EP2616399A1 - Low density and high strength fiber glass for ballistic applications - Google Patents

Low density and high strength fiber glass for ballistic applications

Info

Publication number
EP2616399A1
EP2616399A1 EP11760934.7A EP11760934A EP2616399A1 EP 2616399 A1 EP2616399 A1 EP 2616399A1 EP 11760934 A EP11760934 A EP 11760934A EP 2616399 A1 EP2616399 A1 EP 2616399A1
Authority
EP
European Patent Office
Prior art keywords
weight percent
composite
glass
fabric
glass fibers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11760934.7A
Other languages
German (de)
French (fr)
Inventor
James Carl Peters
Juan Camilo Serrano
Hong Li
Cheryl A. Richards
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PPG Industries Ohio Inc
Original Assignee
PPG Industries Ohio Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US12/940,764 external-priority patent/US8697590B2/en
Priority claimed from US13/229,012 external-priority patent/US8697591B2/en
Application filed by PPG Industries Ohio Inc filed Critical PPG Industries Ohio Inc
Publication of EP2616399A1 publication Critical patent/EP2616399A1/en
Withdrawn legal-status Critical Current

Links

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
    • 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
    • C08J5/24—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
    • 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
    • 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
    • C08J5/04—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
    • 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
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • 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
    • C08J5/248—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using pre-treated fibres
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F41H5/0471—Layered armour containing fibre- or fabric-reinforced layers
    • F41H5/0485—Layered armour containing fibre- or fabric-reinforced layers all the layers being only fibre- or fabric-reinforced layers

Definitions

  • the present invention relates to composites comprising glass fibers adapted for use in high energy impact applications such as ballistic or blast resistance applications.
  • Materials operable to withstand high energy impacts from various sources find use in a wide range of applications, including civilian and military structural reinforcement applications and armored vehicle applications.
  • Ceramic plates and reinforced composite materials have been used to shield vehicles from potential damage caused by various explosive devices. Predicting which materials will exhibit desirable properties for use in ballistic applications is notoriously difficult, however.
  • 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.”
  • S-2 Glass Another commonly used glass composition is commercially available from AGY (Aiken, South Carolina) under the trade name "S-2 Glass.”
  • reinforcing polymeric resins with glass fibers for high energy impact applications such as ballistic or blast resistance applications does not necessarily result in composites having other desirable mechanical properties as well.
  • glass fibers can be produced from small streams of molten glass extruded through small orifices located in a bushing.
  • the fibers of molten glass which issue from the bushing are attenuated to a desired diameter by pulling the fibers until the desired diameter is achieved, during which time the fibers cool and solidify.
  • These cooled fibers or filaments can then be coated with a sizing that can impart desired properties.
  • sizing refers to a coating composition applied to fiber glass filaments immediately after forming, and the term may be used
  • the sized glass fibers can be gathered into bundles or strands comprising a plurality of individual fibers.
  • bundles or strands can be further gathered into rovings comprising a plurality of bundles or strands.
  • Continuous strands or rovings can be wound upon a spool to form a package. Lengths of strands or rovings can then be dispensed from the spool as needed.
  • Various embodiments of the present invention relate generally to low density and high strength glass fibers, and to fiber glass strands, yarns, fabrics, composites, and armor panels comprising low density and high strength glass fibers adapted for use in ballistic or blast resistance applications.
  • 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 comprising:
  • the (Li 2 0 + Na 2 0 + K 2 0) content is less than 2 weight percent, wherein the MgO content is at least twice the content of CaO on a weight percent basis, and wherein the composite is adapted for use in ballistics or blast resistance applications.
  • 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 comprising
  • the composite is adapted for use in ballistics or blast resistance applications.
  • composites of the present invention can exhibit a 0.30 cal FSP V 50 value of at least about 900 fps at an areal density of about 2 lb/ft 2 and a thickness of about 5-6 mm when measured by the U.S. Department of Defense Test Method Standard for V 50 Ballistic Test for Armor, MIL-STD-662F, December 1997.
  • Composites of the present invention in some embodiments, can exhibit a 0.50 cal FSP V 50 value of at least about 1200 fps at an areal density of about 4.8 - 4.9 lb/ft 2 and a thickness of about 13 - 13.5 mm when measured by the U.S. Department of Defense Test Method Standard for V 50 Ballistic Test for Armor, MIL-STD-662F, December 1997.
  • the polymeric resin that can be used in some embodiments of the present invention comprises an epoxy resin.
  • the polymeric resin can comprise at least one of polyethylene, polypropylene, polyamide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, and thermoset polyurethane resins.
  • the plurality of glass fibers used in the composite are arranged to form a fabric.
  • the plurality of glass fibers used in some embodiments of composites of the present invention are woven to form a fabric.
  • Such fabrics can include, in some embodiments, 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 armor panels comprising composites of the present invention.
  • Fiberizable glass compositions have been developed which provide improved electrical performance (i.e., low dielectric constant, Dk, and/or low dissipation factor, Df) relative to standard E-glass, while providing temperature- viscosity relationships that are more conducive to commercially practical fiber forming than previous low Dk 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 composites comprising glass fibers.
  • Composites of the present invention are suitable for use in high mechanical stress applications, including, but not limited to, high energy impact applications.
  • a composite of the present invention comprises a polymeric resin and a plurality of glass fibers disposed in the polymeric resin. Glass fibers useful in some embodiments of the present invention can exhibit properties especially desirable for high energy impact applications such as ballistic or blast resistance applications.
  • 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.
  • composites of the present invention can be suitable for use in armor applications.
  • some embodiments of composites can be used in the production of armor panels.
  • a composite of the present invention can be formed into a panel, wherein the panel can exhibit a 0.30 cal FSP ("fragment simulating projectile") V 50 value of at least about 900 feet per second (fps) at a panel areal density of about 2 lb/ft 2 and a panel thickness of about 5-6 mm when measured by the U.S. Department of Defense Test Method Standard for V 50 Ballistic Test for Armor, MIL-STD-662F, December 1997 (hereinafter "MIL-STD-662F”), the entirety of which is incorporated herein by reference.
  • FSP fragment simulating projectile
  • a composite of the present invention can be formed into a panel, wherein the panel can exhibit a 0.50 cal FSP V 50 value of at least about 1200 fps at a panel areal density of about 4.8 - 4.9 lb/ft 2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F.
  • V 50 values can depend on the panel areal density and the panel thickness
  • composites of the present invention can have different V 50 values depending on how the panel is constructed.
  • One advantage of some embodiments of the present invention is the provision of composites having higher V 50 values than similarly constructed composites assembled using E-glass fibers.
  • 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:
  • 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. In other embodiments, the Li 2 0 content can be greater than either the Na 2 0 content or the K 2 0 content.
  • 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:
  • the composite is adapted for use in ballistics or blast resistance applications.
  • 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.
  • the Li 2 0 content can be greater than either the Na 2 0 content or the K 2 0 content.
  • embodiments of the present invention relate to composites comprising a plurality of glass fibers formed from such compositions.
  • a composite of the present invention can be formed into a panel, wherein the panel exhibits a 0.30 cal FSP V 50 value of at least about 900 fps at a panel areal density of about 2 lb/ft 2 and a panel thickness of about 5-6 mm when measured by MIL-STD-662F.
  • a composite of the present invention can be formed into a panel, wherein the panel exhibits a 0.30 cal FSP V 50 value of at least about 1000 fps at a panel areal density of about 2 lb/ft 2 and a panel thickness of about 5-6 mm when measured by MIL- STD-662F.
  • a composite can be formed into a panel, wherein the panel exhibits a 0.30 cal FSP V 50 value of at least about 1 100 fps at a panel areal density of about 2 lb/ft 2 and a panel thickness of about 5-6 mm when measured MIL-STD-662F.
  • a composite can be formed into a panel, wherein the panel exhibits a 0.30 cal FSP V 50 value of about 900 fps to about 1 140 fps at a panel areal density of about 2 lb/ft 2 and a panel thickness of about 5-6 mm when measured by MIL-STD-662F.
  • a composite of the present invention can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V 50 value of at least about 1200 fps at a panel areal density of about 4.8 - 4.9 lb/ft 2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F.
  • a composite can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V 50 value of at least about 1300 fps at a panel areal density of about 4.8 - 4.9 lb/ft 2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F.
  • a composite can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V 50 value of at least about 1400 fps at a panel areal density of about 4.8 - 4.9 lb/ft 2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F.
  • a composite can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V 50 value of about 1200 fps to about 1440 fps at a panel areal density of about 4.8 - 4.9 lb/ft 2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F.
  • Composites of the present invention can comprise various polymeric resins, depending on the desired properties and applications.
  • a composite 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 as disclosed herein, the composite can be formed into a panel, such as an armor panel for ballistic or blast resistance, and the polymeric resin comprises an epoxy resin.
  • 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 as disclosed herein, the composite can be formed into a panel, such as an armor panel for ballistic or blast resistance, and the polymeric resin comprises a polydicyclopentadiene resin.
  • the polymeric resin can comprise polyethylene, polypropylene, polyamides (including Nylon), polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, thermoset polyurethane, cyanate esters, or bis-maleimide resins.
  • a composite 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 as disclosed herein, the composite can be formed into a panel, such as an armor panel for ballistic or blast resistance, and at least one of the plurality of glass fibers is at least partially coated with a sizing composition.
  • the sizing composition can be compatible with the polymeric resin.
  • a composite 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 as disclosed herein, the composite can be formed into a panel, such as an armor panel for ballistic or blast resistance, and the plurality of glass fibers are arranged to form a fabric.
  • the composite can be formed into a panel, wherein the panel exhibits a 0.30 cal FSP V 50 value of at least about 1000 fps at a panel areal density of about 2 lb/ft 2 and a panel thickness of about 5-6 mm when measured by MIL-STD-662F.
  • the composite in other embodiments of the present invention comprising a plurality of glass fibers arranged to form a fabric, can be formed into a panel, wherein the panel exhibits a 0.30 cal FSP V 50 value of at least about 1100 fps at a panel areal density of about 2 lb/ft 2 and a panel thickness of about 5-6 mm when measured by MIL-STD-662F.
  • the composite can be formed into a panel, wherein the panel exhibits a 0.30 cal FSP V 50 value of about 900 fps to about 1140 fps at a panel areal density of about 2 lb/ft 2 and a panel thickness of about 5-6 mm when measured by MIL-STD-662F.
