositions in Table 8 exhibit satisfactory forming windows.
- Table 8 Some glass compositions useful in some embodiments of the present invention.
- Samples 63 - 73 provide glass compositions (Table 9) by weight percentage: Si0 2 62.35 - 68.35%, B 2 0 3 6.72 - 8.67%, A1 2 0 3 10.53 - 18.04%, MgO 8.14 - 11.44%, CaO 1.67 - 2.12%, Li 2 0 1.07 - 1.38%, Na 2 0 0.02%, K 2 0 0.03 - 0.04%, Fe 2 0 3 0.23 - 0.33%, F 2 0.49- 0.60%, Ti0 2 0.26- 0.61%, and sulfate (expressed as S0 3 ) 0.0%.
- Samples 63-73 provide glass compositions (Table 9) by weight percentage wherein the (MgO + CaO) content is 9.81- 13.34%, the ratio CaO/MgO is 0.16 - 0.20, the (Si0 2 +B 2 0 3 ) content is 69.59 - 76.02%, the ratio A1 2 0 3 /B 2 0 3 is 1.37 - 2.69, the (Li 2 0+Na 2 0+K 2 0) content is 1.09 - 1.40 %, and the ratio Li 2 0/(Li 2 0+Na 2 0+K 2 0) is 0.98.
- compositions of Table 9 have a fiber density of 2.371 - 2.407g/cm 3 and an average fiber tensile strength (or fiber strength) of 3730 - 4076 MPa.
- the fiber tensile strengths for the fibers made from the compositions of Table 9 were measured in the same way as the fiber tensile strengths measured in connection with the compositions of Table 8.
- the fibers formed from the compositions were found to have Young's modulus (E) values ranging from 73.84-81.80 GPa.
- the Young's modulus (E) values for the fibers were measured using the sonic modulus method on fibers.
- Elastic modulus values for the fibers drawn from glass melts having the recited compositions were determined using an ultrasonic acoustic pulse technique on a Panatherm 5010 instrument from Panametrics, Inc. of Waltham, Massachusetts. Extensional wave reflection time was obtained using twenty micro-second duration, 200 kHz pulses. The sample length was measured and the respective extensional wave velocity (V E ) was calculated.
- Fiber density (p) was measured using a Micromeritics AccuPyc 1330 pycnometer. In general, 20
- the glasses were found to have D k of 5.20 - 5.54 and Df of 0.0010 - 0.0020 at 1 GHz.
- the electric properties of the compositions in Table 9 illustrate significantly lower (i.e., improved) D k and D f over standard E-glass with D k of 7.14 and D f of 0.0168 at 1GHz.
- the compositions in Table 9 have forming temperatures (T ) of 1303 - 1388 °C and forming windows (T - T L ) of 51 - 144°C.
- Desirable characteristics that can be exhibited by various but not necessarily all embodiments of the present invention can include, but are not limited to, the following: the provision of glass fibers, fiber glass strands, glass fiber fabrics, composites, and laminates having a relatively low density; the provision of glass fibers, fiber glass strands, glass fiber fabrics, composites, and laminates having a relatively high modulus; the provision of glass fibers, fiber glass strands, glass fiber fabrics, composites, and laminates having a relatively high strain-to- failure; the provision of glass fibers, fiber glass strands, glass fiber fabrics, composites, laminates, and prepregs useful for reinforcement applications; and the provision of glass fibers, fiber glass strands, glass fiber fabrics, composites, laminates, and prepregs having relatively low cost compared to other glass fibers, fiber glass strands, glass fiber fabrics, composites, laminates, and prepregs for reinforcement applications.
