CN103153896A - Low density and high strength fiber glass for reinforcement applications - Google Patents

Low density and high strength fiber glass for reinforcement applications Download PDF

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Publication number
CN103153896A
CN103153896A CN2011800492867A CN201180049286A CN103153896A CN 103153896 A CN103153896 A CN 103153896A CN 2011800492867 A CN2011800492867 A CN 2011800492867A CN 201180049286 A CN201180049286 A CN 201180049286A CN 103153896 A CN103153896 A CN 103153896A
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CN
China
Prior art keywords
weight
resin
glass
fabric
matrix material
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Pending
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CN2011800492867A
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Chinese (zh)
Inventor
J·C·彼得斯
J·C·塞拉诺
李洪
S·J·帕克斯
C·A·理查德斯
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PPG Industries Ohio Inc
PPG Industries Inc
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PPG Industries Inc
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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 Inc filed Critical PPG Industries Inc
Publication of CN103153896A publication Critical patent/CN103153896A/en
Pending legal-status Critical Current

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    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/16—Yarns or threads made from mineral substances
    • D02G3/18—Yarns or threads made from mineral substances from glass or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals

Abstract

The present invention relates to fiber glass strands, yarns, fabrics, composites, prepregs, laminates, fiber-metal laminates, and other products incorporating glass fibers formed from glass compositions. The glass fibers, in some embodiments, are incorporated into composites that can be used in reinforcement 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

Be used for strengthening low density and the high strength glass fiber of using
The related application of cross reference
The application requires the right of priority of the U.S. Provisional Patent Application series number 61/382738 of application on September 14th, 2010, and its whole disclosures are hereby incorporated by.The application require on September 9th, 2011 application U.S. Patent application No.13/229012 right of priority and be its part continuation application, No.13/229012 is the part continuation application of the U.S. Patent application No.12/940764 of application on November 5th, 2010, No.12/940764 is the U.S. Patent application No.11/610761 of application on December 14th, 2006, the continuation application of present U.S. Patent No. 7829490 (being promulgated on November 9th, 2010), its each content all is incorporated herein by reference with it at this.
Invention field
The present invention relates to low density and high strength glass fiber, and be applicable to strengthen the yarn that comprises low density and high strength glass fiber, fabric and the matrix material of application.
Background of invention
Glass fibre has been used to strengthen different fluoropolymer resins for many years.Be used for strengthening the composition that some normally used glass compositions of using comprise " E-glass " and " D-glass " family.Another kind of normally used glass composition is sold by AGY (Aiken, South Carolina state) with trade(brand)name " S-2Glass " city.
For many years glass fibre is arranged to form fabric.In the fiberglass weaving operation of routine, glass fabric is woven in a plurality of warp thread by parallel yarn (also referred to as " weft yarn ") is interweaved.Usually, this is as the realization of getting off: warp thread is arranged on loom with parallel, planar array substantially, with predetermined repeat patterns, the parallel yarn is passed on warp thread afterwards and under, this parallel yarn is knitted in warp thread.Pattern used will depend on the fabric pattern of expectation.
Warp thread is typically and forms by a plurality of molten glass flows of decaying from axle bush or spinning-drawing machine.Coating (perhaps elementary glueing composition) be administered to single glass fibre on, and fibril aggregation together formed precursor thereafter.This precursor is processed into yarn by via twisting framework (twist frame), this precursor being transferred to reel subsequently.In this transfer process, this precursor can be given twisting and help fibrous bundle is kept together.Then the precursor of these twisting be wrapped in reel around, and this reel is used for weaving.
The location of warp thread on loom is typically by weaving machine warp is undertaken.Weaving machine warp comprises the warp thread (also referred to as " warp beam (ends) ") of defined amount, its with substantially parallel arrangement (also referred to as " through sheet ") be wrapped in cylindrical core around.The weaving machine warp preparation typically need to be merged into a plurality of yarn bags (each bag comprises the part of weaving machine warp requisite number purpose warp beam) single packing or weaving machine warp.Although for example and be not limited to this, 50 inches (127cm) is wide, 7781 style fabrics (it utilizes the input of DE75 yarn) typically need 2868 warp beams.But the conventional equipment that is used to form weaving machine warp does not allow these whole warp beams to transfer on single warp beam from reel in an operation.So, produced a plurality of warp beams (typically be called " section warp beam ") of a part that comprises requisite number purpose warp beam, and merged thereafter and form weaving machine warp.In a kind of mode that is similar to weaving machine warp, the section warp beam typically comprises cylindrical core, and it comprises a plurality of substantially parallel warp thread that are wrapped in the there.Although those skilled in the art's section of being recognized that warp beam can comprise the warp thread that is used to form the required any number of final weaving machine warp, the number of the warp beam that common section warp beam comprises is subject to the ability of the creel of warp arrangement.For 7781 style fabrics, each typically is provided is four section warp beams of 717 warp beams of DE75, and provides through 2868 required warp beams of sheet, as mentioned above when merging.
As previously mentioned, elementary glueing composition is administered on glass fibre, is typically after just being shaped and carries out.Traditionally, the filament that is used to form continuous glass fibre precursor used in woven fabric is processed with aqueous starch-oily jointing compound, it typically comprises starch or amylose starch, hydrogenated vegetable oil, positively charged ion wetting agent, emulsifying agent and water part or dextrinization fully, and this is well known to a person skilled in the art.About the more information of such glueing composition, referring to K.Loewenstein, The Manufacturing Technology of Continuous Glass Fibres, (the 3rd edition, 1993) 237-244 page, it clearly is hereby incorporated by.Glueing composition although it is so usually enough by force in fiberizing and the weaving machine warp manufacturing course of processing for fiber provides protection, but they usually can not be for the protection of grinding and the wearing and tearing in the woven process of glass fibre (particularly through yarn fiber) anti-high speed.As a result, common practice is to send slasher sizing machine with warp thread in textile industry, and it is administered to warp thread with sizing glue in the weaving machine warp manufacturing processed, will mode discussed in detail provide required other protection with the back.Clearer and more definite, this sizing operation provides medium that other one-tenth membrane chemical is joined on the fiber that forms warp thread piece.Typically, this sizing glue comprises completely or partially polyvinyl alcohol (PVA) material of hydrolysis, and is the mixture of 6-8% solid scope, and viscosity is 15-20 centipoise (CPS).This sizing glue is typically as getting off to be used: warp thread piece is immersed in the container that contains sizing glue via a series of submergence rollers, then it was sent the extrusion roll system, it is except the permanent load of extrusion roll, the typical squeeze pressure (this squeeze pressure can change according to yarn diameter) to the yarn that applies that has also applied 15-20 pounds/square inch is removed unnecessary sizing glue.This sizing glue can be used at high temperature, for example at 130-150 ℉ (54-66 ℃) or in room temperature, this depends on PVA manufacturer's recommendation.After the yarn sheet has pushed unnecessary sizing material, the sheet that this sizing is glued together carries out drying with any usual manner known in the art, such as but not limited to sending warming mill and/or air oven with this sheet.In the slasher sizing machine with warming mill or tank, the surface temperature of tank is typically 240-280 ℉ (116-138 ℃).The arrangement of depending on tank of dry actual temperature curve meeting part, the number of tank and yarn speed.In air oven, the air themperature in stove is typically 275-300 ℉ (135-149 ℃).After drying, sent a series of separation bar to separate through sheet this warp thread piece, and merge through sheet and guarantee that warp beam does not stick to each other by hook read assembly and comb.Then this yarn sheet is wound on weaving machine warp.
Elementary starch-oil paint and sizing glue are both inconsistent with the polymer resin matrix material of be used for filling with the woven fabric of the yarn that applies.As a result, be incorporated into fabric woven before, these coating must be removed from fabric, for example by thermal cleaning and/or washing from these yarns except going to substrate material.For example, a kind of typical step heating cleaning method can comprise fabric was come except destarching-oily elementary glueing composition and sizing glue in 600-800 ℉ (316-427 ℃) heating in 70-80 hour.In a kind of selectable two steps operation, this fabric is untied by stove, it is exposed to flame here, it has burnt a part of sizing material, then 600-800 ℉ (316-427 ℃) heating 50-60 hour.First step of this two step operation sometimes is called molten coking, and typical be used for adding thermal cleaning by the woven fabric of textured yarn (that is, 7628 style fabrics).
When elementary glueing composition that will be compatible with resin matrix material in forming process is administered on single glass fibre, have been found that using other sizing glue comes the protective glass fiber optional.As a result, the needs of protecting by the other fiber of using sizing glue have been cancelled.But, observed when such warp thread with resin compatible coating simply is wound on weaving machine warp from a plurality of sections warp beams, for example by warp thread being sent slasher sizing machine need not other sizing glue, heating and dry (sometimes being called " dry pulp yarn "), are when forming weaving machine warp, the number of weaving machine warp defective, the number that breaks in the end that for example produces due to roll-in and twisting end is too much.(it is a condition to the roll-in end, wherein adjacent glass strand each other roll-in with twisting be in the same place) be particularly troublesome, because they can cause woven process medial end portions to be broken, its successively with the fabric quality problem for example warp beam deviate from, warp beam villous, the broken warp beam of cutting is relevant with the Yarn connecting of not expecting.
But, do not use sizing glue on slasher sizing machine, but be important with the ability of the warp thread manufacturing weaving machine warp with resin compatible coating, because in textile industry, the main method that forms weaving machine warp is to use slasher sizing machine, and most woven operation has had such device.
Summary of the invention
Various embodiments of the present invention relate in general to low density and high strength glass fiber, and relate to comprising and be applicable to strengthen the low density of application and glass fiber precursor, yarn, fabric and the matrix material of high strength glass fiber.
Embodiments more of the present invention relate to glass fiber precursor.Disclosed herein is many can Fibrotic glass composition as a part of the present invention, and be to be understood that various embodiments of the present invention can comprise glass fibre, glass fiber precursor, yarn and be mixed with other products by so formed glass fibre of composition.
On the one hand, glass fiber precursor of the present invention comprises a plurality of glass fibre, and this fiber comprises the glass composition that contains following component:
SiO 2The 60-68 % by weight;
B 2O 3The 7-12 % by weight;
Al 2O 3The 9-15 % by weight;
MgO 8-15 % by weight;
CaO 0-4 % by weight;
Li 2O 0-2 % by weight;
Na 2O 0-1 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-1 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions are the 0-5 % by weight altogether;
(Li wherein 2O+Na 2O+K 2O) content is less than 2 % by weight, and wherein MgO content is the twice at least of CaO content based on % by weight.
On the other hand, glass fiber precursor of the present invention comprises a plurality of glass fibre, and this fiber comprises the glass composition of following component:
SiO 253.5-77 % by weight;
B 2O 34.5-14.5 % by weight;
Al 2O 34.5-18.5 % by weight;
MgO 4-12.5 % by weight;
CaO 0-10.5 % by weight;
Li 2O 0-4 % by weight;
Na 2O 0-2 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-2 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions are the 0-5 % by weight altogether.
In some embodiments, the diameter of a plurality of glass fibre can be about 5 microns-about 13 microns.In some embodiments, this glass fiber precursor is coated with glueing composition at least in part.