  • the composite can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V 50 value of at least about 1200 fps at a panel areal density of about 4.8 - 4.9 lb/ft 2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F.
  • the composite in other embodiments of the present invention comprising a plurality of glass fibers arranged to form a fabric, can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V 50 value of at least about 1300 fps at a panel areal density of about 4.8 - 4.9 lb/ft 2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F.
  • the composite can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V 50 value of at least about 1400 fps at a panel areal density of about 4.8 - 4.9 lb/ft 2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F.
  • a composite in some embodiments of the present invention comprising a plurality of glass fibers arranged to form a fabric, a composite can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V 50 value of about 1200 fps to about 1440 fps at a panel areal density of about 4.8 - 4.9 lb/ft 2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F.
  • the plurality of glass fibers are woven to form the fabric.
  • the glass fiber 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.
  • the polymeric resin comprises an epoxy resin. In some embodiments of the present invention comprising a plurality of glass fibers arranged to form a fabric, the polymeric resin comprises a polydicyclopentadiene resin. In some embodiments of the present invention, the polymeric resin comprises polyethylene, polypropylene, polyamides (including Nylon), polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, thermoset polyurethane, cyanate esters, or bis-maleimide 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.
  • Glass fiber fabrics useful in 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 single end strands can be subsequently processed into assembled rovings by gathering several ends together and providing a small level of twist. Occasionally, the bundle integrity is increased by treatment with water or steam. The gathered multi-end strand can then be wound onto a 3" cardboard spool. At this point the spools can be used for warp or weft feed by tying the strand ends into a traditional rapier loom for fabric weaving into the predetermined style.
  • 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, reaction injection molding, and pultrusion. Composites of the present invention can be prepared using such molding techniques as known to those of ordinary skill in the art.
  • 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. At this point, the tool is 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.
  • such composites can also be made using vacuum assisted resin infusion technology as described below.
  • 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.
  • polydicyclopentadiene 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 example, for polydicyclopentadiene resins, the resin is mixed with the proper amount of catalyst, and in some cases an inhibitor, in the proportions recommended by the pDCPD supplier or otherwise known to a person of ordinary skill in the art. The DCPD 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. At this point, the tool is set to a temperature of about 120 °C for up to 4 hours. The resulting rigid composites may then be de -molded.
  • composites 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 12 ⁇ .
  • Glass fibers suitable for use in other embodiments of the present invention have a diameter of about 6 ⁇ .
  • the glass fibers can have a diameter of about 6 ⁇ , although other glass fiber diameters could also be used.
  • glass fibers and glass fiber strands suitable for use in the present invention can comprise a variety of glass compositions. 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 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.
  • some embodiments of the glass compositions described herein 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 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. In general, 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
  • 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 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. In some embodiments, the compositions are characterized by a MgO content, for example, on the order of about 8 - 13 weight percent. In yet other embodiments, the MgO content can be on the order of about 9 - 12 weight percent. In some other embodiments, the MgO content can be on the order of about 8 - 12 weight percent. In yet some other embodiments, the MgO content can be on the order of about 8
  • the compositions that can be used in glass fibers or fiber glass strands 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 some embodiments 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.
  • compositions that can be used in some embodiments 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 11 - 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.
  • 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.
  • certain glass compositions within the ranges set forth above can be made that exhibit forming temperatures (T F ) at 1000 poise viscosity no greater than 1370°C.
  • T F forming temperatures
  • the T F of some embodiments are no greater than 1320°C, or no greater than 1300°C, or no greater than 1290°C, or no greater than 1260°C, or no greater than 1250°C.
  • 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.
  • T L liquidus temperature
  • 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 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.
  • minor amounts e.g., up to about 2.0 weight percent
  • the total of optional constituents is no more than 2 weight percent, or no more than 1 weight percent.
  • 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.
  • impurities may also be present from raw materials or from contamination during the melting processes, such as SrO, BaO, Cl 2 , P2O5, 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, particularly as compared to E-glass fibers, fiber glass strands formed from E-glass, and related products. Such mechanical properties may be beneficial in some embodiments of composites (or panels incorporating composites) of the present invention.
  • some embodiments of glass fibers 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 ballistic or impact resistance applications where there is a desire to increase mechanical properties or product performance while reducing the overall weight of the composite.
  • glass fibers are typically at least partially coated with a sizing composition.
  • glass fibers used to form composites of the present invention will be at least partially coated with a sizing composition.
  • One skilled in the art may choose one of many commercially available sizing compositions for the glass fibers based upon a number of factors including, for example, performance properties of the sizing compositions, desired flexibility of the resulting fabric, cost, and other factors.
  • 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, and Hybon 2016, TufRov 4588, as well as sizing compositions often used on yarns, such as 1383, 611 , 900, 610, and 690, each of which refer to sizing compositions for products commercially available from PPG Industries, Inc.
  • suitable sizing compositions can include Hybon 2026 or those sizing compositions described in U.S. Patent No. 6,890,050, which is hereby incorporated by reference.
  • composites of the present invention can comprise a plurality of glass fibers arranged to form a fabric, in some embodiments.
  • Any suitable fabric design known to one of ordinary skill in the art for ballistic applications can be used.
  • 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 tri axial non-crimp fabrics.
  • 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 ballistic applications may be used.
  • warp yarns can comprise 250 yield assembled rovings produced by gathering several ends from G75 yarn, DE75 yarn, and/or DEI 50 yarns.
  • 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 high energy impact applications such as ballistic or blast resistance 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 polydicyclopentadiene 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, and thermoplastic polyurethanes (TPU).
  • polyethylene polypropylene
  • polyamides including Nylon
  • polybutylene terephthalate polycarbonate
  • thermoplastic polyurethanes TPU
  • embodiments of the present invention include Hexion RIMR 135 epoxy with 1366 curing agent (available from Hexion Specialty Chemicals, Columbus, Ohio) and Applied Poleramic MMFCS2 epoxy (available from Applied Poleramic, Inc., Benicia, California).
  • Dicyclopentadiene resins useful in some embodiments of the present invention, along with catalysts and/or other materials useful in curing the resin, are commercially available from Materia, Inc. of Pasadena, CA.
  • glass fibers useful in some embodiments of the present invention were measured under controlled processing conditions and are listed in Table 1. Physical properties from standard E-glass fibers are included for reference.
  • “Specific Modulus” in Table 1 is the Young's modulus in N/m 2 divided by the specific weight in N/m 3 , measured at a temperature of 296 ⁇ 2 K (23 ⁇ 2 °C) and a relative humidity of 50 ⁇ 5 percent.
  • “Specific Tensile Strength” in Table 1 is the ultimate
  • 8 oz/yd 2 unidirectional fabrics useful in some embodiments of the present invention were produced on a rapier loom and infused with high modulus epoxy resin (Hexion RIMR 135) for mechanical property characterization.
  • the fabrics comprised E-225 yarns sized with a starch-oil sizing composition, and the yarns comprised glass fibers comprising the glass composition of Sample 1 in Table 1.
  • Equivalent unidirectional fabric and composites were also produced with E-glass input as controls. Vacuum assisted resin infusion technology was used to make the composites comprising the unidirectional fabrics.
  • a filament wound unidirectional fiber preform was cut to a desired size and placed on a silicone release treated glass table.
  • the stack was then covered with a peel ply, fitted with a flow enhancing media, and vacuum bagged using nylon bagging film.
  • the so-called "preform" was subjected to a vacuum pressure of about 27 inches Hg.
  • an amine-curable epoxy resin was mixed with an amine curing agent in the proportions recommended by the resin manufacturer.
  • the combined resin was then degassed in a vacuum chamber for 30 minutes and infused through the fabric preform until complete wet out of the fabric stack was achieved.
  • the table was covered with heated blankets (set to a temperature of about 45 - 50 °C) for 12 hours.
  • the resulting rigid composites were then de-molded and post cured at about 176 °F for 5 hours in a programmable convection oven.
  • the ballistic performance of various composites was evaluated by producing and testing panels at different areal densities.
  • reference panels were made with standard S-2 Glass ® (24 oz/yd 2 ) woven roving from AGY (Aiken, South Carolina) and with Hybon 2006 (25 oz/yd 2 ) E-glass woven roving from PPG Industries, Inc.
  • the control polymeric resin matrix material for the reference panels was MMFCS2 Epoxy from Applied Poleramic (Benicia, California).
  • the reference panels were screened against the 0.30 cal FSP at different areal densities.
  • the six-point ballistic limit (V 50 ) was calculated according to MIL-STD-662F.
  • damage analysis was performed on two representative reference panels to determine the extent of damage caused by the ballistic event. For this analysis, the six largest damage patterns observed in a panel under high intensity light were measured using image analysis software, and the mean damage zone was calculated.
  • Panels comprising composites of the present invention were produced via resin infusion using the benchmark epoxy resin MMFCS2 Epoxy from Applied Poleramic (Benicia, California) at 2 lb/ft 2 and 5 lb/ft 2 for ballistic screening against the 0.30 cal FSP and 0.50 cal FSP, respectively. Physical characteristics and ballistic performances of the panels are provided below in Table 3. Table 4 provides a comparison of the ballistic performances of panels comprising composites of the present invention with panels comprising composites comprising E-glass and S-2 Glass ® .
  • Tables 3 and 4 indicate that panels comprising composites of the present invention unexpectedly show a considerable increase in ballistic performance compared to panels comprising E-glass at comparable areal densities and are not out-performed by panels comprising costly S-2 Glass ® .
  • the damage observed on panels comprising composites of the present invention was equivalent to the damage extent calculated for panels comprising S-2 Glass ® , though panels comprising E-glass exhibited lesser damage.
  • Table 3 Physical characteristics and ballistic performance of panels comprising composites of the present invention.
  • Table 5 indicates that panels comprising composites of the present invention resulted in higher V 50 at equivalent areal density or equivalent V 50 at lower areal density than the panels formed from E-glass.
  • 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 6) 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 1 GHz.
  • the compositions in Table 6 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 6 exhibit satisfactory forming windows. Although the compositions of Table 6 have higher forming temperatures than E-glass, they have significantly lower forming temperatures than D-glass (typically about 1410°C). Table 6. Some glass compositions useful in some embodiments of the present invention.
  • 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 7 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 7 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 7 are also significantly higher than D-glass which is about 55 GPa based on literature data.
  • the compositions of Table 7 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 7 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 7 compositions have lower forming temperatures than those of D-glass (1410°C), although higher than E-glass. Table 7.
  • Table 8 Some glass compositions useful in some embodiments of the present invention.