Abstract
Description
Claims
Priority Applications (5)
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KR1020137009355A KR20140005876A (en) | 2010-09-14 | 2011-09-14 | Low density and high strength fiber glass for reinforcement applications |
CN2011800492867A CN103153896A (en) | 2010-09-14 | 2011-09-14 | Low density and high strength fiber glass for reinforcement applications |
MX2013002777A MX2013002777A (en) | 2010-09-14 | 2011-09-14 | Low density and high strength fiber glass for reinforcement applications. |
JP2013528393A JP2013542904A (en) | 2010-09-14 | 2011-09-14 | Low density, high strength fiber glass for reinforcement applications |
EP11760937.0A EP2616400A1 (en) | 2010-09-14 | 2011-09-14 | Low density and high strength fiber glass for reinforcement applications |
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US38273810P | 2010-09-14 | 2010-09-14 | |
US61/382,738 | 2010-09-14 | ||
US12/940,764 US8697590B2 (en) | 2006-12-14 | 2010-11-05 | Low dielectric glass and fiber glass for electronic applications |
US12/940,764 | 2010-11-05 | ||
US13/229,012 | 2011-09-09 | ||
US13/229,012 US8697591B2 (en) | 2006-12-14 | 2011-09-09 | Low dielectric glass and fiber glass |
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WO2012037219A1 true WO2012037219A1 (en) | 2012-03-22 |
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EP (1) | EP2616400A1 (en) |
JP (1) | JP2013542904A (en) |
KR (1) | KR20140005876A (en) |
CN (1) | CN103153896A (en) |
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Cited By (6)
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CN103360725A (en) * | 2013-07-02 | 2013-10-23 | 广东生益科技股份有限公司 | Thermosetting resin composition with high insulating property, prepreg and metal-clad foil plate |
JP2015006973A (en) * | 2013-05-31 | 2015-01-15 | 日本電気硝子株式会社 | Composition for glass fiber, glass fiber and manufacturing method of glass fiber |
WO2016015736A1 (en) * | 2014-07-31 | 2016-02-04 | Vestas Wind Systems A/S | Improvements relating to reinforcing structures for wind turbine blades |
WO2017176577A1 (en) * | 2016-04-04 | 2017-10-12 | Ppg Industries Ohio, Inc. | Fiberglass containing composites with improved retained glass fiber length, impact strength, and tensile properties |
US10927254B2 (en) | 2016-12-02 | 2021-02-23 | Ems-Patent Ag | Polyamide moulding compounds with low relative permittivity |
WO2023213614A1 (en) * | 2022-05-02 | 2023-11-09 | Delcotex Delius Techtex Gmbh & Co. Kg | Prepreg layer and use thereof |
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KR101427166B1 (en) * | 2013-07-08 | 2014-08-07 | 주식회사 제이에프코리아 | radome for antenna and manufacturing method thereof |
US9278883B2 (en) * | 2013-07-15 | 2016-03-08 | Ppg Industries Ohio, Inc. | Glass compositions, fiberizable glass compositions, and glass fibers made therefrom |
KR101641544B1 (en) * | 2013-11-29 | 2016-07-21 | 니토 보세키 가부시기가이샤 | Glass fiber fabric-resin composition laminate |
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US20230373845A1 (en) * | 2021-02-24 | 2023-11-23 | Nitto Boseki Co., Ltd. | Glass composition for glass fiber, glass fiber, glass fiber fabric, and glass fiber-reinforced resin composition |
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- 2011-09-14 JP JP2013528393A patent/JP2013542904A/en not_active Withdrawn
- 2011-09-14 WO PCT/US2011/051555 patent/WO2012037219A1/en active Application Filing
- 2011-09-14 KR KR1020137009355A patent/KR20140005876A/en not_active Application Discontinuation
- 2011-09-14 TW TW100133113A patent/TW201217295A/en unknown
- 2011-09-14 CN CN2011800492867A patent/CN103153896A/en active Pending
- 2011-09-14 EP EP11760937.0A patent/EP2616400A1/en not_active Withdrawn
- 2011-09-14 MX MX2013002777A patent/MX2013002777A/en not_active Application Discontinuation
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JP2015006973A (en) * | 2013-05-31 | 2015-01-15 | 日本電気硝子株式会社 | Composition for glass fiber, glass fiber and manufacturing method of glass fiber |
CN103360725A (en) * | 2013-07-02 | 2013-10-23 | 广东生益科技股份有限公司 | Thermosetting resin composition with high insulating property, prepreg and metal-clad foil plate |
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WO2016015736A1 (en) * | 2014-07-31 | 2016-02-04 | Vestas Wind Systems A/S | Improvements relating to reinforcing structures for wind turbine blades |
US11644006B2 (en) | 2014-07-31 | 2023-05-09 | Vestas Wind Systems A/S | Reinforcing structures for wind turbine blades |
WO2017176577A1 (en) * | 2016-04-04 | 2017-10-12 | Ppg Industries Ohio, Inc. | Fiberglass containing composites with improved retained glass fiber length, impact strength, and tensile properties |
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WO2023213614A1 (en) * | 2022-05-02 | 2023-11-09 | Delcotex Delius Techtex Gmbh & Co. Kg | Prepreg layer and use thereof |
Also Published As
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KR20140005876A (en) | 2014-01-15 |
JP2013542904A (en) | 2013-11-28 |
EP2616400A1 (en) | 2013-07-24 |
CN103153896A (en) | 2013-06-12 |
MX2013002777A (en) | 2013-10-28 |
TW201217295A (en) | 2012-05-01 |
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