Embodiments more of the present invention relate to the yarn that is formed by at least a glass fiber precursor, and this glass strand is that described glass composition forms from here.Embodiments more of the present invention relate to the fabric that contains at least a glass fiber precursor, and this glass strand is that described glass composition forms from here.In some embodiments, in fabric, weft yarn used can comprise at least a glass fiber precursor.Warp thread can comprise at least a glass fiber precursor in some embodiments.In some embodiments, glass fiber precursor can be used to form fabric of the present invention weft yarn used and warp thread both in.In some embodiments, fabric of the present invention can comprise plain weave fabric, twilled fabric, woven fabric, satin woven fabric, stitch bonded fabric or 3D woven fabric.
Embodiments more of the present invention relate to matrix material, and it comprises fluoropolymer resin and the formed glass fibre of one of described different glass composition from here.This glass fibre can form glass fiber precursor in some embodiments of the present invention.In some embodiments, this glass fibre can be incorporated into fabric for example in woven fabric.For example, this glass fibre can be in the weft yarn and/or warp thread of woven formation fabric.This matrix material comprises in the embodiment of fabric therein, and this fabric can comprise plain weave fabric, twilled fabric, woven fabric, satin woven fabric, stitch bonded fabric or 3D woven fabric.This glass fibre can be incorporated in other forms and following matrix material discussed in detail.
About fluoropolymer resin, matrix material of the present invention can comprise one or more multiple polymers resin.In some embodiments, this fluoropolymer resin comprises following at least a: polyvinyl resin, acrylic resin, polyamide resin, polyimide resin, polybutylene terephthalate resin, polycarbonate resin, TPU(Thermoplastic polyurethanes), phenolic resin, vibrin, vinyl ester resin, polydicyclopentadiene resins, polyphenylene sulfide, polyether-ether-ketone resin, cyanate ester resin, bimaleimide resin and thermosetting polyurethane resin.This fluoropolymer resin can comprise epoxy resin in some embodiments.
Matrix material of the present invention can have various ways, and can be used for multiple application.For example and be not limited to this, this matrix material can comprise aerospace matrix material, aviation matrix material, radome, laminate, fiber-metal level zoarium and other materials.As an example, fiber-metal level zoarium can comprise layer and the tinsel of the matrix material of various glass strengthenings.In one embodiment, fiber-metal level zoarium can comprise prepreg (it comprises fluoropolymer resin) and fabric (it comprises the formed a plurality of glass fibre of one of described various glass composition from here), be adhesively secured to lip-deep first tinsel of this prepreg, with the second tinsel that is adhesively secured on this prepreg second surface, so that this prepreg is between two tinsels.In another embodiment, the second prepreg is between the second tinsel and the 3rd tinsel.In one embodiment, this tinsel can comprise aluminium and can comprise epoxy with this fluoropolymer resin.
These and other embodiments will be discussed in the following detailed description in more detail.
Embodiment
In this manual, unless indication is separately arranged, it is with term " approximately " modification that whole numerals of expression amount of composition used, reaction conditions etc. in specification sheets are understood to be in whole situations.Therefore, unless opposite indication is arranged, otherwise the digital parameters of illustrating in following specification sheets is similar to, its can look for according to the present invention acquisition expectation performance and change.At least, and be not that plan limits the scope of claim with doctrine of equivalents, each digital parameters should be at least according to the numerical value of the significant figure of reporting with by explaining with the common technology of rounding up.
Be similar to although illustrate digital scope and the parameter of the wide scope of the present invention, as far as possible accurately report at the numerical value described in specific embodiment.But any numerical value comprises the error that must be formed by the standard deviation that exists in applicable thermometrically in essence.
Be noted that in addition as used in this specification sheets, singulative " ", " a kind of " and " being somebody's turn to do " have comprised plural indicator, unless clear and definite and beyond all doubt being restricted to outside a kind of indicator.
Strengthen some materials such as fluoropolymer resin can produce the matrix material with improved shock resistance and/or other mechanical propertys of making us expecting with glass fibre.Strengthen for some glass fibre and use, be desirable to and use stronger, more light weight and the effective glass fibre of cost more.High strength and/or high-modulus and low-density combination are particularly importants for some aerospace and transport applications, and weight is often an important design variable therein.Compare with the glass fibre that comprises glass, useful glass fibre can show high strain inefficacy, high strength and/or low fibre density in some embodiments of the present invention, this combination can produce the matrix material that glass fibre strengthens, and it has for given fiber volume fraction or given composite property and has lower area density.In some embodiments, this glass fibre can be arranged in fabric.In some embodiments, glass fibre of the present invention can provide with other forms, comprises such as and is not limited to chopped strand (do or wet), yarn, fabric, prepreg etc.In brief, the glass composition of various embodiments (with any fiber that is formed by it) can be used for multiple application.
Having developed can Fibrotic glass composition, and it provides the improved electrical property of E-glass (that is, the low-k D with respect to standard kAnd/or low dissipation coefficient D f), provide simultaneously and former low D kThe glass scheme is compared the temperature-viscosity relationship that more is of value to the fiberizing in business practice.Such glass composition is described in the U.S. Patent Application Serial 13/229012 of U.S. Patent No. 7829490 and application on September 9th, 2011, and content both all is incorporated herein by reference with them at this.Another the optional aspect that is described in the glass composition in U.S. Patent No. 7829490 and U.S. Patent Application Serial 13/229012 is that the said composition of at least some can be used with respect to low raw material batch and becomes original business manufacturing.
Embodiments more of the present invention relate to glass fiber precursor.Embodiments more of the present invention relate to the yarn that comprises glass fiber precursor.The yarn of some embodiments of the present invention is particularly suitable for woven application.In addition, embodiments more of the present invention relate to glasscloth.The glasscloth of some embodiments of the present invention is specially adapted to strengthen and uses, and particularly wherein low density and high-modulus, high strength and/or high strain inefficacy are during important enhancing is used.In addition, embodiments more of the present invention relate to matrix material, and it contains glass fiber precursor, glass fiber yarn and glasscloth, for example fiber reinforced polymer composites.Matrix materials more of the present invention are specially adapted to strengthen and use, and particularly wherein low density and high-modulus, high strength and/or high strain inefficacy are during important enhancing is used, for example aerospace, aviation, wind energy, radome and other application.Matrix materials more of the present invention can be specially adapted to any such application, and high impact properties and low density make us expecting therein.Exemplary application comprises aerospace applications, aerospace applications, automobile application, marine applications, wind energy application, bridge construction and radome etc.Embodiments more of the present invention relate to the aerospace matrix material.Other embodiments of the application relate to the aviation matrix material.Still other embodiments of the present invention relate to and are applicable to the applicable matrix material of wind.Embodiments more of the present invention relate to prepreg.Other embodiments of the present invention relate to laminate.Embodiments more of the present invention relate to fiber-metal level fit (for example glass fibre prepreg between tinsel), and it can for example be used for secondary aircraft structure.Other embodiments of the present invention relate to radome.
Embodiments more of the present invention relate to glass fiber precursor.In some embodiments, glass fiber precursor of the present invention comprises a plurality of glass fibre, and this fiber comprises the glass composition that contains following component:
SiO 2The 60-68 % by weight;
B 2O 3The 7-12 % by weight;
Al 2O 3The 9-15 % by weight;
MgO 8-15 % by weight;
CaO 0-4 % by weight;
Li 2O 0-2 % by weight;
Na 2O 0-1 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-1 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions are the 0-5 % by weight altogether.
In some embodiments, (Li 2O+Na 2O+K 2O) content can be less than 2 % by weight, and MgO content can be the twice at least of CaO content based on % by weight.
In some embodiments, glass fiber precursor of the present invention comprises a plurality of glass fibre, and this fiber comprises the glass composition of following component:
SiO 253.5-77 % by weight;
B 2O 34.5-14.5 % by weight;
Al 2O 34.5-18.5 % by weight;
MgO 4-12.5 % by weight;
CaO 0-10.5 % by weight;
Li 2O 0-4 % by weight;
Na 2O 0-2 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-2 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions are the 0-5 % by weight altogether.
In some embodiments, glass fiber precursor of the present invention comprises the glass composition that contains following component:
SiO 2The 60-68 % by weight;
B 2O 3The 7-12 % by weight;
Al 2O 3The 9-15 % by weight;
MgO 8-15 % by weight;
CaO 0-4 % by weight;
Li 2O〉the 0-2 % by weight;
Na 2O 0-1 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-1 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions are the 0-5 % by weight altogether;
Li wherein 2O content is greater than Na 2O content or greater than K 2O content.
Disclosed herein is other many glass compositions as a part of the present invention, and other embodiments of the present invention relate to by the formed glass fiber precursor of such composition.
In some embodiments, the formed glass fiber precursor of described glass composition can show the performance of making us expecting from here, for example improved fibre strength, Young's modulus, inefficacy strain and/or thermal linear expansion coefficient, also show relatively low density simultaneously.The glass fiber precursor that comprises other glass compositions disclosed herein also can show one or more and make us like this performance expected.
Glass fiber precursor can comprise the glass fibre of different diameter, and this depends on the application of expectation.In some embodiments, glass fiber precursor of the present invention comprises at least a glass fibre that diameter is the about 13 μ m of about 5-.In other embodiments, the diameter of this at least a glass fibre is the about 7 μ m of about 5-.
In some embodiments, glass fiber precursor of the present invention can form rove.Rove can comprise the vertical pulling rove of plying, bull or single head.The rove that comprises glass fiber precursor of the present invention can comprise the vertical pulling single head rove with different diameter and density, and this depends on the application of expectation.In some embodiments, the rove that comprises glass fiber precursor of the present invention shows high density to about 112yd/lb.
Embodiments more of the present invention relate to the yarn that comprises at least a glass fiber precursor disclosed herein.In some embodiments, yarn of the present invention comprises at least a glass fiber precursor, and the glass composition that this precursor comprises comprises the SiO of 60-68 % by weight 2, the B of 7-12 % by weight 2O 3, the Al of 9-15 % by weight 2O 3, the MgO of 8-15 % by weight, the CaO of 0-4 % by weight, the Li of 0-2 % by weight 2O, the Na of 0-1 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-1 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.In some embodiments, yarn comprises at least a glass fiber precursor, and its contained glass composition comprises the SiO of 53.5-77 % by weight 2, the B of 4.5-14.5 % by weight 2O 3, the Al of 4.5-18.5 % by weight 2O 3, the MgO of 4-12.5 % by weight, the CaO of 0-10.5 % by weight, the Li of 0-4 % by weight 2O, the Na of 0-2 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-2 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.In other embodiments, yarn of the present invention can comprise at least a glass fiber precursor, and it comprises one of other glass compositions as a part of the present invention disclosed herein.
In some embodiments, yarn of the present invention comprises at least a glass fiber precursor disclosed herein, and wherein this at least a glass fiber precursor is coated with glueing composition at least in part.In some embodiments, this glueing composition and thermosetting polymer resin compatible.In other embodiments, this glueing composition can comprise starch-oily glueing composition.
Yarn can have different linear quality density, and this depends on the application of expectation.In some embodiments, the linear quality density of yarn of the present invention is the about 10000yd/lb of 5000yd/lb-.