  • Samples 29 - 62 provide glass compositions (Table 10) 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 10) 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 10 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 10 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 10 have forming temperatures (T F ) of 1247 - 1439 °C and forming windows (T F - T L ) of 53 - 243°C.
  • the compositions in Table 10 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 10 exhibit satisfactory forming windows.
  • Samples 63 - 73 provide glass compositions (Table 11) 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 1 1) 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.
  • the compositions of Table 11 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 11 were measured in the same way as the fiber tensile strengths measured in connection with the compositions of Table 10.
  • 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 11 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 1 1 have forming temperatures (T ) of 1303 - 1388 °C and forming windows (T - T L ) of 51 - 144°C.
  • Table 1 Some glass compositions useful in some embodiments of the present invention.
  • 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 having a relatively low density; the provision of glass fibers having a relatively high strength; the provision of glass fibers having a relatively high strain-to-failure; the provision of composites having relatively low areal density for a given fiber volume fraction or a given composite performance; the provision of glass fibers and composites useful for ballistic applications; and the provision of glass fibers and composites having relatively low cost compared to glass fibers and composites of similar ballistic performance.

Abstract

The present invention relates to fabrics, composites, prepregs, laminates, and other products incorporating glass fibers formed from glass compositions. The glass fibers, in some embodiments, are incorporated into composites that can be adapted for use in high energy impact applications such as ballistic or blast resistance applications. Glass fibers formed from some embodiments of the glass compositions can have certain desirable properties that can include, for example, desirable electrical properties (e.g. low Dk) or desirable mechanical properties (e.g., specific strength).

Description

LOW DENSITY AND HIGH STRENGTH FIBER
GLASS FOR BALLISTIC APPLICATIONS
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
This invention was made with government support under contract W911NF-09-9- 0003 awarded by the Army Research Laboratory. The government has certain rights in the invention. CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. Provisional Patent Application Serial No. 61/382,794, filed on September 14, 2010, the entire disclosure of which is hereby incorporated by reference. This application claims priority to and is a continuation-in- part of U.S. Patent Application No. 13/229,012, filed on September 9, 201 1, which is a continuation-in-part of U.S. Patent Application No. 12/940,764, filed on November 05, 2010, which is a continuation of U.S. Patent Application No. 11/610,761, filed on December 14, 2006, now U.S. Patent No. 7,829,490, which issued November 09, 2010, the contents of which are each hereby incorporated by reference in their entireties. FIELD OF INVENTION
The present invention relates to composites comprising glass fibers adapted for use in high energy impact applications such as ballistic or blast resistance applications.
BACKGROUND
Materials operable to withstand high energy impacts from various sources, such as projectiles and blast compression waves, find use in a wide range of applications, including civilian and military structural reinforcement applications and armored vehicle applications. Ceramic plates and reinforced composite materials, for example, have been used to shield vehicles from potential damage caused by various explosive devices. Predicting which materials will exhibit desirable properties for use in ballistic applications is notoriously difficult, however. 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." However, reinforcing polymeric resins with glass fibers for high energy impact applications such as ballistic or blast resistance applications does not necessarily result in composites having other desirable mechanical properties as well.
In general, glass fibers can be produced from small streams of molten glass extruded through small orifices located in a bushing. The fibers of molten glass which issue from the bushing are attenuated to a desired diameter by pulling the fibers until the desired diameter is achieved, during which time the fibers cool and solidify. These cooled fibers or filaments can then be coated with a sizing that can impart desired properties. As used herein, the term "sizing" refers to a coating composition applied to fiber glass filaments immediately after forming, and the term may be used
interchangeably with the terms "size," "sizing composition," "primary sizing," "binder composition," and "binder." After their formation and treatment, the sized glass fibers can be gathered into bundles or strands comprising a plurality of individual fibers.
Similarly, bundles or strands can be further gathered into rovings comprising a plurality of bundles or strands. Continuous strands or rovings can be wound upon a spool to form a package. Lengths of strands or rovings can then be dispensed from the spool as needed.
SUMMARY
Various embodiments of the present invention relate generally to low density and high strength glass fibers, and to fiber glass strands, yarns, fabrics, composites, and armor panels comprising low density and high strength glass fibers adapted for use in ballistic or blast resistance applications.
In one embodiment, 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 comprising:
Si02 60 - 68 weight percent;
B203 7 - 12 weight percent;
A1203 9 - 15 weight percent; MgO 8 - 15 weight percent;
CaO 0 - 4 weight percent;
Li20 0 - 2 weight percent;
Na20 0 - 1 weight percent;
K20 0 - 1 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 1 weight percent;
Ti02 0 - 2 weight percent; and
other constituents 0 - 5 weight percent total,
wherein the (Li20 + Na20 + K20) content is less than 2 weight percent, wherein the MgO content is at least twice the content of CaO on a weight percent basis, and wherein the composite is adapted for use in ballistics or blast resistance applications.
In another embodiment, 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 comprising
Si02 53.5-77 weight percent;
B203 4.5-14.5 weight percent;
A1203 94.5-18.5 weight percent;
MgO 4-12.5 weight percent;
CaO 0 - 10.5 weight percent;
Li20 0 - 4 weight percent;
Na20 0 - 2 weight percent;
K20 0 - 1 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 2 weight percent;
Ti02 0 - 2 weight percent; and
other constituents 0 - 5 weight percent total;
wherein the composite is adapted for use in ballistics or blast resistance applications.
In some embodiments, composites of the present invention can exhibit a 0.30 cal FSP V50 value of at least about 900 fps at an areal density of about 2 lb/ft2 and a thickness of about 5-6 mm when measured by the U.S. Department of Defense Test Method Standard for V50 Ballistic Test for Armor, MIL-STD-662F, December 1997. Composites of the present invention, in some embodiments, can exhibit a 0.50 cal FSP V50 value of at least about 1200 fps at an areal density of about 4.8 - 4.9 lb/ft2 and a thickness of about 13 - 13.5 mm when measured by the U.S. Department of Defense Test Method Standard for V50 Ballistic Test for Armor, MIL-STD-662F, December 1997.
The polymeric resin that can be used in some embodiments of the present invention comprises an epoxy resin. In some embodiments, the polymeric resin can comprise at least one of polyethylene, polypropylene, polyamide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, and thermoset polyurethane resins.
In some embodiments, the plurality of glass fibers used in the composite are arranged to form a fabric. The plurality of glass fibers used in some embodiments of composites of the present invention are woven to form a fabric. Such fabrics can include, in some embodiments, 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 armor panels comprising composites of the present invention.
These and other embodiments are discussed in greater detail in the detailed description which follows.
DETAILED DESCRIPTION
For the purposes of this specification, unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains errors necessarily resulting from the standard deviation found in applicable testing measurements.
It is further noted that, as used in this specification, the singular forms "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent.
Fiberizable glass compositions have been developed which provide improved electrical performance (i.e., low dielectric constant, Dk, and/or low dissipation factor, Df) relative to standard E-glass, while providing temperature- viscosity relationships that are more conducive to commercially practical fiber forming than previous low Dk 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 composites comprising glass fibers. Composites of the present invention, in some embodiments, are suitable for use in high mechanical stress applications, including, but not limited to, high energy impact applications. In some embodiments, for example, a composite of the present invention comprises a polymeric resin and a plurality of glass fibers disposed in the polymeric resin. Glass fibers useful in some embodiments of the present invention can exhibit properties especially desirable for high energy impact applications such as ballistic or blast resistance applications. Compared to glass fibers comprising E-glass, 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.
In some embodiments, composites of the present invention can be suitable for use in armor applications. For example, some embodiments of composites can be used in the production of armor panels. In some embodiments, a composite of the present invention can be formed into a panel, wherein the panel can exhibit a 0.30 cal FSP ("fragment simulating projectile") V50 value of at least about 900 feet per second (fps) at a panel areal density of about 2 lb/ft2 and a panel thickness of about 5-6 mm when measured by the U.S. Department of Defense Test Method Standard for V50 Ballistic Test for Armor, MIL-STD-662F, December 1997 (hereinafter "MIL-STD-662F"), the entirety of which is incorporated herein by reference. In this context, the term "composite" refers generically to a material comprising a polymeric resin and a plurality of glass fibers disposed in the polymeric resin, whereas the term "panel" refers to a composite having sheet-like physical dimensions or shape. In other embodiments, a composite of the present invention can be formed into a panel, wherein the panel can exhibit a 0.50 cal FSP V50 value of at least about 1200 fps at a panel areal density of about 4.8 - 4.9 lb/ft2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F. As V50 values can depend on the panel areal density and the panel thickness, composites of the present invention can have different V50 values depending on how the panel is constructed. One advantage of some embodiments of the present invention is the provision of composites having higher V50 values than similarly constructed composites assembled using E-glass fibers.
In some embodiments, 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:
Si02 60 - 68 weight percent;
B203 7 - 12 weight percent;
A1203 9 - 15 weight percent;
MgO 8 - 15 weight percent;
CaO 0 - 4 weight percent;
Li20 0 - 2 weight percent;
Na20 0 - 1 weight percent;
K20 0 - 1 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 1 weight percent;
Ti02 0 - 2 weight percent; and
other constituents 0-5 weight percent total; wherein the composite is adapted for use in ballistics or blast resistance applications. In some embodiments, the (Li20 + Na20 + K20) 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. In other embodiments, the Li20 content can be greater than either the Na20 content or the K20 content.
In some embodiments, 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:
Si02 53.5-77 weight percent;
B203 4.5-14.5 weight percent;
A1203 4.5-18.5 weight percent;
MgO 4-12.5 weight percent;
CaO 0 - 10.5 weight percent;
Li20 0 - 4 weight percent;
Na20 0 - 2 weight percent;
K20 0 - 1 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 2 weight percent;
Ti02 0 - 2 weight percent; and
other constituents 0 - 5 weight percent total;
wherein the composite is adapted for use in ballistics or blast resistance applications. In some embodiments, the (Li20 + Na20 + K20) 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. In other embodiments, the Li20 content can be greater than either the Na20 content or the K20 content.
A number of other glass compositions are disclosed herein, and other
embodiments of the present invention relate to composites comprising a plurality of glass fibers formed from such compositions.