Yarn can have different amount of twist and direction, and this depends on the application of expectation.In some embodiments, the twisting of yarn of the present invention on the z direction is about 2 circles of about 0.5-/inch.In other embodiments, the amount of twist of yarn of the present invention on the z direction is about 0.7 circle/inch.
Yarn can by one or more twisting together and/or the bending precursor make, this depends on the application of expectation.Yarn can by one or more twisting together but the precursor that does not bend make; Such yarn is called " single line ".Yarn of the present invention can by one or more twisting together but the precursor that does not bend make.In some embodiments, yarn of the present invention comprises a twisting 1-4 together precursor.In other embodiments, yarn of the present invention comprises the precursor of 1 twisting.
After thermal cleaning and finishing, to compare with the yarn of being made by the glass composition of routine, the yarn that comprises glass composition of the present invention of some embodiments can confirm improved breaking load retentivity.
Embodiments more of the present invention relate to the fabric that comprises at least a glass fiber precursor.In some embodiments, fabric comprises at least a glass fiber precursor, and its contained glass composition comprises the SiO of 60-68 % by weight 2, the B of 7-12 % by weight 2O 3, the Al of 9-15 % by weight 2O 3, the MgO of 8-15 % by weight, the CaO of 0-4 % by weight, the Li of 0-2 % by weight 2O, the Na of 0-1 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-1 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.In some embodiments, fabric comprises at least a glass fiber precursor, and its contained glass composition comprises the SiO of 53.5-77 % by weight 2, the B of 4.5-14.5 % by weight 2O 3, the Al of 4.5-18.5 % by weight 2O 3, the MgO of 4-12.5 % by weight, the CaO of 0-10.5 % by weight, the Li of 0-4 % by weight 2O, the Na of 0-2 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-2 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.In other embodiments, fabric of the present invention can comprise at least a glass fiber precursor, and it comprises one of other glass compositions as a part of the present invention disclosed herein.In some embodiments, fabric of the present invention comprises yarn disclosed herein.Fabric of the present invention can comprise at least a weft yarn in some embodiments, and it comprises at least a glass fiber precursor disclosed herein.Fabric of the present invention can comprise at least a warp thread in some embodiments, and it comprises at least a glass fiber precursor disclosed herein.In some embodiments, fabric of the present invention comprises at least a weft yarn (it comprises at least a glass fiber precursor disclosed herein) and at least a warp thread (it comprises at least a glass fiber precursor disclosed herein).
In some embodiments that comprise fabric of the present invention, glasscloth is according to the woven fabric of technical fabric style No.7781.In other embodiments, this fabric comprises plain weave fabric, twilled fabric, woven fabric, satin woven fabric, stitch bonded fabric (also referred to as non-crimping fabric) or " three-dimensional " woven fabric.
Embodiments more of the present invention relate to matrix material.In some embodiments, matrix material of the present invention comprises fluoropolymer resin and a plurality of glass fibre that is arranged in this fluoropolymer resin, wherein at least a glass composition that contains following component that comprises in these a plurality of glass fibre: the SiO of 60-68 % by weight 2, the B of 7-12 % by weight 2O 3, the Al of 9-15 % by weight 2O 3, the MgO of 8-15 % by weight, the CaO of 0-4 % by weight, the Li of 0-2 % by weight 2O, the Na of 0-1 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-1 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.Matrix material of the present invention comprises fluoropolymer resin and a plurality of glass fibre that is arranged in this fluoropolymer resin in some embodiments, wherein at least a glass composition that contains following component that comprises in these a plurality of glass fibre: the SiO of 53.5-77 % by weight 2, the B of 4.5-14.5 % by weight 2O 3, the Al of 4.5-18.5 % by weight 2O 3, the MgO of 4-12.5 % by weight, the CaO of 0-10.5 % by weight, the Li of 0-4 % by weight 2O, the Na of 0-2 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-2 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.In other embodiments, matrix material of the present invention can comprise fluoropolymer resin and a plurality of glass fibre that is arranged in this fluoropolymer resin, and wherein at least a in these a plurality of glass fibre is that one of disclosed other glass compositions as a part of the present invention form from here.In some embodiments, matrix material of the present invention comprises fluoropolymer resin and the glass fiber precursor at least a disclosed herein that is arranged in this fluoropolymer resin.In some embodiments, matrix material of the present invention comprises fluoropolymer resin and is arranged in the rove of at least a portion of this fluoropolymer resin, and this rove comprises at least a glass fiber precursor disclosed herein.In other embodiments, matrix material of the present invention comprises fluoropolymer resin and the yarn at least a disclosed herein that is arranged in this fluoropolymer resin.In other embodiments still, matrix material of the present invention comprises fluoropolymer resin and is arranged in the fabric at least a disclosed herein of this fluoropolymer resin.In some embodiments, matrix material of the present invention comprises at least a weft yarn (it comprises at least a glass fiber precursor disclosed herein) and at least a warp thread (it comprises at least a glass fiber precursor disclosed herein).
Matrix material of the present invention can comprise different fluoropolymer resins, and this depends on performance and the application of expectation.Comprise in some embodiments of matrix material in the present invention, this fluoropolymer resin comprises epoxy resin.In other embodiments that comprise matrix material of the present invention, this fluoropolymer resin can comprise polyvinyl resin, acrylic resin, polyamide resin, polyimide resin, polybutylene terephthalate resin, polycarbonate resin, TPU(Thermoplastic polyurethanes), phenolic resin, vibrin, vinyl ester resin, polydicyclopentadiene resins, polyphenylene sulfide, polyether-ether-ketone resin, cyanate ester resin, bimaleimide resin and thermosetting polyurethane resin.
Embodiments more of the present invention relate to the aerospace matrix material.In some embodiments, aerospace matrix material of the present invention shows the performance that is expected to be useful in aerospace applications, high-modulus for example, high inefficacy strain and/or low density.It is special expectation in aerospace applications that the low density of aerospace matrix materials more of the present invention can make such matrix material, and the weight that reduces therein is important.The cost of aerospace matrix material of the present invention also can be less than other matrix materials used in aerospace applications.
In some embodiments, aerospace matrix material of the present invention comprises fluoropolymer resin and a plurality of glass fibre that are arranged in this fluoropolymer resin, the wherein at least a glass composition that contains following component that comprises in these a plurality of glass fibre: the SiO of 60-68 % by weight 2, the B of 7-12 % by weight 2O 3, the Al of 9-15 % by weight 2O 3, the MgO of 8-15 % by weight, the CaO of 0-4 % by weight, the Li of 0-2 % by weight 2O, the Na of 0-1 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-1 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.Aerospace matrix material of the present invention comprises in some embodiments fluoropolymer resin and is arranged in a plurality of glass fibre of this fluoropolymer resin, the wherein at least a glass composition that contains following component that comprises of these a plurality of glass fibre: the SiO of 53.5-77 % by weight 2, the B of 4.5-14.5 % by weight 2O 3, the Al of 4.5-18.5 % by weight 2O 3, the MgO of 4-12.5 % by weight, the CaO of 0-10.5 % by weight, the Li of 0-4 % by weight 2O, the Na of 0-2 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-2 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.In other embodiments, aerospace matrix material of the present invention can comprise fluoropolymer resin and be arranged in a plurality of glass fibre of this fluoropolymer resin, and wherein this a plurality of glass fibre at least a is one of disclosed other glass compositions as a part of the present invention formation from here.
In some embodiments, aerospace matrix material of the present invention comprises fluoropolymer resin and the glass fiber precursor at least a disclosed herein that is arranged in this fluoropolymer resin.In some embodiments, aerospace matrix material of the present invention comprises fluoropolymer resin and is arranged in the rove of at least a portion of this fluoropolymer resin, and this rove comprises as at least a glass fiber precursor disclosed herein.In other embodiments, aerospace matrix material of the present invention comprises fluoropolymer resin and the yarn at least a disclosed herein that is arranged in fluoropolymer resin.In other embodiments still, aerospace matrix material of the present invention comprises fluoropolymer resin and is arranged in the fabric at least a disclosed herein of this fluoropolymer resin.In some embodiments, aerospace matrix material of the present invention comprises at least a weft yarn (it comprises at least a glass fiber precursor disclosed herein) and at least a warp thread (it comprises at least a glass fiber precursor disclosed herein).
Aerospace matrix material of the present invention can comprise different fluoropolymer resins, and this depends on performance and the application of expectation.In some embodiments that comprise the aerospace matrix material of the present invention, this fluoropolymer resin comprises epoxy resin.In other embodiments that comprise the aerospace matrix material of the present invention, this fluoropolymer resin can comprise polyvinyl resin, acrylic resin, polyamide resin, polyimide resin, polybutylene terephthalate resin, polycarbonate resin, TPU(Thermoplastic polyurethanes), phenolic resin, vibrin, vinyl ester resin, polydicyclopentadiene resins, polyphenylene sulfide, polyether-ether-ketone resin, cyanate ester resin, bimaleimide resin and thermosetting polyurethane resin.The example that aerospace matrix material of the present invention can be used in part wherein can include but not limited to for example vertisplane rotor blade of floor panel, overhead bin, kitchen (galleys), backrest and other inner compartments (its potential being easy to is impacted) and external component.
Embodiments more of the present invention relate to the aviation matrix material.In some embodiments, aviation matrix material of the present invention shows for the desired performance of aerospace applications, high-modulus for example, high strain inefficacy and/or low density.It is special expectation in aerospace applications that the height inefficacy strain meeting of aviation matrix materials more of the present invention makes such matrix material, and high impact properties is important therein, and for example interior of aircraft is used.In some embodiments, compare with the matrix material that is formed by the E-glass fabric, aviation matrix material of the present invention can confirm the impact property that improves.The cost of aviation matrix material of the present invention also can be less than other matrix materials used in aerospace applications.Aviation matrix material of the present invention goes for interior of aircraft (comprising luggage torage tank, seat and floor etc.).
In some embodiments, aviation matrix material of the present invention comprises fluoropolymer resin and is arranged in a plurality of glass fibre of this fluoropolymer resin, the wherein at least a glass composition that contains following component that comprises of these a plurality of glass fibre: the SiO of 60-68 % by weight 2, the B of 7-12 % by weight 2O 3, the Al of 9-15 % by weight 2O 3, the MgO of 8-15 % by weight, the CaO of 0-4 % by weight, the Li of 0-2 % by weight 2O, the Na of 0-1 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-1 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.Aviation matrix material of the present invention comprises in some embodiments fluoropolymer resin and is arranged in a plurality of glass fibre of this fluoropolymer resin, the wherein at least a glass composition that contains following component that comprises of these a plurality of glass fibre: the SiO of 53.5-77 % by weight 2, the B of 4.5-14.5 % by weight 2O 3, the Al of 4.5-18.5 % by weight 2O 3, the MgO of 4-12.5 % by weight, the CaO of 0-10.5 % by weight, the Li of 0-4 % by weight 2O, the Na of 0-2 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-2 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.In other embodiments, aviation matrix material of the present invention can comprise fluoropolymer resin and be arranged in a plurality of glass fibre of this fluoropolymer resin, and wherein this a plurality of glass fibre at least a is one of disclosed other glass compositions as a part of the present invention formation from here.