Some embodiments of the present invention relate to panels, such as armor panels, comprising composites of the present invention. In some embodiments, a composite of the present invention can be formed into a panel, wherein the panel exhibits a 0.30 cal FSP V50 value of at least about 900 fps at a panel areal density of about 2 lb/ft2 and a panel thickness of about 5-6 mm when measured by MIL-STD-662F. In other embodiments, a composite of the present invention can be formed into a panel, wherein the panel exhibits a 0.30 cal FSP V50 value of at least about 1000 fps at a panel areal density of about 2 lb/ft2 and a panel thickness of about 5-6 mm when measured by MIL- STD-662F. In still other embodiments of the present invention, a composite can be formed into a panel, wherein the panel exhibits a 0.30 cal FSP V50 value of at least about 1 100 fps at a panel areal density of about 2 lb/ft2 and a panel thickness of about 5-6 mm when measured MIL-STD-662F. In some embodiments of the present invention, a composite can be formed into a panel, wherein the panel exhibits a 0.30 cal FSP V50 value of about 900 fps to about 1 140 fps at a panel areal density of about 2 lb/ft2 and a panel thickness of about 5-6 mm when measured by MIL-STD-662F.
In some embodiments, a composite of the present invention can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V50 value of at least about 1200 fps at a panel areal density of about 4.8 - 4.9 lb/ft2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F. In other embodiments of the present invention, a composite can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V50 value of at least about 1300 fps at a panel areal density of about 4.8 - 4.9 lb/ft2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F. In still other embodiments of the present invention, a composite can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V50 value of at least about 1400 fps at a panel areal density of about 4.8 - 4.9 lb/ft2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F. In some embodiments of the present invention, a composite can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V50 value of about 1200 fps to about 1440 fps at a panel areal density of about 4.8 - 4.9 lb/ft2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F.
Composites of the present invention can comprise various polymeric resins, depending on the desired properties and applications. In some embodiments of the present invention, a composite 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 as disclosed herein, the composite can be formed into a panel, such as an armor panel for ballistic or blast resistance, and the polymeric resin comprises an epoxy resin. 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 as disclosed herein, the composite can be formed into a panel, such as an armor panel for ballistic or blast resistance, and the polymeric resin comprises a polydicyclopentadiene resin. In some embodiments of the present invention, the polymeric resin can comprise polyethylene, polypropylene, polyamides (including Nylon), polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, thermoset polyurethane, cyanate esters, or bis-maleimide resins.
In some embodiments of the present invention, a composite 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 as disclosed herein, the composite can be formed into a panel, such as an armor panel for ballistic or blast resistance, and at least one of the plurality of glass fibers is at least partially coated with a sizing composition. In some embodiments of the present invention, the sizing composition can be compatible with the polymeric resin.
In some embodiments of the present invention, a composite 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 as disclosed herein, the composite can be formed into a panel, such as an armor panel for ballistic or blast resistance, and the plurality of glass fibers are arranged to form a fabric. In some embodiments of the present invention comprising a plurality of glass fibers arranged to form a fabric, the composite can be formed into a panel, wherein the panel exhibits a 0.30 cal FSP V50 value of at least about 1000 fps at a panel areal density of about 2 lb/ft2 and a panel thickness of about 5-6 mm when measured by MIL-STD-662F. In other embodiments of the present invention comprising a plurality of glass fibers arranged to form a fabric, the composite can be formed into a panel, wherein the panel exhibits a 0.30 cal FSP V50 value of at least about 1100 fps at a panel areal density of about 2 lb/ft2 and a panel thickness of about 5-6 mm when measured by MIL-STD-662F. In still other embodiments of the present invention comprising a plurality of glass fibers arranged to form a fabric, the composite can be formed into a panel, wherein the panel exhibits a 0.30 cal FSP V50 value of about 900 fps to about 1140 fps at a panel areal density of about 2 lb/ft2 and a panel thickness of about 5-6 mm when measured by MIL-STD-662F. In some embodiments of the present invention comprising a plurality of glass fibers arranged to form a fabric, the composite can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V50 value of at least about 1200 fps at a panel areal density of about 4.8 - 4.9 lb/ft2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F. In other embodiments of the present invention comprising a plurality of glass fibers arranged to form a fabric, the composite can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V50 value of at least about 1300 fps at a panel areal density of about 4.8 - 4.9 lb/ft2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F. In still other embodiments of the present invention comprising a plurality of glass fibers arranged to form a fabric, the composite can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V50 value of at least about 1400 fps at a panel areal density of about 4.8 - 4.9 lb/ft2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F. In some embodiments of the present invention comprising a plurality of glass fibers arranged to form a fabric, a composite can be formed into a panel, wherein the panel exhibits a 0.50 cal FSP V50 value of about 1200 fps to about 1440 fps at a panel areal density of about 4.8 - 4.9 lb/ft2 and a panel thickness of about 13 - 13.5 mm when measured by MIL-STD-662F.
In some embodiments of the present invention comprising a plurality of glass fibers arranged to form a fabric, the plurality of glass fibers are woven to form the fabric. In other embodiments of the present invention, the glass fiber 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.
In some embodiments of the present invention comprising a plurality of glass fibers arranged to form a fabric, the polymeric resin comprises an epoxy resin. In some embodiments of the present invention comprising a plurality of glass fibers arranged to form a fabric, the polymeric resin comprises a polydicyclopentadiene resin. In some embodiments of the present invention, the polymeric resin comprises polyethylene, polypropylene, polyamides (including Nylon), polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, thermoset polyurethane, cyanate esters, or bis-maleimide 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. Glass fiber fabrics useful in 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. Such 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 single end strands can be subsequently processed into assembled rovings by gathering several ends together and providing a small level of twist. Occasionally, the bundle integrity is increased by treatment with water or steam. The gathered multi-end strand can then be wound onto a 3" cardboard spool. At this point the spools can be used for warp or weft feed by tying the strand ends into a traditional rapier loom for fabric weaving into the predetermined style.
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, reaction injection molding, and pultrusion. Composites of the present invention can be prepared using such molding techniques as known to those of ordinary skill in the art.
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. Separately, 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. For example, for some polymeric resins, an appropriate resin (e.g., an amine-curable epoxy resin) may be mixed with an appropriate curing agent (e.g., an amine for an amine-curable epoxy resin) in the proportions recommended by the resin manufacturer or otherwise known to a person of ordinary skill in the art. 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. At this point, the tool is 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. As is known to persons of ordinary skill in the art, however, various parameters such as degassing time, heating time, and post curing conditions may vary based on the specific resin system used, and persons of ordinary skill in the art understand how to select such parameters based on a particular resin system.
In some embodiments of composites of the present invention where the polymer resin comprises polydicyclopentadiene, such composites can also be made using vacuum assisted resin infusion technology as described below. 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. Separately, the
polydicyclopentadiene 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 example, for polydicyclopentadiene resins, the resin is mixed with the proper amount of catalyst, and in some cases an inhibitor, in the proportions recommended by the pDCPD supplier or otherwise known to a person of ordinary skill in the art. The DCPD 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. At this point, the tool is set to a temperature of about 120 °C for up to 4 hours. The resulting rigid composites may then be de -molded. As is known to persons of ordinary skill in the art, however, various parameters such as degassing time, heating time, and post curing conditions may vary based on the specific resin system used, and persons of ordinary skill in the art understand how to select such parameters based on a particular resin system. As noted above, composites 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 12 μηι. Glass fibers suitable for use in other embodiments of the present invention have a diameter of about 6 μηι. For example, in some embodiments where glass fibers are to be used in composites for use in high energy impact applications such as ballistic or blast resistance applications, the glass fibers can have a diameter of about 6 μηι, although other glass fiber diameters could also be used.
In addition, glass fibers and glass fiber strands suitable for use in the present invention can comprise a variety of glass compositions. 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
Si02 60 - 68 weight percent;
B203 7 - 12 weight percent;
A1203 9 - 15 weight percent;
MgO 8 - 15 weight percent;
CaO 0 - 4 weight percent;
Li20 0 - 2 weight percent;
Na20 0 - 1 weight percent;
K20 0 - 1 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 1 weight percent;
Ti02 0 - 2 weight percent; and
other constituents 0-5 weight percent total.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising
Si02 60 - 68 weight percent;
B203 7 - 12 weight percent;
A1203 9 - 15 weight percent;
MgO 8 - 15 weight percent; CaO 0 - 4 weight percent;
Li20 >0 - 2 weight percent;
Na20 0 - 1 weight percent;
K20 0 - 1 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 1 weight percent;
Ti02 0 - 2 weight percent; and
other constituents 0 - 5 weight percent total;
wherein the Li20 content is greater than either the Na20 content or the K20 content. In other embodiments, 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. In some embodiments of the present invention, the MgO content is 8-13 weight percent. In other embodiments, the MgO content is 9-12 weight percent. In some embodiments, the Ti02 content is 0-1 weight percent. In some embodiments, the B203 content is no more than 10 weight percent. In some embodiments of the present invention, the A1203 content is 9-14 weight percent. In other embodiments, the A1203 content is 10-13 weight percent. In some embodiments, the (Li20 + Na20 + K20) content is less than 2 weight percent. In some embodiments, 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. In some embodiments, 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. In some embodiments, the Li20 content is 0.4-2.0 weight percent. In other embodiments comprising a Li20 content of 0.4-2.0 weight percent, the Li20 content is greater than the (Na20 + K20) content.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising
Si02 60 - 68 weight percent;
B203 7 - 13 weight percent;
A1203 9 - 15 weight percent;
MgO 8 - 15 weight percent;
CaO 0 - 4 weight percent; Li20 0 - 2 weight percent;
Na20 0 - 1 weight percent;
K20 0 - 1 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 1 weight percent; and
Ti02 0 - 2 weight percent.
In some embodiments, the glass compositions are characterized by relatively low content of CaO, for example on the order of about 0 - 4 weight percent. In yet other
embodiments, 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. Some glass compositions suitable for use in some
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 of BaO are present, the BaO content can be characterized as being no more than 0.05 weight percent.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising
Si02 60 - 68 weight percent;
B203 7 - 12 weight percent;
A1203 9 - 15 weight percent;
MgO 8 - 15 weight percent;
CaO 0 - 4 weight percent;
Li20 >0 - 2 weight percent;
Na20 0 - 1 weight percent;
K20 0 - 1 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 1 weight percent;
Ti02 0 - 2 weight percent; and
other constituents 0 - 5 weight percent total;
wherein the Li20 content is greater than either the Na20 content or the K20 content, and wherein the constituents are selected to provide a glass having a dielectric constant (Dk) less than 6.7 at 1 MHz frequency. In other embodiments, the constituents are selected to provide a glass having a dielectric constant (Dk) less than 6 at 1 MHz frequency. In still other embodiments, the constituents are selected to provide a glass having a dielectric constant (Dk) less than 5.8 at 1 MHz frequency. In some embodiments, the constituents are selected to provide a glass having a dielectric constant (Dk) less than 5.6 at 1 MHz frequency.