In some embodiments, aviation matrix material of the present invention comprises fluoropolymer resin and the glass fiber precursor at least a disclosed herein that is arranged in this fluoropolymer resin.In some embodiments, aviation matrix material of the present invention comprises fluoropolymer resin and is arranged in the rove of at least a portion of this fluoropolymer resin, and this rove comprises at least a glass fiber precursor disclosed herein.In other embodiments, aviation matrix material of the present invention comprises fluoropolymer resin and the yarn at least a disclosed herein that is arranged in this fluoropolymer resin.In other embodiments still, aviation matrix material of the present invention comprises fluoropolymer resin and is arranged in the fabric at least a disclosed herein of this fluoropolymer resin.In some embodiments, aviation matrix material of the present invention comprises at least a weft yarn (it comprises at least a glass fiber precursor disclosed herein) and at least a warp thread (it comprises at least a glass fiber precursor disclosed herein).
Aviation matrix material of the present invention can comprise different fluoropolymer resins, and this depends on performance and the application of expectation.In some embodiments that comprise the aviation matrix material of the present invention, this fluoropolymer resin comprises phenol tree lipoid.In other embodiments that comprise the aviation matrix material of the present invention, this fluoropolymer resin can comprise epoxy resin, polyvinyl resin, acrylic resin, polyamide resin, polyimide resin, the polybutylene terephthalate resin, polycarbonate resin, TPU(Thermoplastic polyurethanes), phenolic resin, vibrin, vinyl ester resin, polydicyclopentadiene resins, polyphenylene sulfide, polyether-ether-ketone resin, cyanate ester resin, bimaleimide resin and thermosetting polyurethane resin.The example that aerospace matrix material of the present invention can be used in part wherein can include but not limited to for example vertisplane rotor blade of floor panel, overhead bin, kitchen (galleys), backrest and other inner compartments (its potential being easy to is impacted) and external component.
Embodiments more of the present invention relate to and can be used in the applicable matrix material of wind and use.In some embodiments, the applicable matrix material of wind that is applicable to of the present invention shows for the desired performance of wind energy application, for example high-modulus/high inefficacy strain and low density.Other matrix materials used during the cost that is applicable to the applicable matrix material of wind of the present invention also can be used less than wind energy.Matrix material of the present invention goes in wind turbine blade, the wind turbine blade of particularly growing, and it is lighter weight, but still is better than the wind turbine blade of other length.
In some embodiments, a plurality of glass fibre that the applicable matrix material of wind comprises fluoropolymer resin and is arranged in this fluoropolymer resin, the wherein at least a glass composition that contains following component that comprises of these a plurality of glass fibre of being applicable to of the present invention: the SiO of 60-68 % by weight 2, the B of 7-12 % by weight 2O 3, the Al of 9-15 % by weight 2O 3, the MgO of 8-15 % by weight, the CaO of 0-4 % by weight, the Li of 0-2 % by weight 2O, the Na of 0-1 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-1 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.A plurality of glass fibre that the applicable matrix material of wind comprises in some embodiments fluoropolymer resin and is arranged in this fluoropolymer resin, the wherein at least a glass composition that contains following component that comprises of these a plurality of glass fibre of being applicable to of the present invention: the SiO of 53.5-77 % by weight 2, the B of 4.5-14.5 % by weight 2O 3, the Al of 4.5-18.5 % by weight 2O 3, the MgO of 4-12.5 % by weight, the CaO of 0-10.5 % by weight, the Li of 0-4 % by weight 2O, the Na of 0-2 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-2 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.In other embodiments, aviation matrix material of the present invention can comprise fluoropolymer resin and be arranged in a plurality of glass fibre of this fluoropolymer resin, and wherein this a plurality of glass fibre at least a is one of disclosed other glass compositions as a part of the present invention formation from here.
In some embodiments, the applicable matrix material of wind that is applicable to of the present invention comprises fluoropolymer resin and the glass fiber precursor at least a disclosed herein that is arranged in this fluoropolymer resin.In some embodiments, the applicable matrix material of wind that is applicable to of the present invention comprises fluoropolymer resin and the rove that is arranged at least a portion of this fluoropolymer resin, and this rove comprises at least a glass fiber precursor disclosed herein.In other embodiments, the applicable matrix material of wind that is applicable to of the present invention comprises fluoropolymer resin and the yarn at least a disclosed herein that is arranged in this fluoropolymer resin.In other embodiments still, the applicable matrix material of wind that is applicable to of the present invention comprises fluoropolymer resin and the fabric at least a disclosed herein that is arranged in this fluoropolymer resin.In some embodiments, the applicable matrix material of wind that is applicable to of the present invention comprises at least a weft yarn (it comprises at least a glass fiber precursor disclosed herein) and at least a warp thread (it comprises at least a glass fiber precursor disclosed herein).
The applicable matrix material of wind that is applicable to of the present invention can comprise different fluoropolymer resins, and this depends on performance and the application of expectation.Comprise of the present invention some embodiments that are applicable to the applicable matrix material of wind, this fluoropolymer resin comprises epoxy resin.Comprise of the present invention other embodiments that are applicable to the applicable matrix material of wind, this fluoropolymer resin can comprise vibrin, vinyl ester resin, thermosetting polyurethane resin or polydicyclopentadiene resins.
Embodiments more of the present invention relate to laminate.Laminate of the present invention can comprise a plurality of platy layers and make up form layers fit.In some embodiments, laminate of the present invention comprises at least a layer, and this layer comprises matrix material described herein.In some embodiments, laminate of the present invention comprises at least a layer that comprises matrix material, this matrix material comprises fluoropolymer resin and is arranged in a plurality of glass fibre of this fluoropolymer resin, the wherein at least a glass composition that contains following component that comprises of these a plurality of glass fibre: the SiO of 60-68 % by weight 2, the B of 7-12 % by weight 2O 3, the Al of 9-15 % by weight 2O 3, the MgO of 8-15 % by weight, the CaO of 0-4 % by weight, the Li of 0-2 % by weight 2O, the Na of 0-1 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-1 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.Laminate of the present invention comprises at least a layer that comprises matrix material in some embodiments, this matrix material comprises fluoropolymer resin and is arranged in a plurality of glass fibre of this fluoropolymer resin, the wherein at least a glass composition that contains following component that comprises of these a plurality of glass fibre: the SiO of 53.5-77 % by weight 2, the B of 4.5-14.5 % by weight 2O 3, the Al of 4.5-18.5 % by weight 2O 3, the MgO of 4-12.5 % by weight, the CaO of 0-10.5 % by weight, the Li of 0-4 % by weight 2O, the Na of 0-2 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-2 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.In other embodiments, laminate of the present invention can comprise at least a layer that comprises matrix material, this matrix material comprises fluoropolymer resin and is arranged in a plurality of glass fibre of this fluoropolymer resin, and wherein this a plurality of glass fibre at least a is one of disclosed other glass compositions as a part of the present invention formation from here.
In some embodiments, laminate of the present invention comprises matrix material, the glass fiber precursor at least a disclosed herein that it comprises fluoropolymer resin and is arranged in this fluoropolymer resin.In some embodiments, laminate of the present invention comprises fluoropolymer resin and is arranged in the rove of at least a portion of this fluoropolymer resin, and this rove comprises at least a glass fiber precursor disclosed herein.In other embodiments, laminate of the present invention comprises matrix material, the yarn at least a disclosed herein that it comprises fluoropolymer resin and is arranged in this fluoropolymer resin.In other embodiments still, laminate of the present invention comprises matrix material, the fabric at least a disclosed herein that it comprises fluoropolymer resin and is arranged in this fluoropolymer resin.In some embodiments, laminate of the present invention comprises at least a weft yarn (it comprises at least a glass fiber precursor disclosed herein) and at least a warp thread (it comprises at least a glass fiber precursor disclosed herein).
Laminate of the present invention can comprise different fluoropolymer resins, and this depends on performance and the application of expectation.In some embodiments that comprise laminate of the present invention, this fluoropolymer resin comprises epoxy resin.In other embodiments that comprise matrix material of the present invention, this fluoropolymer resin can comprise polyvinyl resin, acrylic resin, polyamide resin, polyimide resin, polybutylene terephthalate resin, polycarbonate resin, TPU(Thermoplastic polyurethanes), phenolic resin, vibrin, vinyl ester resin, polydicyclopentadiene resins, polyphenylene sulfide, polyether-ether-ketone resin, cyanate ester resin, bimaleimide resin and thermosetting polyurethane resin.
Embodiments more of the present invention relate to prepreg.Prepreg of the present invention can comprise fluoropolymer resin and at least a glass fiber precursor disclosed herein.In some embodiments, prepreg of the present invention comprises fluoropolymer resin and a plurality of glass fibre that contact with this fluoropolymer resin, wherein at least a glass composition that contains following component that comprises of these a plurality of glass fibre: the SiO of 60-68 % by weight 2, the B of 7-12 % by weight 2O 3, the Al of 9-15 % by weight 2O 3, the MgO of 8-15 % by weight, the CaO of 0-4 % by weight, the Li of 0-2 % by weight 2O, the Na of 0-1 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-1 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.Prepreg of the present invention comprises fluoropolymer resin and a plurality of glass fibre that contact with this fluoropolymer resin in some embodiments, wherein at least a glass composition that contains following component that comprises of these a plurality of glass fibre: the SiO of 53.5-77 % by weight 2, the B of 4.5-14.5 % by weight 2O 3, the Al of 4.5-18.5 % by weight 2O 3, the MgO of 4-12.5 % by weight, the CaO of 0-10.5 % by weight, the Li of 0-4 % by weight 2O, the Na of 0-2 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-2 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.In other embodiments, prepreg of the present invention can comprise fluoropolymer resin and a plurality of glass fibre that contact with this fluoropolymer resin, and wherein this a plurality of glass fibre at least a is that one of disclosed other glass compositions as a part of the present invention form from here.
In some embodiments, prepreg of the present invention comprises fluoropolymer resin and the glass fiber precursor at least a disclosed herein that contacts with this fluoropolymer resin.In some embodiments, prepreg of the present invention comprises fluoropolymer resin and is arranged in the rove of at least a portion of this fluoropolymer resin, and this rove comprises at least a glass fiber precursor disclosed herein.In other embodiments, prepreg of the present invention comprises fluoropolymer resin and the yarn at least a disclosed herein that contacts with this fluoropolymer resin.In other embodiments still, prepreg of the present invention comprises fluoropolymer resin and the fabric at least a disclosed herein that contacts with this fluoropolymer resin.In some embodiments, prepreg of the present invention comprises at least a weft yarn (it comprises at least a glass fiber precursor disclosed herein) and at least a warp thread (it comprises at least a glass fiber precursor disclosed herein).
Prepreg of the present invention can comprise different fluoropolymer resins, and this depends on performance and the application of expectation.In some embodiments that comprise prepreg of the present invention, this fluoropolymer resin comprises epoxy resin.In other embodiments that comprise prepreg of the present invention, this fluoropolymer resin can comprise polyvinyl resin, acrylic resin, polyamide resin, polyimide resin, polybutylene terephthalate resin, polycarbonate resin, TPU(Thermoplastic polyurethanes), phenolic resin, vibrin, vinyl ester resin, polydicyclopentadiene resins, polyphenylene sulfide, polyether-ether-ketone resin, cyanate ester resin, bimaleimide resin and thermosetting polyurethane resin.
Prepreg of the present invention can be incorporated in other products in some embodiments.For example in some embodiments, prepreg of the present invention can be incorporated in fiber-metal level zoarium.It can be favourable that prepreg of the present invention is incorporated in fiber-metal level zoarium, because in some embodiments, this prepreg can have excellent crackle stagnation performance and proportion, for the tinsel that may use (for example aluminum alloy sheet).Several fibers-metal laminate style such as GLARE and ARALL are known, and prepreg of the present invention can be easy to be incorporated in those structures.Fiber-metal laminate style such as GLARE (" epoxy resin that the fit aluminium of glass coating strengthens ") and ARALL (a kind of aramid fiber base fiber-metal level is fit) develop as the light weight fuselage material that is used for aerospace applications, and GLARE is generally used for fuselage and uses, and ARALL is generally used for wing and uses.The traditional structure of GLARE fiber-metal level zoarium be glass fibre/epoxy prepreg base (single shaft to or biax) with pretreated aluminium foil (namely, 0.2-0.4mm thick 2024T3 paper tinsel is brought up to sticking power on composite layer with the proprietary method etching) alternating layer.These laminate structures can have wide adaptability in aircraft structure, this is owing to the fatigue property of their excellence, the corrosion rate of reduction and crack expansion characteristic slowly under stress rising head (for example hole, rivet, edge) exists.Such laminate is typically molded in autoclave or in heat and pressure lower compression.An example of GLARE fiber-metal level zoarium can be with 3 layers of aluminium and 2 layers of twin shaft to matrix material, and sometimes is called the GLARE3/2 laminate.Can also have such embodiment, it is with the aluminium of 4 layers and the matrix material of 3 layers, perhaps the matrix material of the aluminium of 5 layers and 4 layers.
Prepreg of the present invention can replace in such GLARE and ARALL fiber-metal level fit (perhaps other fibers-metal level is fit), as being used at present the substitute of the glass fibre prepreg of such product.Therefore, fiber-metal level zoarium can comprise the prepreg according to embodiments more of the present invention, be adhesively secured to lip-deep first tinsel of this prepreg and the second tinsel that is adhesively secured on this prepreg second surface, so that this prepreg is between two tinsels.in some embodiments, the multilayer prepreg for example can be mixed and 3/2 be arranged (in metal/prepreg/metal/prepreg/metal arrangements, be in two prepreg layer between three tinsels), 4/3 arranges (in metal/prepreg/metal/prepreg/metal/prepreg/metal arrangements, be in three prepreg layer between four tinsels), 5/4 arranges (in metal/prepreg/metal/prepreg/metal/prepreg/metal/prepreg/metal arrangements, be in four prepreg layer between five tinsels) or during other arrange.In some embodiments, this tinsel can comprise aluminium or typically be used for other metals of fiber-metal level zoarium.In some embodiments, in this prepreg, fluoropolymer resin used comprises epoxy.In some embodiments, this prepreg is to use the film adhesive bonds that is used for controlled joint line thickness to be fixed on tinsel, and is such as is known to persons skilled in the art.In some embodiments, minute other caking agent is unwanted, because in prepreg, fluoropolymer resin (for example epoxy) used can adhere to this prepreg on tinsel.
Embodiments more of the present invention relate to radome.Radome is radome or structurizing shell, and it is typically with such material and builds, this material provide low specific inductivity make to/minimum from the signal reflex of radar.Expensive fiber for example quartzy and fragrant acid amides and high strength glass fiber by successfully for the production of from the combined radome of different resin systems.Except radar transparency required, the material that is used for radome preferably provided high rigidity/intensity and excellent durability characteristics, stood carrying capacity of environment (wind, snow, rain, hail, temperature fluctuation and UV degraded).The glass fibre of some embodiments can have the specific inductivity of 5.3@1MHz according to the present invention, although it is higher than quartzy (approximately 3.5), but lower than E-glass (6.3-6.6@1MHz) and suitable with S-2Glass (5-5.4@1MHz), this makes it is a kind of suitable glass fibre of using for radome.
In some embodiments, radome of the present invention comprises fluoropolymer resin and is arranged in a plurality of glass fibre of this fluoropolymer resin, the wherein at least a glass composition that contains following component that comprises of these a plurality of glass fibre: the SiO of 60-68 % by weight 2, the B of 7-12 % by weight 2O 3, the Al of 9-15 % by weight 2O 3, the MgO of 8-15 % by weight, the CaO of 0-4 % by weight, the Li of 0-2 % by weight 2O, the Na of 0-1 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-1 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.Radome of the present invention comprises in some embodiments fluoropolymer resin and is arranged in a plurality of glass fibre of this fluoropolymer resin, the wherein at least a glass composition that contains following component that comprises of these a plurality of glass fibre: the SiO of 53.5-77 % by weight 2, the B of 4.5-14.5 % by weight 2O 3, the Al of 4.5-18.5 % by weight 2O 3, the MgO of 4-12.5 % by weight, the CaO of 0-10.5 % by weight, the Li of 0-4 % by weight 2O, the Na of 0-2 % by weight 2O, the K of 0-1 % by weight 2O, the F of 0-1 % by weight 2O 3, the F of 0-2 % by weight 2, the TiO of 0-2 % by weight 2Other compositions of 0-5 % by weight altogether.In other embodiments, radome of the present invention can comprise fluoropolymer resin and be arranged in a plurality of glass fibre of this fluoropolymer resin, and wherein this a plurality of glass fibre at least a is one of disclosed other glass compositions as a part of the present invention formation from here.
In some embodiments, radome of the present invention comprises radome or structurizing shell, the glass fiber precursor at least a disclosed herein that it comprises fluoropolymer resin and is arranged in this fluoropolymer resin.In some embodiments, radome of the present invention comprises fluoropolymer resin and is arranged in the rove of at least a portion of this fluoropolymer resin, and this rove comprises at least a glass fiber precursor disclosed herein.In other embodiments, radome of the present invention comprises fluoropolymer resin and the yarn at least a disclosed herein that is arranged in this fluoropolymer resin.In other embodiments still, radome of the present invention comprises fluoropolymer resin and is arranged in the fabric at least a disclosed herein of this fluoropolymer resin.In some embodiments, radome of the present invention comprises at least a weft yarn (it comprises at least a glass fiber precursor disclosed herein) and at least a warp thread (it comprises at least a glass fiber precursor disclosed herein).
Radome of the present invention can comprise different fluoropolymer resins, and this depends on performance and the application of expectation.In the present invention relates to some embodiments of radome, this fluoropolymer resin can comprise epoxy resin, the phenolic resin resin, polyvinyl resin, acrylic resin, polyamide resin, polyimide resin, the polybutylene terephthalate resin, polycarbonate resin, TPU(Thermoplastic polyurethanes), the phenolic resin resin, vibrin, vinyl ester resin, polydicyclopentadiene resins, polyphenylene sulfide, polyether-ether-ketone resin, cyanate ester resin, bimaleimide resin and thermosetting polyurethane resin.
Useful glass fibre can be made by any suitable method well known by persons skilled in the art in the present invention, such as but not limited to this above method.In addition, elementary glueing composition can use any suitable method well known by persons skilled in the art to be administered on glass fibre.In some embodiments, this glueing composition can be used after forming glass fibre immediately.This glueing composition can comprise well known by persons skilled in the art for strengthening any suitable glueing composition of using.In some embodiments, this glueing composition does not comprise starch-oily glueing composition.Comprise glueing composition some embodiments of (it does not comprise starch-oily glueing composition) of the present invention, use fiber or precursor in woven application before, the glass fibre of applying glue or glass fiber precursor do not need further to use the sizing compositions-treated.In comprising glueing composition other embodiments of (it does not comprise starch-oily glueing composition), use fiber or precursor in woven application before, the glass fibre of applying glue or glass fiber precursor can be chosen wantonly further uses the sizing compositions-treated.In some embodiments that comprise elementary glueing composition of the present invention, this glueing composition can comprise starch-oily glueing composition.In some embodiments that comprise starch-oily glueing composition of the present invention, this starch-oily glueing composition can be after a while from by removing the glass fibre of at least a applying glue or the formed fabric of glass fiber precursor.In some embodiments, this starch-factice knot can use any suitable method well known by persons skilled in the art to remove from fabric, such as but not limited to thermal cleaning.In the embodiment that comprises fabric (having removed from it starch-oily glueing composition) of the present invention, fabric of the present invention can further be processed with finish paint.
Glass fiber precursor of the present invention can prepare by any suitable method well known by persons skilled in the art.Glasscloth of the present invention can be made by any suitable method well known by persons skilled in the art usually, such as but not limited to parallel yarn (also referred to as " weft yarn ") is interweaved in a plurality of warp thread.Interweaving like this can be completed as getting off: warp thread is arranged on loom with common parallel, planar array, and with predetermined repeat patterns, the parallel yarn was sent on warp thread thereafter and under, with this parallel woven yarn in warp thread.Pattern used will depend on the fabric pattern of expectation.
Warp thread can prepare with technology well known by persons skilled in the art usually.Warp thread can form by a plurality of molten glass flows of decaying from axle bush or spinning-drawing machine., glueing composition be administered to single glass fibre on, and fibril aggregation is formed precursor together thereafter.This precursor is processed into yarn by via the twisting framework, this precursor being transferred to reel subsequently.In this transfer process, this precursor can be given twisting and help fibrous bundle is kept together.The precursor of these twisting then be wrapped in reel around, and this reel is used for woven method.
The location of warp thread on loom can be carried out with technology well known by persons skilled in the art usually.The location of warp thread on loom can be undertaken by weaving machine warp.Weaving machine warp comprises the warp thread (also referred to as " warp beam ") of defined amount, its with substantially parallel arrangement (also referred to as " through sheet ") be wrapped in cylindrical core around.The weaving machine warp preparation can comprise a plurality of yarn bags (each bag comprises the part of weaving machine warp requisite number purpose warp beam) are merged into singly packs or weaving machine warp.Although for example and be not limited to this, 50 inches (127cm) is wide, 7781 style fabrics (it utilizes the input of DE75 yarn) typically need 2868 warp beams.But the conventional equipment that is used to form weaving machine warp does not allow these whole warp beams to transfer on single warp beam from reel in an operation.So, can produce a plurality of warp beams (typically be called " section warp beam ") of a part that comprises requisite number purpose warp beam, and merge thereafter and form weaving machine warp.In a kind of mode that is similar to weaving machine warp, the section warp beam can comprise cylindrical core, and it comprises a plurality of substantially parallel warp thread that are wrapped in the there.Although those skilled in the art's section of being recognized that warp beam can comprise the warp thread that is used to form the required any number of final weaving machine warp, the number of the warp beam that common section warp beam comprises is subject to the ability of the creel of warp arrangement.For 7781 style fabrics, four section warp beams of 717 warp beams typically are provided, each DE75, and provide through 2868 required warp beams of sheet, as mentioned above when merging.