The constituents of a glass composition suitable for use in some embodiments of the present invention can be selected based on a desired forming temperature (defined as the temperature at which the viscosity is 1000 poise) and/or a desired liquidus temperature. In some embodiments, a glass fiber or fiber glass strand suitable for use in the present invention comprises a glass composition comprising
Si02 60 - 68 weight percent;
B203 7 - 12 weight percent;
A1203 9 - 15 weight percent;
MgO 8 - 15 weight percent;
CaO 0 - 4 weight percent;
Li20 >0 - 2 weight percent;
Na20 0 - 1 weight percent;
K20 0 - 1 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 1 weight percent;
Ti02 0 - 2 weight percent; and
other constituents 0 - 5 weight percent total;
wherein the Li20 content is greater than either the Na20 content or the K20 content, and wherein the constituents are selected to provide a forming temperature TF at 1000 poise viscosity no greater than 1370 °C. In other embodiments, the constituents are selected to provide a forming temperature TF at 1000 poise viscosity no greater than 1320 °C. In still other embodiments, the constituents are selected to provide a forming temperature TF at 1000 poise viscosity no greater than 1300 °C. In some embodiments, the constituents are selected to provide a forming temperature TF at 1000 poise viscosity no greater than 1290 °C. In some embodiments, the constituents are selected to provide a forming temperature TF at 1000 poise viscosity no greater than 1370 °C and a liquidus temperature TL at least 55 °C below the forming temperature. In other embodiments, the constituents are selected to provide a forming temperature TF at 1000 poise viscosity no greater than 1320 °C and a liquidus temperature TL at least 55 °C below the forming temperature. In still other embodiments, the constituents are selected to provide a forming temperature TF at 1000 poise viscosity no greater than 1300 °C and a liquidus temperature TL at least 55 °C below the forming temperature. In some embodiments, the constituents are selected to provide a forming temperature TF at 1000 poise viscosity no greater than 1290 °C and a liquidus temperature TL at least 55 °C below the forming temperature.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising
B203 less than 12 weight percent;
A1203 9 - 15 weight percent;
MgO 8 - 15 weight percent;
CaO 0 - 4 weight percent;
Si02 60 - 68 weight percent;
Li20 >0 - 2 weight percent;
Na20 0 - 1 weight percent;
K20 0 - 1 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 1 weight percent; and
Ti02 0 - 2 weight percent;
wherein the glass exhibits a dielectric constant (Dk) less than 6.7 and forming temperature (TF) at 1000 poise viscosity no greater than 1370 °C and wherein the Li20 content is greater than either the Na20 content or the K20 content. In some embodiments, the CaO content is 0-1 weight percent.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising
- 68 weight percent;
12 weight percent;
15 weight percent;
15 weight percent; CaO 0 - 3 weight percent;
Li20 0.4 - 2 weight percent;
Na20 0 - 1 weight percent;
K20 0 - 1 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 1 weight percent; and
Ti02 0 - 2 weight percent;
wherein the glass exhibits a dielectric constant (Dk) less than 5.9 and forming temperature (TF) at 1000 poise viscosity no greater than 1300 °C and wherein the Li20 content is greater than either the Na20 content or the K20 content.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition consisting essentially of
Si02 60 - 68 weight percent;
B203 7 - 11 weight percent;
A1203 9 - 13 weight percent;
MgO 8 - 13 weight percent;
CaO 0 - 3 weight percent;
Li20 0.4 - 2 weight percent;
Na20 0 - 1 weight percent;
K20 0 - 1 weight percent;
(Na20 + K20 + Li20) 0 - 2 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 1 weight percent; and
Ti02 0 - 2 weight percent;
wherein the Li20 content is greater than either the Na20 content or the K20 content. In some embodiments, the CaO content is 0-1 weight percent. In some embodiments comprising a CaO content of 0-1 weight percent, the B203 content is no more than 10 weight percent.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising
Si02 60 - 68 weight percent; B203 7 - 10 weight percent;
A1203 9 - 15 weight percent;
MgO 8 - 15 weight percent;
CaO 0 - 4 weight percent;
Li20 >0 - 2 weight percent;
Na20 0 - 1 weight percent;
K20 0 - 1 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 1 weight percent;
Ti02 0 - 2 weight percent; and
other constituents 0 - 5 weight percent;
wherein the Li20 content is greater than either the Na20 content or the K20 content. In some embodiments, the constituents are selected to provide a glass having a dielectric constant (Dk) less than 6.7 at 1 MHz frequency. In other embodiments, the constituents are selected to provide a glass having a dielectric constant (Dk) less than 6 at 1 MHz frequency. In still other embodiments, the constituents are selected to provide a glass having a dielectric constant (Dk) less than 5.8 at 1 MHz frequency. In some
embodiments, the constituents are selected to provide a glass having a dielectric constant (Dk) less than 5.6 at 1 MHz frequency.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising:
5 - 77 weight percent;
- 14.5 weight percent;
- 18.5 weight percent;
12.5 weight percent;
10.5 weight percent;
4 weight percent;
2 weight percent;
1 weight percent;
1 weight percent;
2 weight percent;
2 weight percent; and other constituents 0 - 5 weight percent total.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising:
- 77 weight percent;
- 14.5 weight percent;
- 18.5 weight percent;
12.5 weight percent;
4 weight percent;
3 weight percent;
2 weight percent;
1 weight percent;
1 weight percent;
2 weight percent;
2 weight percent; and
other constituents 0 - 5 weight percent total.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising:
Si02 at least 60 weight percent;
B203 5 - 11 weight percent;
A1203 5 - 18 weight percent;
MgO 5 - 12 weight percent;
CaO 0 - 10 weight percent;
Li20 0 - 3 weight percent;
Na20 0 - 2 weight percent;
K20 0 - 1 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 2 weight percent;
Ti02 0 - 2 weight percent; and
other constituents 0 - 5 weight percent total.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising:
Si02 60-68 weight percent; B203 5- 10 weight percent;
A1203 10 - 18 weight percent;
MgO 8- 12 weight percent;
CaO 0- 4 weight percent;
Li20 0- 3 weight percent;
Na20 0- 2 weight percent;
K20 0- 1 weight percent;
Fe203 0- 1 weight percent;
F2 0- 2 weight percent;
Ti02 0- 2 weight percent; and
other constituents 0-5 weight percent total.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising:
Si02 62 -68 weight percent;
B203 7- 9 weight percent;
A1203 11 - 18 weight percent;
MgO 8- 11 weight percent;
CaO 1 - 2 weight percent;
Li20 1 - 2 weight percent;
Na20 0- 0.5 weight percent;
K20 0- 0.5 weight percent;
Fe203 0- 0.5 weight percent;
F2 0.5 - 1 weight percent;
Ti02 0- 1 weight percent; and
other constituents 0-5 weight percent total.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising:
Si02 62 - 68 weight percent;
B203 less than about 9 weight percent;
A1203 10- 18 weight percent;
MgO 8-12 weight percent; and
CaO 0-4 weight percent; wherein the glass exhibits a dielectric constant (Dk) less than 6.7 and a forming temperature (TF) at 1000 poise viscosity no greater than 1370°C.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising:
B203 less than 14 weight percent;
A1203 9 - 15 weight percent;
MgO 8 - 15 weight percent;
CaO 0 - 4 weight percent; and
Si02 60 - 68 weight percent;
wherein the glass exhibits a dielectric constant (Dk) less than 6.7 and forming temperature (TF) at 1000 poise viscosity no greater than 1370°C.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising:
B203 less than 9 weight percent;
A1203 11 - 18 weight percent;
MgO 8 - 11 weight percent;
CaO 1 - 2 weight percent; and
Si02 62 - 68 weight percent;
wherein the glass exhibits a dielectric constant (Dk) less than 6.7 and forming temperature (TF) at 1000 poise viscosity no greater than 1370°C.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising:
Si02 60 - 68 weight percent;
B203 7 - 13 weight percent;
A1203 9 - 15 weight percent;
MgO 8- 15 weight percent;
CaO 0 - 3 weight percent;
Li20 0.4 - 2 weight percent;
Na20 0 - 1 weight percent;
K20 0 - 1 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 1 weight percent; and Ti02 0 - 2 weight percent;
wherein the glass exhibits a dielectric constant (Dk) less than 5.9 and forming temperature (TF) at 1000 poise viscosity no greater than 1300°C.
Another example of a glass fiber or fiber glass strand suitable for use in some embodiments of the present invention comprises a glass composition comprising:
Si02 60 - 68 weight percent;
B203 7 - 11 weight percent;
A1203 9 - 13 weight percent;
MgO 8 - 13 weight percent;
CaO 0 - 3 weight percent;
Li20 0.4 - 2 weight percent;
Na20 0 - 1 weight percent;
K20 0 - 1 weight percent;
(Na20 + K20 + Li20) 0 - 2 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 1 weight percent; and
Ti02 0 - 2 weight percent.
In addition to or instead of the features of the invention described above, some embodiments of the glass compositions described herein can be utilized to provide glasses having dissipation factors (Df) lower than standard electronic E-glass. In some embodiments, DF may be no more than 0.0150 at 1 GHz, and in other embodiments no more than 0.0100 at 1 GHz.
In some embodiments of glass compositions, DF 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.
In some embodiments, the glass compositions that can be used in glass fibers or fiber glass strands are characterized by relatively low content of CaO, for example, on the order of about 0 - 4 weight percent. In yet other embodiments, the CaO content can be on the order of about 0 - 3 weight percent. In yet other embodiments, the CaO content can be on the order of about 0 - 2 weight percent. In general, 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. In some other embodiments, the CaO content can be on the order of about 1
- 2 weight percent.
On the other hand, 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 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. In some embodiments, the compositions are characterized by a MgO content, for example, on the order of about 8 - 13 weight percent. In yet other embodiments, the MgO content can be on the order of about 9 - 12 weight percent. In some other embodiments, the MgO content can be on the order of about 8 - 12 weight percent. In yet some other embodiments, the MgO content can be on the order of about 8
- 10 weight percent.
In some embodiments, the compositions that can be used in glass fibers or fiber glass strands 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.