Matrix material of the present invention can prepare by any suitable method well known by persons skilled in the art, and is molded such as but not limited to the vacuum assisted resin perfusion, extrudes mixing, compression molded, resin transfer moulding, filament wound, prepreg/autoclave cured, and draw the agent moulding.Matrix material of the present invention can prepare with such molding technique well known by persons skilled in the art.Concrete, the matrix material of embodiment of the present invention (it is mixed with woven glasscloth) can prepare with the technology for the preparation of such matrix material well known by persons skilled in the art.
As an example, matrix materials more of the present invention can be made with vacuum aided is compression molded, and this technology is well known by persons skilled in the art, and is briefly described below.As well known by persons skilled in the art, when using vacuum aided compression molded, the glass fabric of stacking preimpregnation is placed in the platen of press.In some embodiments of the present invention, this stacking preimpregnation glass fabric can comprise said one or more fabrics of the present invention herein, and it has been cut into desired size and shape.By completing the stack operation for the corresponding number of plies, with the press sealing, and platen is connected on vacuum pump, so that top platen is pressed onto on stacking fabric, until reach the pressure of expectation.Vacuum helps the Bas Discharged of carrying secretly in stacked body and the hole of reducing in moulding layer zoarium content is provided.After platen is connected to vacuum pump, then platen temperature is raise accelerate the transformation efficiency of resin (for example thermosetting resin), be warmed up to for the concrete preset temperature of resin used and set, and set maintenance at this temperature and pressure, until this laminate is realized solidifying fully.At this moment, close described heating, and this platen is cooling by water cycle, until they reach room temperature.Then can open this platen, and molded laminate can be removed from press.
As another example, matrix materials more of the present invention can be made with the vacuum assisted resin perfusion technique, as further describe herein.Stacking glasscloth of the present invention can cut into desired size, and is placed on the glass table of organosilicon release processing.Then this stacked body can cover with peeling off lamella, and the amplified medium that flows is installed, and comes vacuum bagging with nylon pack film.Then, so-called " storage thing (lay up) " can be subject to the vacuum pressure of about 27 inches Hg.Divide other, this fluoropolymer resin (its plan strengthens with glasscloth) can prepare with the technology for concrete resin well known by persons skilled in the art.For example for some fluoropolymer resins, suitable resin (for example curable epoxy resin of amine) can mix with ratio or ratio well known by persons skilled in the art that the resin manufacturer recommends with suitable solidifying agent (amine that for example is used for the amine curable epoxy).The resin of this merging then can be at vacuum chamber degassed 30 minutes, and perfusion passes the fabric preform, until realize basically soaking completely of fabric stacked body.At this moment, described desk can cover 24 hours with the blanket (being set to the temperature of about 45-50 ℃) of heating.The then demoulding of formed rigid composite material, and in programmable convection furnace was about 250 ℉ after fixing 4 hours.But, as well known by persons skilled in the art, different parameter for example degassed time, heat-up time and after fixing condition can change based on concrete resin system used, and those skilled in the art understand how to select such parameter based on concrete resin system.
Laminate of the present invention can prepare by any suitable means well known by persons skilled in the art, such as but not limited to perfusion.
Prepreg of the present invention can prepare by any suitable means well known by persons skilled in the art, such as but not limited to sending resin bath with glass fiber precursor, rove or fabric; Use solvent-based resin; Perhaps use resin molding.
Fiber of the present invention-metal level zoarium can by any suitable means well known by persons skilled in the art, prepare with prepreg of the present invention.
Radome of the present invention can prepare by any suitable means well known by persons skilled in the art.
As mentioned above, embodiments more of the present invention can comprise a plurality of glass fibre.Be applicable to glass fibre of the present invention and can have any suitable diameter well known by persons skilled in the art, this depends on the application of expectation.The diameter that is applicable to the glass fibre of embodiments more of the present invention is the about 13 μ m of about 5-.The diameter that is applicable to the glass fibre of other embodiments of the present invention is about 5-7 μ m.
In addition, be applicable to glass fibre of the present invention and glass fiber precursor and can comprise multiple glass composition, it has also represented embodiment of the present invention.Such glass fibre and the glass fiber precursor of some embodiments are as above, and other scheme is described below.As mentioned above, be applicable to the glass fibre of embodiments more of the present invention or an example of glass fiber precursor and comprise glass composition, it comprises:
SiO 2The 60-68 % by weight;
B 2O 3The 7-12 % by weight;
Al 2O 3The 9-15 % by weight;
MgO 8-15 % by weight;
CaO 0-4 % by weight;
Li 2O 0-2 % by weight;
Na 2O 0-1 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-1 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions are the 0-5 % by weight altogether.
Be applicable to the glass fibre of embodiments more of the present invention or another example of glass fiber precursor and comprise glass composition, it comprises:
SiO 2The 60-68 % by weight;
B 2O 3The 7-12 % by weight;
Al 2O 3The 9-15 % by weight;
MgO 8-15 % by weight;
CaO 0-4 % by weight;
Li 2O〉the 0-2 % by weight;
Na 2O 0-1 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-1 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions are the 0-5 % by weight altogether;
Li wherein 2O content is greater than Na 2O content or greater than K 2O content.In other embodiments, CaO content is the 0-3 % by weight.In other embodiments still, CaO content is the 0-2 % by weight.In some embodiments, CaO content is the 0-1 % by weight.In some embodiments of the present invention, MgO content is the 8-13 % by weight.In other embodiments, MgO content is the 9-12 % by weight.In some embodiments, TiO 2Content is the 0-1 % by weight.In some embodiments, B 2O 3Content is not more than 10 % by weight.In some embodiments of the present invention, Al 2O 3Content is the 9-14 % by weight.In other embodiments, Al 2O 3Content is the 10-13 % by weight.In some embodiments, (Li 2O+Na 2O+K 2O) content is less than 2 % by weight.In some embodiments, said composition comprises the BaO of 0-1 % by weight and the ZnO of 0-2 % by weight.In other embodiments, said composition is substantially free of BaO and is substantially free of ZnO.In some embodiments, the total amount that exists of other compositions (if any) is the 0-2 % by weight.In other embodiments, the total amount that exists of other compositions (if any) is the 0-1 % by weight.In some embodiments, Li 2O content is the 0.4-2.0 % by weight.Comprising Li 2O content is in other embodiments of 0.4-2.0 % by weight, Li 2O content is greater than (Na 2O+K 2O) content.
Be applicable to the glass fibre of embodiments more of the present invention or another example of glass fiber precursor and comprise glass composition, it comprises
SiO 2The 60-68 % by weight;
B 2O 3The 7-13 % by weight;
Al 2O 3The 9-15 % by weight;
MgO 8-15 % by weight;
CaO 0-4 % by weight;
Li 2O 0-2 % by weight;
Na 2O 0-1 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-1 % by weight; With
TiO 2The 0-2 % by weight.
In some embodiments, this glass composition is characterised in that the CaO of relative low levels, for example is in the magnitude of about 0-4 % by weight.In other embodiments still, CaO content can be in the magnitude of about 0-3 % by weight.In some embodiments, MgO content is double (based on the % by weight) of CaO content.The MgO content of embodiments more of the present invention can be greater than about 6.0 % by weight, and in other embodiments, MgO content can be greater than about 7.0 % by weight.Some glass compositions that are applicable to embodiments more of the present invention are characterised in that the BaO that exists less than 1.0 % by weight.Only exist therein in those embodiments of BaO of impurity level of trace, the feature of BaO content can be to be not more than 0.05 % by weight.
Be applicable to the glass fibre of embodiments more of the present invention or another example of glass fiber precursor and comprise glass composition, it comprises
SiO 2The 60-68 % by weight;
B 2O 3The 7-12 % by weight;
Al 2O 3The 9-15 % by weight;
MgO 8-15 % by weight;
CaO 0-4 % by weight;
Li 2O〉the 0-2 % by weight;
Na 2O 0-1 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-1 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions are the 0-5 % by weight altogether;
Li wherein 2O content is greater than Na 2O content or greater than K 2O content and is wherein selected the described specific inductivity (D that becomes to assign to provide k) in the 1MHz frequency less than 6.7 glass.In other embodiments, select described one-tenth to assign to provide specific inductivity (D k) in the 1MHz frequency less than 6 glass.In other embodiments still, select described one-tenth to assign to provide specific inductivity (D k) in the 1MHz frequency less than 5.8 glass.In some embodiments, select described one-tenth to assign to provide specific inductivity (D k) in the 1MHz frequency less than 5.6 glass.
The composition that is applicable to the glass composition of embodiments more of the present invention can be based on the mold temperature (temperature when being defined as viscosity and being 1000 pool) of expectation and/or the liquidus temperature of expectation.In some embodiments, be applicable to glass fibre of the present invention or glass fiber precursor and comprise glass composition, it comprises
SiO 2The 60-68 % by weight;
B 2O 3The 7-12 % by weight;
Al 2O 3The 9-15 % by weight;
MgO 8-15 % by weight;
CaO 0-4 % by weight;
Li 2O〉the 0-2 % by weight;
Na 2O 0-1 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-1 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions are the 0-5 % by weight altogether;
Li wherein 2O content is greater than Na 2O content or greater than K 2O content and is wherein selected described mold temperature T when becoming to assign to be provided at 1000 pool viscosity FBe not more than 1370 ℃.Mold temperature T when in other embodiments, selecting described one-tenth to assign to be provided at 1000 pool viscosity FBe not more than 1320 ℃.In other embodiments still, the mold temperature T when selecting described one-tenth to assign to be provided at 1000 pool viscosity FBe not more than 1300 ℃.Mold temperature T when in some embodiments, selecting described one-tenth to assign to be provided at 1000 pool viscosity FBe not more than 1290 ℃.Mold temperature T when in some embodiments, selecting described one-tenth to assign to be provided at 1000 pool viscosity FBe not more than 1370 ℃ and liquidus temperature T LAt least lower than 55 ℃ of this mold temperatures.Mold temperature T when in other embodiments, selecting described one-tenth to assign to be provided at 1000 pool viscosity FBe not more than 1320 ℃ and liquidus temperature T LAt least lower than 55 ℃ of this mold temperatures.In other embodiments still, the mold temperature T when selecting described one-tenth to assign to be provided at 1000 pool viscosity FBe not more than 1300 ℃ and liquidus temperature T LAt least lower than 55 ℃ of this mold temperatures.Mold temperature T when in some embodiments, selecting described one-tenth to assign to be provided at 1000 pool viscosity FBe not more than 1290 ℃ and liquidus temperature T LAt least lower than 55 ℃ of mold temperatures.
Be applicable to the glass fibre of embodiments more of the present invention or the other example of glass fiber precursor and comprise glass composition, it comprises
B 2O 3Less than 12 % by weight;
Al 2O 3The 9-15 % by weight;
MgO 8-15 % by weight;
CaO 0-4 % by weight;
SiO 2The 60-68 % by weight;
Li 2O〉the 0-2 % by weight;
Na 2O 0-1 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-1 % by weight; With
TiO 2The 0-2 % by weight;
Wherein this glass shows specific inductivity (D k) less than 6.7 and mold temperature (T F) be not more than 1370 ℃ in 1000 pool viscosity, and Li wherein 2O content is greater than Na 2O content or greater than K 2O content.In some embodiments, CaO content is the 0-1 % by weight.