In yet some other embodiments, the compositions can be characterized by a ratio of (MgO + CaO)/(Li20 + Na20 + K20) content on the order of about 9.0. In certain embodiments, the ratio of Li20/(MgO + CaO) content can be on the order of about 0 - 2.0. In yet some other embodiments, the ratio of Li20/(MgO + CaO) content can be on the order of about 1 - 2.0. In certain embodiments, the ratio of Li20/(MgO + CaO) content can be on the order of about 1.0.
In some other embodiments, the (Si02 + B203) content can be on the order of 70
- 76 weight percent. In yet other embodiments, the (Si02 + B203) content can be on the order of 70 weight percent. In other embodiments, the (Si02 + B203) content can be on the order of 73 weight percent. In still other embodiments, the ratio of the weight percent of A1203 to the weigh percent of B203 is on the order of 1 - 3. In some other
embodiments, the ratio of the weight percent of A1203 to the weight percent of B203 is on the order of 1.5 - 2.5. In certain embodiments, the Si02 content is on the order of 65 - 68 weight percent. As noted above, some low Dk compositions of the prior art have the
disadvantage of requiring the inclusion of substantial amounts of BaO, and it can be noted that BaO is not required in some embodiments of glass compositions for use in some embodiments of the present invention. Although the advantageous electrical and manufacturing properties of the invention do not preclude the presence of BaO, the absence of deliberate inclusions of BaO can be considered an additional advantage of some embodiments of the present invention. Thus, 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.
The compositions that can be used in some embodiments of the invention include B203 in amounts less that the prior art approaches that rely upon high B203 to achieve low Dk. This results in significant cost savings. In some embodiments the B203 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 B203.
In some embodiments, the compositions are characterized by a B203 content, for example, on the order of about 5 - 1 1 weight percent. In some embodiments, the B203 content can be 6-11 weight percent. The B203 content, in some embodiments, can be 6-9 weight percent. In some embodiments, the B203 content can be 5-10 weight percent. In some other embodiments, the B203 content is not greater than 9 weight percent. In yet some other embodiments, the B203 content is not greater than 8 weight percent.
In some embodiments, the compositions that can be used in some embodiments of the present invention are characterized by a A1203 content, for example on the order of about 5 - 18 weight percent. The A1203 content, in some embodiments, can be 9-18 weight percent. In yet other embodiments, the A1203 content is on the order of about 10 - 18 weight percent. In some other embodiments, the A1203 content is on the order of about 10 - 16 weight percent. In yet some other embodiments, the A1203 content is on the order of about 10 - 14 weight percent. In certain embodiments, the A1203 content is on the order of about 11 - 14 weight percent.
In some embodiments, Li20 is an optional constituent. In some embodiments, the compositions are characterized by a Li20 content, for example on the order of about 0.4 - 2.0 weight percent. In some embodiments, the Li20 content is greater than the (Na20 + K20) content. In some embodiments, the (Li20 + Na20 + K20) content is not greater than 2 weight percent. In some embodiments, the (Li20 + Na20 + K20) content is on the order of about 1 - 2 weight percent.
In certain embodiments, the compositions of the invention are characterized by a Ti02 content for example on the order of about 0 - 1 weight percent.
In some embodiments of the compositions set forth above, 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. In other embodiments, the dielectric constant (Dk) may be less than 6 at 1 MHz frequency. In other embodiments, the dielectric constant (Dk) may be less than 5.8 at 1 MHz frequency. Further embodiments exhibit dielectric constants (Dk) less than 5.6 or even lower at 1 MHz frequency. In other embodiments, the dielectric constant (Dk) may be less than 5.4 at 1 MHz frequency. In yet other embodiments, the dielectric constant (Dk) may be less than 5.2 at 1 MHz frequency. In yet other embodiments, the dielectric constant (Dk) may be less than 5.0 at 1 MHz frequency.
The 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 (TF) at 1000 poise viscosity no greater than 1370°C. The TF of some embodiments are no greater than 1320°C, or no greater than 1300°C, or no greater than 1290°C, or no greater than 1260°C, or no greater than 1250°C. These compositions can also encompass glasses in which the difference between the forming temperature and the liquidus temperature (TL) 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. In general, minimizing alkali oxide content of the glass compositions used to form the glass fibers or fiber glass strands can assist in lowering Dk. In those
embodiments in which it is desired to optimize reduction of Dk the total alkali oxide content may be no more than 2 weight percent of the glass composition. In some embodiments, it has been found that minimizing Na20 and K20 are more effective in this regard than Li20. 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, Li20 is included in significant amounts, e.g. at least 0.4 weight percent. For this purpose, in some embodiments the Li20 content is greater than either the Na20 or K20 contents, and in other embodiments the Li20 content is greater than the sum of the Na20 and K20 contents, in some embodiments greater by a factor of two or more.
One advantageous aspect in some of the embodiments is reliance upon constituents that are conventional in the fiber glass industry and avoidance of substantial amounts of constituents whose raw material sources are costly. For this aspect, constituents in addition to those explicitly set forth in the compositional definition of the glasses 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. Relative to some prior art low Dk glasses, 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. Likewise, 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.
The choice of batch ingredients and their cost are significantly dependent upon their purity requirements. Typical commercial ingredients, such as for E-glass making, contain impurities of Na20, K20, Fe203 or FeO, SrO, F2, Ti02, S03, etc. in various chemical forms. A majority of the cations from these impurities would increase the Dk of the glasses by forming nonbridging oxygens with Si02 and/or B203 in the glass. Sulfate (expressed as S03) 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, Cl2, P2O5, Cr203, or NiO (not limited to these particular chemical forms). Other refining agents and/or processing aids may also be present such as As203, MnO, Mn02, Sb203, or Sn02, (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. Optionally, 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, particularly as compared to E-glass fibers, fiber glass strands formed from E-glass, and related products. Such mechanical properties may be beneficial in some embodiments of composites (or panels incorporating composites) of the present invention. For example, some embodiments of glass fibers 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/m2 divided by the specific weight in N/m3. Specific modulus refers to the Young's modulus in N/m2 divided by the specific weight in N/m3. Glass fibers having relatively high specific strength and/or relatively high specific modulus may be desirable in ballistic or impact resistance applications where there is a desire to increase mechanical properties or product performance while reducing the overall weight of the composite.
As is known in the art, after formation, glass fibers are typically at least partially coated with a sizing composition. In general, glass fibers used to form composites of the present invention will be at least partially coated with a sizing composition. One skilled in the art may choose one of many commercially available sizing compositions for the glass fibers based upon a number of factors including, for example, performance properties of the sizing compositions, desired flexibility of the resulting fabric, cost, and other factors. 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, and Hybon 2016, TufRov 4588, as well as sizing compositions often used on yarns, such as 1383, 611 , 900, 610, and 690, each of which refer to sizing compositions for products commercially available from PPG Industries, Inc. For glass fibers to be used in the reinforcement of polydicyclopentadiene resins, suitable sizing compositions can include Hybon 2026 or those sizing compositions described in U.S. Patent No. 6,890,050, which is hereby incorporated by reference.
As noted above, composites of the present invention can comprise a plurality of glass fibers arranged to form a fabric, in some embodiments. Any suitable fabric design known to one of ordinary skill in the art for ballistic applications can be used. 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 tri axial 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.
As noted above, 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 ballistic applications may be used. In some embodiments, for example, warp yarns can comprise 250 yield assembled rovings produced by gathering several ends from G75 yarn, DE75 yarn, and/or DEI 50 yarns.
As noted above, 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 high energy impact applications such as ballistic or blast resistance applications, can be particularly useful in some embodiments. 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. In some embodiments, the polymeric resin can comprise an epoxy resin. In some embodiments, the polymeric resin can comprise a polydicyclopentadiene resin. In other embodiments, 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, and thermoplastic polyurethanes (TPU). Non- limiting examples of commercially available polymeric resins useful in some
embodiments of the present invention include Hexion RIMR 135 epoxy with 1366 curing agent (available from Hexion Specialty Chemicals, Columbus, Ohio) and Applied Poleramic MMFCS2 epoxy (available from Applied Poleramic, Inc., Benicia, California). Dicyclopentadiene resins useful in some embodiments of the present invention, along with catalysts and/or other materials useful in curing the resin, are commercially available from Materia, Inc. of Pasadena, CA.
EXAMPLES
Some exemplary embodiments of the present invention will now be illustrated in the following specific, non-limiting examples.
EXAMPLE 1
The physical properties of glass fibers useful in some embodiments of the present invention were measured under controlled processing conditions and are listed in Table 1. Physical properties from standard E-glass fibers are included for reference. "Specific Modulus" in Table 1 is the Young's modulus in N/m2 divided by the specific weight in N/m3, measured at a temperature of 296 ± 2 K (23 ± 2 °C) and a relative humidity of 50 ± 5 percent. "Specific Tensile Strength" in Table 1 is the ultimate
tensile strength in N/m2 divided by specific weight in N/m3, measured at a temperature of 296 ± 2 K (23 ± 2 °C). Single fiber tensile strengths were tested using a procedure based on ASTM D3379-75(1989)el "Standard Test Method for Tensile Strength and Young's Modulus for High-Modulus Single-Filament Materials," as would be understood by one of ordinary skill in the art. The testing involved measuring/breaking 65 - 72 individual fibers made within 4 hours on the same day. As measured by x-ray fluorescence spectroscopy, the glass fibers of Sample 1 in Table 1 comprised a glass composition comprising
Si02 65.80 weight percent;
B203 8.90 weight percent;
A1203 12.35 weight percent;
MgO 10.27 weight percent;
CaO 1.52 weight percent;
Na20 0.27 weight percent;
K20 0.13 weight percent;
Fe203 0.17 weight percent;
F2 0.35 weight percent;
Ti02 0.14 weight percent;
SrO 0.02 weight percent;
S03 0.00 weight percent
ZrO 0.06 weight percent; and
Cr203 0.01 weight percent.
Table 1. Comparison of properties of E-glass and a glass composition useful embodiments of the present invention.
Specific Modulus 2.87 3.03
(10~6 m)
EXAMPLE 2
To evaluate the strength of some composites of the present invention, 8 oz/yd2 unidirectional fabrics useful in some embodiments of the present invention were produced on a rapier loom and infused with high modulus epoxy resin (Hexion RIMR 135) for mechanical property characterization. The fabrics comprised E-225 yarns sized with a starch-oil sizing composition, and the yarns comprised glass fibers comprising the glass composition of Sample 1 in Table 1. Equivalent unidirectional fabric and composites were also produced with E-glass input as controls. Vacuum assisted resin infusion technology was used to make the composites comprising the unidirectional fabrics. To make a composite, a filament wound unidirectional fiber preform was cut to a desired size and placed on a silicone release treated glass table. The stack was then covered with a peel ply, fitted with a flow enhancing media, and vacuum bagged using nylon bagging film. Next, the so-called "preform" was subjected to a vacuum pressure of about 27 inches Hg. Separately, an amine-curable epoxy resin was mixed with an amine curing agent in the proportions recommended by the resin manufacturer. The combined resin was then degassed in a vacuum chamber for 30 minutes and infused through the fabric preform until complete wet out of the fabric stack was achieved. At this point, the table was covered with heated blankets (set to a temperature of about 45 - 50 °C) for 12 hours. The resulting rigid composites were then de-molded and post cured at about 176 °F for 5 hours in a programmable convection oven.
Some measured mechanical properties of composites of the present invention and control E-glass composites are shown below in Table 2. Where appropriate, the relevant standard ISO method is also listed for each mechanical property. The entirety of each of these standard methods is incorporated herein by reference. Table 2 shows the increased tensile performance of composites of the present invention compared to commercial E-glass fiber composites at equivalent fiber weight fractions. Table 2. Comparison of properties of E-glass composites and composites of the present invention.
EXAMPLE 3
The ballistic performance of various composites was evaluated by producing and testing panels at different areal densities. As references, reference panels were made with standard S-2 Glass® (24 oz/yd2) woven roving from AGY (Aiken, South Carolina) and with Hybon 2006 (25 oz/yd2) E-glass woven roving from PPG Industries, Inc. The control polymeric resin matrix material for the reference panels was MMFCS2 Epoxy from Applied Poleramic (Benicia, California). The reference panels were screened against the 0.30 cal FSP at different areal densities. The six-point ballistic limit (V50) was calculated according to MIL-STD-662F. In addition, damage analysis was performed on two representative reference panels to determine the extent of damage caused by the ballistic event. For this analysis, the six largest damage patterns observed in a panel under high intensity light were measured using image analysis software, and the mean damage zone was calculated.
For comparison with the reference panels comprising S-2 Glass® and E-glass, exemplary composites of the present invention were prepared as follows. Rovings of glass fibers useful in the present invention were formed using a marble melt fiber production technique. A fixed number of small G150 forming cakes were produced, and subsequently twisted and assembled into a 250 yield fiber glass roving. The roving comprised glass fibers treated with 1383 sizing composition and having a nominal diameter of about 9 μηι. The rovings were then woven into a 25 oz/yd2 plain weave fabric (5.0 ppi x 5.3 ppi, where ppi = picks per inch) on a rapier loom. Panels comprising composites of the present invention were produced via resin infusion using the benchmark epoxy resin MMFCS2 Epoxy from Applied Poleramic (Benicia, California) at 2 lb/ft2 and 5 lb/ft2 for ballistic screening against the 0.30 cal FSP and 0.50 cal FSP, respectively. Physical characteristics and ballistic performances of the panels are provided below in Table 3. Table 4 provides a comparison of the ballistic performances of panels comprising composites of the present invention with panels comprising composites comprising E-glass and S-2 Glass®. Tables 3 and 4 indicate that panels comprising composites of the present invention unexpectedly show a considerable increase in ballistic performance compared to panels comprising E-glass at comparable areal densities and are not out-performed by panels comprising costly S-2 Glass®. In addition, the damage observed on panels comprising composites of the present invention was equivalent to the damage extent calculated for panels comprising S-2 Glass®, though panels comprising E-glass exhibited lesser damage. Table 3. Physical characteristics and ballistic performance of panels comprising composites of the present invention.
Table 4. Comparison of the ballistic performance of panels comprising composites (1 -8) of the present invention with panels (9-19) comprising S-2 Glass® and E-glass.
EXAMPLE 4
The ballistic performance of other composites were evaluated against National Institute of Justice (NIJ) Standard 0108.01. As references, reference panels were made with Hybon 2006 (24 oz/yd2) E-glass woven roving from PPG Industries, Inc. The control polymeric resin matrix material for the reference panels was MMFCS2 Epoxy from Applied Poleramic (Benicia, California).
For comparison with the reference panels comprising E-glass, exemplary composites of the present invention were prepared as follows. Rovings of glass fibers useful in the present invention were formed using a direct melt fiber production furnace. A fixed number of small DEI 50 forming cakes were produced, and subsequently twisted and assembled into a 250 yield fiber glass roving. The roving comprised glass fibers treated with 1383 sizing composition and having a nominal diameter of about 6.5 μηι. The rovings were then woven into a 24 oz/yd2 plain weave fabric (5.0 ppi x 5.3 ppi, where ppi = picks per inch) on a rapier loom. Panels comprising composites of the present invention were produced via resin infusion using the benchmark epoxy resin MMFCS2 Epoxy from Applied Poleramic (Benicia, California).
The composites were tested against a .44 mag 240 SWCGC projectile. The results of the NIJ Standard 0108.01 testing are summarized in Table 5 below.
Table 5. Physical characteristics and ballistic performance of panels comprising composites of the present invention.
Table 5 indicates that panels comprising composites of the present invention resulted in higher V50 at equivalent areal density or equivalent V50 at lower areal density than the panels formed from E-glass.
EXAMPLE 5
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 B203 (typically about 5% of the total target B203 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 B203, the as-batched compositions illustrated are considered to be close to the measured compositions.
Melt viscosity as a function of temperature and liquidus temperature were determined by using ASTM Test Method C965 "Standard Practice for Measuring
Viscosity of Glass Above the Softening Point," and C829 "Standard Practices for
Measurement of Liquidus Temperature of Glass by the Gradient Furnace Method," respectively.
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 (Dk) and dissipation factor (Df) of each glass were determined from 1 MHz to 1 GHz by ASTM Test Method D150
"Standard Test Methods for A-C Loss Characteristics and Permittivity (Dielectric Constant) of Solid Electrical Insulating Materials." According to the procedure, all samples were preconditioned at 25°C under 50% humidity for 40 hours. Selective tests were performed for glass density using ASTM Test Method C729 "Standard Test Method for Density of Glass by the Sink-Float Comparator," for which all samples were annealed.
For selected compositions, 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
indentation load and the maximum indentation depth). For the tests, the same disk samples, which had been tested for Dk and Df, were used. Five indentation measurements were made to obtain average Young's modulus and microhardness data. The
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.
All compositional values in the examples are expressed in weight percent. In the Tables below, "E" refers to Young's modulus; "H" refers to microhardness; of refers to filament strength; and "Std" refers to standard deviation. Table 6 Compositions
Samples 1 - 8 provide glass compositions (Table 6) by weight percentage: Si02 62.5 - 67.5%, B203 8.4 - 9.4%, A1203 10.3 - 16.0%, MgO 6.5 - 11.1%, CaO 1.5 - 5.2%, Li20 1.0%, Na20 0.0%, K20 0.8%, Fe203 0.2 - 0.8%, F2 0.0%, Ti02 0.0%, and sulfate (expressed as S03) 0.0%.
The glasses were found to have Dk of 5.44 - 5.67 and Df of 0.0006 - 0.0031 at 1 MHz, and Dk of 5.47 - 6.67 and Df of 0.0048 - 0.0077 at 1 GHz frequency. The electric properties of the compositions in Series III illustrate significantly lower (i.e., improved) Dk and Df over standard E-glass with Dk of 7.29 and Df of 0.003 at 1 MHz and Dk of 7.14 and Df of 0.0168 at 1 GHz.
In terms of fiber forming properties, the compositions in Table 6 have forming temperatures (TF) of 1300 - 1372 °C and forming windows (TF - TL) of 89 - 222°C. This can be compared to a standard E-glass which has TF typically in the range 1170 - 1215°C. To prevent glass devitrification in fiber forming, a forming window (TF - TL) greater than 55°C is desirable. All of the compositions in Table 6 exhibit satisfactory forming windows. Although the compositions of Table 6 have higher forming temperatures than E-glass, they have significantly lower forming temperatures than D-glass (typically about 1410°C). Table 6. Some glass compositions useful in some embodiments of the present invention.
SAMPLES: 1 2 3 4 5 6 7 8
A1203 1 1.02 9.45 11.64 12.71 15.95 10.38 10.37 11.21
B203 8.55 8.64 8.58 8.56 8.46 8.71 9.87 9.28
CaO 5.10 5.15 3.27 2.48 1.50 2.95 2.01 1.54
CoO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.62
Fe203 0.39 0.40 0.39 0.39 0.39 0.53 0.80 0.27
20 0.77 0.78 0.77 0.77 0.76 0.79 0.79 0.78
Li20 0.98 0.99 0.98 0.98 0.97 1.00 1.00 1.00
MgO 6.70 7.44 8.04 8.69 9.24 10.39 11.05 11.04
Si02 66.48 67.16 66.32 65.42 62.72 65.26 64.12 64.26
Properties
Dk, 1 MHz 5.62 5.59 5.44 5.47 5.50 5.67 5.57 5.50 Dk, 1 GHz 5.65 5.62 5.46 5.47 5.53 5.67 5.56 5.50
Df, 1 MHz 0.0010 0.0006 0.0016 0.0008 0.0020 0.0031 0.0012 0.0010
Df, 1 GHz 0.0048 0.0059 0.0055 0.0051 0.0077 0.0051 0.0053 0.0049
TL (°C) 1209 1228 1215 1180 1143 1219 121 1 1213
TF (°C) 1370 1353 1360 1372 1365 1319 1300 1316
TF - TL (°C) 161 125 145 192 222 100 89 103
Table 7 Compositions
Samples 9 - 15 provide glass compositions: Si02 60.8 - 68.0%, B203 8.6 and 11.0%, A1203 8.7 - 12.2%, MgO 9.5 - 12.5%, CaO 1.0 - 3.0%, Li20 0.5 - 1.5%, Na20 0.5%, K20 0.8%, Fe203 0.4%, F2 0.3%, Ti02 0.2%, and sulfate (expressed as S03) 0.0%.
The glasses were found to have Dk of 5.55 - 5.95 and Df of 0.0002 - 0.0013 at 1 MHz, and Dk of 5.54 - 5.94 and Df of 0.0040 - 0.0058 at 1 GHz frequency. The electric properties of the compositions in Table 7 illustrate significantly lower (improved) Dk and Df over standard E-glass with Dk of 7.29 and Df of 0.003 at 1 MHz, and Dk of 7.14 and Df of 0.0168 at 1GHz.