Be applicable to the glass fibre of embodiments more of the present invention or the other example of glass fiber precursor and comprise glass composition, it comprises
SiO 2The 60-68 % by weight;
B 2O 3The 7-12 % by weight;
Al 2O 3The 9-15 % by weight;
MgO 8-15 % by weight;
CaO 0-3 % by weight;
Li 2O 0.4-2 % by weight;
Na 2O 0-1 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-1 % by weight; With
TiO 2The 0-2 % by weight;
Wherein this glass shows specific inductivity (D k) less than 5.9 and mold temperature (T F) be not more than 1300 ℃ in 1000 pool viscosity, and Li wherein 2O content is greater than Na 2O content or greater than K 2O content.
Be applicable to the glass fibre of embodiments more of the present invention or another example of glass fiber precursor and comprise glass composition, it basic composition is
SiO 2The 60-68 % by weight;
B 2O 3The 7-11 % by weight;
Al 2O 3The 9-13 % by weight;
MgO 8-13 % by weight;
CaO 0-3 % by weight;
Li 2O 0.4-2 % by weight;
Na 2O 0-1 % by weight;
K 2O 0-1 % by weight;
(Na 2O+K 2O+Li 2O) 0-2 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-1 % by weight; With
TiO 2The 0-2 % by weight;
Li wherein 2O content is greater than Na 2O content or greater than K 2O content.In some embodiments, CaO content is the 0-1 % by weight.In comprising some embodiments that CaO content is the 0-1 % by weight, B 2O 3Content is not more than 10 % by weight.
Be applicable to the glass fibre of embodiments more of the present invention or another example of glass fiber precursor and comprise glass composition, it comprises
SiO 2The 60-68 % by weight;
B 2O 3The 7-10 % by weight;
Al 2O 3The 9-15 % by weight;
MgO 8-15 % by weight;
CaO 0-4 % by weight;
Li 2O〉the 0-2 % by weight;
Na 2O 0-1 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-1 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions 0-5 % by weight;
Li wherein 2O content is greater than Na 2O content or greater than K 2O content.In some embodiments, select described one-tenth to assign to provide specific inductivity (D k) at 1MHz less than 6.7 glass.In other embodiments, select described one-tenth to assign to provide specific inductivity (D k) at 1MHz less than 6 glass.In other embodiments still, select described one-tenth to assign to provide specific inductivity (D k) at 1MHz less than 5.8 glass.In some embodiments, select described one-tenth to assign to provide specific inductivity (D k) at 1MHz less than 5.6 glass.
Be applicable to the glass fibre of embodiments more of the present invention or another example of glass fiber precursor and comprise glass composition, it comprises:
SiO 253.5-77 % by weight;
B 2O 34.5-14.5 % by weight;
Al 2O 34.5-18.5 % by weight;
MgO 4-12.5 % by weight;
CaO 0-10.5 % by weight;
Li 2O 0-4 % by weight;
Na 2O 0-2 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-2 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions are the 0-5 % by weight altogether.
Be applicable to the glass fibre of embodiments more of the present invention or another example of glass fiber precursor and comprise glass composition, it comprises:
SiO 2The 60-77 % by weight;
B 2O 34.5-14.5 % by weight;
Al 2O 34.5-18.5 % by weight;
MgO 8-12.5 % by weight;
CaO 0-4 % by weight;
Li 2O 0-3 % by weight;
Na 2O 0-2 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-2 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions are the 0-5 % by weight altogether.
Be applicable to the glass fibre of embodiments more of the present invention or another example of glass fiber precursor and comprise glass composition, it comprises:
SiO 2At least 60 % by weight;
B 2O 3The 5-11 % by weight;
Al 2O 3The 5-18 % by weight;
MgO 5-12 % by weight;
CaO 0-10 % by weight;
Li 2O 0-3 % by weight;
Na 2O 0-2 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-2 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions are the 0-5 % by weight altogether.
Be applicable to the glass fibre of embodiments more of the present invention or another example of glass fiber precursor and comprise glass composition, it comprises:
SiO 2The 60-68 % by weight;
B 2O 3The 5-10 % by weight;
Al 2O 3The 10-18 % by weight;
MgO 8-12 % by weight;
CaO 0-4 % by weight;
Li 2O 0-3 % by weight;
Na 2O 0-2 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-2 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions are the 0-5 % by weight altogether.
Be applicable to the glass fibre of embodiments more of the present invention or another example of glass fiber precursor and comprise glass composition, it comprises:
SiO 2The 62-68 % by weight;
B 2O 3The 7-9 % by weight;
Al 2O 3The 11-18 % by weight;
MgO 8-11 % by weight;
CaO 1-2 % by weight;
Li 2O 1-2 % by weight;
Na 2O 0-0.5 % by weight;
K 2O 0-0.5 % by weight;
Fe 2O 30-0.5 % by weight;
F 20.5-1 % by weight;
TiO 2The 0-1 % by weight; With
Other compositions are the 0-5 % by weight altogether.
Be applicable to the glass fibre of embodiments more of the present invention or another example of glass fiber precursor and comprise glass composition, it comprises:
SiO 2The 62-68 % by weight;
B 2O 3Less than about 9 % by weight;
Al 2O 3The 10-18 % by weight;
MgO 8-12 % by weight; With
CaO 0-4 % by weight;
Wherein this glass shows specific inductivity (D k) less than 6.7 and mold temperature (T F) be not more than 1370 ℃ in 1000 pool viscosity.
Be applicable to the glass fibre of embodiments more of the present invention or another example of glass fiber precursor and comprise glass composition, it comprises:
B 2O 3Less than 14 % by weight;
Al 2O 3The 9-15 % by weight;
MgO 8-15 % by weight;
CaO 0-4 % by weight; With
SiO 2The 60-68 % by weight;
Wherein this glass shows specific inductivity (D k) less than 6.7 and mold temperature (T F) be not more than 1370 ℃ when 1000 pool viscosity.
Be applicable to glass fibre in embodiments more of the present invention or another example of glass fiber precursor and comprise glass composition, it comprises:
B 2O 3Less than 9 % by weight;
Al 2O 3The 11-18 % by weight;
MgO 8-11 % by weight;
CaO 1-2 % by weight; With
SiO 2The 62-68 % by weight;
Wherein this glass shows specific inductivity (D k) less than 6.7 and mold temperature (T F) be not more than 1370 ℃ when 1000 pool viscosity.
Be applicable to the glass fibre of embodiments more of the present invention or another example of glass fiber precursor and comprise glass composition, it comprises:
SiO 2The 60-68 % by weight;
B 2O 3The 7-13 % by weight;
Al 2O 3The 9-15 % by weight;
MgO 8-15 % by weight;
CaO 0-3 % by weight;
Li 2O 0.4-2 % by weight;
Na 2O 0-1 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-1 % by weight; With
TiO 2The 0-2 % by weight;
Wherein this glass shows specific inductivity (D k) less than 5.9 and mold temperature (T F) be not more than 1300 ℃ when 1000 pool viscosity.
Be applicable to the glass fibre of embodiments more of the present invention or another example of glass fiber precursor and comprise glass composition, it comprises:
SiO 2The 60-68 % by weight;
B 2O 3The 7-11 % by weight;
Al 2O 3The 9-13 % by weight;
MgO 8-13 % by weight;
CaO 0-3 % by weight;
Li 2O 0.4-2 % by weight;
Na 2O 0-1 % by weight;
K 2O 0-1 % by weight;
(Na 2O+K 2O+Li 2O) 0-2 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-1 % by weight; With
TiO 2The 0-2 % by weight.
Except or replace above-mentioned feature of the present invention, the glass composition of embodiments more of the present invention can be used for providing dissipation factor (D f) lower than the glass of the electronics E-glass of routine.In some embodiments, D FCan be not more than 0.0150 when 1GHz, and be not more than 0.0100 in other embodiments when 1GHz.
In the glass composition of some embodiments, D FBe not more than 0.007 when 1GHz, and be not more than 0.003 in other embodiments when 1GHz, and be not more than 0.002 during at 1GHz in other embodiments still.
In some embodiments, can be used in the CaO that glass composition in glass fibre of the present invention or glass fiber precursor is characterised in that relative low levels, for example be in the magnitude of about 0-4 % by weight.In other embodiments still, CaO content can be in the magnitude of about 0-3 % by weight.In other embodiments still, CaO content can be in the magnitude of about 0-2 % by weight.Usually, make CaO content minimize the improvement that has produced electrical property, and CaO content has been reduced to low like this level in some embodiments, to such an extent as to the composition that it can be considered to choose wantonly.In some other embodiments, CaO content can be in the magnitude of about 1-2 % by weight.
On the other hand, the MgO content of such glass is relatively high, and wherein in some embodiments, MgO content is double (based on the % by weight) of CaO content.The MgO content of embodiments more of the present invention can be greater than about 5.0 % by weight, and MgO content can be greater than 8.0 % by weight in other embodiments.In some embodiments, composition is characterised in that MgO content for example is in the magnitude of about 8-13 % by weight.In other embodiments still, MgO content can be in the magnitude of about 9-12 % by weight.In some other embodiments, MgO content can be in the magnitude of about 8-12 % by weight.In some other embodiments still, MgO content can be in the magnitude of about 8-10 % by weight.
In some embodiments, the composition that can be used in glass fibre of the present invention or glass fiber precursor is characterised in that (MgO+CaO) content, and it is for example less than 16 % by weight.In other embodiments still, (MgO+CaO) content is less than 13 % by weight.In some other embodiments, (MgO+CaO) content is the 7-16 % by weight.In some other embodiments still, (MgO+CaO) content can be in the magnitude of about 10-13 % by weight.
In some other embodiments still, the feature of said composition can be (MgO+CaO)/(Li 2O+Na 2O+K 2O) content is than the magnitude that is in about 9.0.In certain embodiments, Li 2O/ (MgO+CaO) content is than the magnitude that can be in about 0-2.0.In some other embodiments still, Li 2O/ (MgO+CaO) content is than the magnitude that can be in about 1-2.0.In certain embodiments, Li 2O/ (MgO+CaO) content is than the magnitude that can be in about 1.0.
In some other embodiments, (SiO 2+ B 2O 3) content can be in the magnitude of 70-76 % by weight.In other embodiments still, (SiO 2+ B 2O 3) content can be in the magnitude of 70 % by weight.In other embodiments, (SiO 2+ B 2O 3) content can be in the magnitude of 73 % by weight.In other embodiments still, Al 2O 3% by weight and B 2O 3The ratio of % by weight be in the magnitude of 1-3.In some other embodiments, Al 2O 3% by weight and B 2O 3The ratio of % by weight be in the magnitude of 1.5-2.5.In certain embodiments, SiO 2Content is in the magnitude of 65-68 % by weight.
As mentioned above, some low D of prior art kComposition has the shortcoming that need to comprise a large amount of BaO, and is noted that does not need BaO in the glass composition of embodiments more of the present invention.Although the electricity that the present invention is favourable and manufacturing property are not got rid of the existence of BaO, lack another advantage that the BaO that has a mind to comprise can be considered to embodiments more of the present invention.Therefore, the feature of embodiment of the present invention can be to exist the BaO less than 1.0 % by weight.Only exist therein in those embodiments of impurity level of trace, BaO content can be characterized by and be not more than 0.05 % by weight.