In terms of mechanical properties, the compositions of Table 7 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 7 are also significantly higher than D-glass which is about 55 GPa based on literature data.
In terms of fiber forming properties, the compositions of Table 7 have forming temperature (TF) of 1224 - 1365 °C, and forming windows (TF - TL) of 6 - 105°C as compared to standard E-glass having TF in the range 1 170 - 1215°C. Some, but not all, of the Table 7 compositions have a forming window (TF - TL) greater than 55°C, which is considered preferable in some circumstances to avoid glass devitrification in commercial fiber forming operations. The Table 7 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.
Table 8. Some glass compositions useful in some embodiments of the present invention.
Table 8 (continued).
Table 9. Some glass compositions useful in some embodiments of the present invention.
Samples 29 - 62 provide glass compositions (Table 10) by weight percentage: Si02 53.74 - 76.97%, B203 4.47 - 14.28%, A1203 4.63 - 15.44%, MgO 4.20 - 12.16%, CaO 1.04 - 10.15%, Li20 0.0 - 3.2%, Na20 0.0- 1.61%, K20 0.01 - 0.05%, Fe203 0.06 - 0.35%, F2 0.49- 1.48%, Ti02 0.05- 0.65%, and sulfate (expressed as S03) 0.0- 0.16%.
Samples 29-62 provide glass compositions (Table 10) by weight percentage wherein the (MgO + CaO) content is 7.81- 16.00%, the ratio CaO/MgO is 0.09 - 1.74%, the (Si02+B203) content is 67.68 - 81.44%, the ratio A1203/B203 is 0.90 - 1.71%, the (Li20+Na20+K20) content is 0.03 - 3.38 %, and the ratio Li20/(Li20+Na20+K20) is 0.00 - 0.95%.
In terms of mechanical properties, the compositions of Table 10 have a fiber density of 2.331 - 2.416g/cm3 and an average fiber tensile strength (or fiber strength) of 3050 - 3578 MPa.
To measure fiber tensile strength, 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 μηι 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 Dk of 4.83 - 5.67 and Df of 0.003 - 0.007 at 1 GHz. The electric properties of the compositions in Table 10 illustrate significantly lower (i.e., improved) Dk and Df over standard E-glass which has a Dk of 7.14 and a Df of 0.0168 at 1GHz.
In terms of fiber forming properties, the compositions in Table 10 have forming temperatures (TF) of 1247 - 1439 °C and forming windows (TF - TL) of 53 - 243°C. The compositions in Table 10 have liquidus temperature (TL) of 1058 - 1279 °C. This can be compared to a standard E-glass which has TF typically in the range 1170 - 1215°C. To prevent glass devitrification in fiber forming, a forming window (TF - TL) greater than 55°C is sometimes desirable. All of the compositions in Table 10 exhibit satisfactory forming windows.
Table 10. Some glass compositions useful in some embodiments of the present invention.
Table 10 (Continued)
Table 10 (Continued)
Table 10 (Continued)
Table 10 (Continued)
Table 10 (Continued)
Table 10 (Continued)
Samples 63 - 73 provide glass compositions (Table 11) by weight percentage: Si02 62.35 - 68.35%, B203 6.72 - 8.67%, A1203 10.53 - 18.04%, MgO 8.14 - 11.44%, CaO 1.67 - 2.12%, Li20 1.07 - 1.38%, Na20 0.02%, K20 0.03 - 0.04%, Fe203 0.23 - 0.33%, F2 0.49- 0.60%, Ti02 0.26- 0.61%, and sulfate (expressed as S03) 0.0%. Samples 63-73 provide glass compositions (Table 1 1) by weight percentage wherein the (MgO + CaO) content is 9.81- 13.34%, the ratio CaO/MgO is 0.16 - 0.20, the (Si02+B203) content is 69.59 - 76.02%, the ratio A1203/B203 is 1.37 - 2.69, the (Li20+Na20+K20) content is 1.09 - 1.40 %, and the ratio Li20/(Li20+Na20+K20) is 0.98. In terms of mechanical properties, the compositions of Table 11 have a fiber density of 2.371 - 2.407g/cm3 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 11 were measured in the same way as the fiber tensile strengths measured in connection with the compositions of Table 10. 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 (VE) was calculated. Fiber density (p) was measured using a Micromeritics AccuPyc 1330 pycnometer. In general, 20
measurements were made for each composition and the average Young's modulus (E) was calculated according to the formula E = VE 2* p . The fiber failure strain was calculated using Hooke's Law based on the known fiber strength and Young's modulus values.
The glasses were found to have Dk of 5.20 - 5.54 and Df of 0.0010 - 0.0020 at 1 GHz. The electric properties of the compositions in Table 11 illustrate significantly lower (i.e., improved) Dk and Df over standard E-glass with Dk of 7.14 and Df of 0.0168 at 1GHz. In terms of fiber forming properties, the compositions in Table 1 1 have forming temperatures (T ) of 1303 - 1388 °C and forming windows (T - TL) of 51 - 144°C.
Table 1 1. Some glass compositions useful in some embodiments of the present invention.
Table 11 (Continued)
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 having a relatively low density; the provision of glass fibers having a relatively high strength; the provision of glass fibers having a relatively high strain-to-failure; the provision of composites having relatively low areal density for a given fiber volume fraction or a given composite performance; the provision of glass fibers and composites useful for ballistic applications; and the provision of glass fibers and composites having relatively low cost compared to glass fibers and composites of similar ballistic performance.
Various embodiments of the invention have been described in fulfillment of the various objectives of the invention. It should be recognized that these embodiments are merely illustrative of the principles of the present invention. Numerous modifications and adaptations thereof will be readily apparent to those of skill in the art without departing from the spirit and scope of the invention.
That which is claimed:

Claims

1. A composite comprising:
a polymeric resin; and
a plurality of glass fibers disposed in the polymeric resin, wherein at least the plurality of glass fibers comprises a glass composition comprising
Si02 60 - 68 weight percent;
B203 7 - 12 weight percent;
A1203 9 - 15 weight percent;
MgO 8 - 15 weight percent;
CaO 0 - 4 weight percent;
Li20 0 - 2 weight percent;
Na20 0 - 1 weight percent;
K20 0 - 1 weight percent;
Fe203 0 - 1 weight percent;
F2 0 - 1 weight percent;
Ti02 0 - 2 weight percent; and
other constituents 0 - 5 weight percent total;
wherein the (Li20 + Na20 + K20) content is less than 2 weight percent, wherein the MgO content is at least twice the content of CaO on a weight percent basis, and wherein the composite is adapted for use in ballistics or blast resistance applications.
2. The composite of claim 1 , wherein the composite exhibits a 0.30 cal FSP V50 value of at least about 900 fps at an areal density of about 2 lb/ft2 and a thickness of about 5-6 mm when measured by the U.S. Department of Defense Test Method Standard for V50 Ballistic Test for Armor, MIL-STD-662F, December 1997.
3. The composite of claim 1 , wherein the composite exhibits a 0.50 cal FSP V50 value of at least about 1200 fps at an areal density of about 4.8 - 4.9 lb/ft2 and a thickness of about 13 - 13.5 mm when measured by the U.S. Department of Defense Test Method Standard for V50 Ballistic Test for Armor, MIL-STD-662F, December 1997.
4. The composite of claim 1 , wherein the polymeric resin comprises an epoxy resin.
5. The composite of claim 1, wherein the polymeric resin comprises at least one of polyethylene, polypropylene, polyamide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, and thermoset polyurethane resins.
6. The composite of claim 1 , wherein the at least one of the plurality of glass fibers is at least partially coated with a sizing composition.
7. The composite of claim 1 , wherein the plurality of glass fibers are arranged to form a fabric.
8. The composite of claim 7, wherein the plurality of glass fibers are woven to form the fabric.
9. The composite of claim 7, wherein the fabric comprises a plain weave fabric, a twill fabric, a crowfoot fabric, a satin weave fabric, a stitch bonded fabric, or a 3D woven fabric.
10. An armor panel comprising the composite of claim 7.
1 1. 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 comprising
Si02 53.5-77 weight percent;
B203 4.5-14.5 weight percent;
A1203 94.5-18.5 weight percent;
MgO 4-12.5 weight percent;
CaO 0 - 10.5 weight percent;
Li20 0 - 4 weight percent;
Na20 0 - 2 weight percent;
K20 0 - 1 weight percent; Fe203 0 - 1 weight percent;
F2 0 - 2 weight percent;
Ti02 0 - 2 weight percent; and
other constituents 0 - 5 weight percent total;
wherein the composite is adapted for use in ballistics or blast resistance applications.
12. The composite of claim 1 1, wherein the composite exhibits a 0.30 cal FSP V50 value of at least about 900 fps at an areal density of about 2 lb/ft2 and a thickness of about 5-6 mm when measured by the U.S. Department of Defense Test Method Standard for V50 Ballistic Test for Armor, MIL-STD-662F, December 1997.
13. The composite of claim 1 1, wherein the composite exhibits a 0.50 cal FSP V50 value of at least about 1200 fps at an areal density of about 4.8 - 4.9 lb/ft2 and a thickness of about 13 - 13.5 mm when measured by the U.S. Department of Defense Test Method Standard for V50 Ballistic Test for Armor, MIL-STD-662F, December 1997.
14. The composite of claim 1 1 , wherein the polymeric resin comprises an epoxy resin.
15. The composite of claim 11 , wherein the polymeric resin comprises at least one of polyethylene, polypropylene, polyamide, polybutylene terephthalate, polycarbonate, thermoplastic polyurethane, phenolic, polyester, vinyl ester, and thermoset polyurethane resins.
16. The composite of claim 1 1 , wherein the at least one of the plurality of glass fibers is at least partially coated with a sizing composition.
17. The composite of claim 1 1 , wherein the plurality of glass fibers are arranged to form a fabric.
18. The composite of claim 17, wherein the plurality of glass fibers are woven to form the fabric.
19. The composite of claim 17, wherein the fabric comprises a plain weave fabric, a twill fabric, a crowfoot fabric, a satin weave fabric, a stitch bonded fabric, or a 3D woven fabric.
20. An armor panel comprising the composite of claim 17.
EP11760934.7A 2010-09-14 2011-09-14 Low density and high strength fiber glass for ballistic applications Withdrawn EP2616399A1 (en)

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