The composition that can be used in glass fibre of the present invention or glass fiber precursor comprises such B 2O 3, (it relies on high B to its amount less than the scheme of prior art 2O 3Realize low D k).This has caused obvious cost savings.In some embodiments, B 2O 3Content need to be not more than 13 % by weight or be not more than 12 % by weight.Embodiments more of the present invention also fall into the ASTM definition of electronics E-glass,, are not more than the B of 10 % by weight that is 2O 3
In some embodiments, described composition is characterised in that B 2O 3Content for example is in the magnitude of about 5-11 % by weight.In some embodiments, B 2O 3Content can be the 6-11 % by weight.B 2O 3Content can be the 6-9 % by weight in some embodiments.In some embodiments, B 2O 3Content can be the 5-10 % by weight.In some other embodiments, B 2O 3Content is not more than 9 % by weight.In some other embodiments still, B 2O 3Content is not more than 8 % by weight.
In some embodiments, the composition that can be used in glass fibre of the present invention or glass fiber precursor is characterised in that Al 2O 3Content for example is in the magnitude of about 5-18 % by weight.Al 2O 3Content can be the 9-18 % by weight in some embodiments.In other embodiments still, Al 2O 3Content is the magnitude of about 10-18 % by weight.In some other embodiments, Al 2O 3Content is the magnitude of about 10-16 % by weight.In some other embodiments still, Al 2O 3Content is the magnitude of about 10-14 % by weight.In certain embodiments, Al 2O 3Content is the magnitude of about 11-14 % by weight.
In some embodiments, Li 2O is the composition of choosing wantonly.In some embodiments, described composition is characterised in that Li 2O content for example is in the magnitude of about 0.4-2.0 % by weight.In some embodiments, Li 2O content is greater than (Na 2O+K 2O) content.In some embodiments, (Li 2O+Na 2O+K 2O) content is not more than 2 % by weight.In some embodiments, (Li 2O+Na 2O+K 2O) content is in the magnitude of about 1-2 % by weight.
In certain embodiments, composition of the present invention is characterised in that TiO 2Content is for example the magnitude of about 0-1 % by weight.
In some embodiments of above-mentioned composition, described composition is proportional, produces the glass of the substandard E-glass of specific inductivity.With respect to being used for conventional electrical E-glass relatively, these can be less than about 6.7 in the 1MHz frequency.In other embodiments, specific inductivity (D k) can be less than 6 in the 1MHz frequency.In other embodiments, specific inductivity (D k) can be less than 5.8 in the 1MHz frequency.Other embodiments show specific inductivity (D k) in the 1MHz frequency less than 5.6 or even lower.In other embodiments, specific inductivity (D k) can be less than 5.4 in the 1MHz frequency.In other embodiments still, specific inductivity (D k) can be less than 5.2 in the 1MHz frequency.In other embodiments still, specific inductivity (D k) can be less than 5.0 in the 1MHz frequency.
Above-mentioned composition can also have the temperature-viscosity relationship of making us expecting of the business manufacturing of the reality that is of value to glass fibre.Compare with the composition of the D-type of glass of prior art, usually need lower temperature make fiber.This characteristic of making us expecting can be expressed in several ways, and they can by the composition of some embodiments described herein single or the combination obtain.For example, can make some glass composition that is in above-mentioned scope, it shows the mold temperature (T in 1000 pool viscosity F) be not more than 1370 ℃.The T of some embodiments FBe not more than 1320 ℃ or be not more than 1300 ℃ or be not more than 1290 ℃ or be not more than 1260 ℃ or be not more than 1250 ℃.These compositions can also comprise glass, therein mold temperature and liquidus temperature (T L) between difference be positive, and in some embodiments, mold temperature is higher 55 ℃ than liquidus temperature at least, this is conducive to come business to make fiber by these glass compositions.
Usually, the content of basic oxide that is used to form the glass composition of glass fibre or glass fiber precursor is minimized to help to reduce D kWhat expect therein is to optimize D kThose embodiments of reduction in, the content of total alkaline oxide compound can be not more than 2 % by weight of glass composition.In some embodiments, have been found that in this, with Na 2O and K 2O minimizes and compares Li 2O is more effective.The existence of basic oxide causes having reduced mold temperature usually.So, in wherein preferential those embodiments that are to provide relatively low mold temperature of the present invention, included Li 2O obviously measures, for example at least 0.4 % by weight.For this purpose, in some embodiments, Li 2O content is greater than Na 2O or greater than K 2O content, and in other embodiments, Li 2O content is greater than Na 2O and K 2O content sum in some embodiments, has gone out greatly twice or many times.
In some embodiments, favourable aspect is to rely on composition conventional in fiber glass industry, and avoids the very expensive composition of raw material source of a large amount of it.For this aspect, can comprise except clearly provide in the definition of the composition of glass of the present invention those composition (even they are optional), but total amount otherwise greater than 5 % by weight.These optional compositions comprise melting auxiliary agent, finings, tinting material, trace impurity and glass manufacturing area other additives known to the skilled.Low D with respect to some prior aries kGlass, BaO is optional in composition of the present invention, can not comprise a small amount of BaO (for example high to about 1 % by weight) but do not get rid of.Equally, a large amount of ZnO is optional in the present invention, but also can comprise in some embodiments a small amount of (for example high to about 2.0 % by weight).In minimum those embodiments of the present invention of optional composition, optional composition total amount is not more than 2 % by weight or is not more than 1 % by weight therein.Selectable, embodiments more of the present invention can it is said and basically are grouped into by described one-tenth.
The selection of batch composition and their cost depends primarily on their purity requirement.The typical commercially available composition composition of E-glass (for example for the manufacture of) comprises the Na that is in the different chemical form 2O, K 2O, Fe 2O 3Perhaps FeO, SrO, F 2, TiO 2, SO 3Deng impurity.From most of positively charged ion of these impurity will by with glass in SiO 2And/or B 2O 3Form non-bridged property oxygen, and improve the D of glass k
Vitriol (is expressed as SO 3) also can be used as refining agent and exist.A small amount of impurity also can or come from pollutent in the melt-processed process from starting material, for example SrO, BaO, Cl 2, P 2O 5, Cr 2O 3Perhaps NiO (being not limited to these concrete chemical form).Also can there be for example As in other refining agents and/or processing aid 2O 3, MnO, MnO 2, Sb 2O 3Perhaps SnO 2(being not limited to these concrete chemical form).These impurity and refining agent when existing each typical amount less than 0.5 % by weight of total glass composition.Choose wantonly, the element of the rare earth element family of the periodic table of elements can join composition of the present invention, comprises atomicity 21 (Sc), 39 (Y) and 57 (La)-71 (Lu).They can serve as processing aid or for improvement of electricity, physics (calorifics and optics), machinery and the chemical property of glass.This rare earth addition can comprise with initial chemical species and oxidation state.Add rare earth element to be considered to choose wantonly, particularly of the present invention all the more so in having those embodiments that make raw-material minimizing costs target, this is because they will improve job costs, is also even like this when lower concentration.In any situation, their cost typically will be stipulated rare earth component (measuring as oxide compound) when comprising, its amount is not more than about 0.1-1.0 % by weight of total glass composition.
Glass fibre, glass fiber precursor and other products that mixed such fiber or precursor can show the mechanical property of making us expecting in some embodiments of the present invention, particularly with the E-glass fibre, all the more so when the glass fiber precursor that formed by E-glass is compared with related products.For example particularly when comparing with the E-glass fibre, the glass fibre of embodiments more of the present invention can have relatively high specific tenacity or relatively high specific modulus.Specific tenacity refers to tensile strength (N/m 2) divided by weight/power ratio (N/m 3).Specific modulus refers to Young's modulus (N/m 2) divided by weight/power ratio (N/m 3).Expectation therein improves mechanical property or product performance, reduces simultaneously in the application of overall weight of matrix material, is desirable to the glass fibre with relatively high specific tenacity and/or relatively high specific modulus.The example of such matrix material is illustrated in the above, and for example comprises that aerospace or aerospace applications (for example interior of aircraft floor), wind energy use that (for example air vane), fiber-metal level is fit to be used and other.Another one example as mechanical property, the glass fiber precursor of the rove form of embodiments more of the present invention can show the tensile strength (for example be in some embodiments according to ASTM D2343 is the magnitude of 400-430ksi) of raising, and this forms contrast with the rove (for example be according to ASTM D2343 is the magnitude of 350-400ksi) that is mixed with E-glass glass fiber precursor.
As known in the art, after formation, glass fibre typically is coated with glueing composition at least in part.Usually, the glass fibre that is used to form glass fiber precursor of the present invention, fabric, matrix material, laminate and prepreg will be coated with glueing composition at least in part.Those skilled in the art can select a kind of for glass fibre in many commercially available glueing compositions, described factor to comprise flexible, cost and other factors of use properties, the expectation of formed fabric of glueing composition for example based on many factors.The example that can be used in the commercially available glueing composition indefiniteness in embodiments more of the present invention comprises through being usually used in the glueing composition of single-ended rove, for example Hybon2026, Hybon2002, Hybon1383, Hybon2006, Hybon2022, Hybon2032, Hybon2016 and Hybon1062, and through being usually used in the glueing composition on yarn, for example 1383,611,900,610,695 and 690, its each refer to for the city and be sold by PPG Industries, the glueing composition of the product of Inc..
As mentioned above, embodiments more of the present invention can comprise fabric.Can use well known by persons skilled in the art for strengthening any suitable Fabric Design of using.Suitable fabric can comprise the fabric that uses conventional Weaving device (for example thorn is penetrated (rapier), emission or air spray loom) to produce.The example of such fabric indefiniteness comprises that plain weave, twill, reticulate pattern and satin knit.Loop bonding or non-crimping fabric also can be used for embodiments more of the present invention.Such fabric can comprise for example unidirectional, two-way and non-crimping fabric three-dimensional.In addition, the 3D woven fabric also can be used for embodiments more of the present invention.Such fabric can be produced with multilayer warp warp beam, has race, uses dobbies or jacquard weave head.
As mentioned above, matrix material of the present invention can comprise warp and parallel yarn.Can use well known by persons skilled in the art for strengthening any suitable warp and the parallel yarn of using.In some embodiments, for example warp thread can comprise G75 yarn, DE75 yarn, DE150 yarn and/or G150 yarn.
As mentioned above, matrix material of the present invention can comprise fluoropolymer resin, in some embodiments.Can use the multiple polymers resin.The known fluoropolymer resin that can be used in the enhancing application can be useful especially in some embodiments.In some embodiments, this fluoropolymer resin can comprise thermosetting resin.Useful aathermoset resin system can include but not limited to epoxy-resin systems, phenol resin, polyester in some embodiments of the present invention, vinyl ester, heat-curable urethane, poly-Dicyclopentadiene (DCPD) (pDCPD) resin, cyanate and bismaleimides.In some embodiments, this fluoropolymer resin can comprise epoxy resin.In other embodiments, this fluoropolymer resin can comprise thermoplastic resin.Useful thermoplastic polymer includes but not limited to polyethylene in some embodiments of the present invention, polypropylene, polymeric amide (comprising nylon), polybutylene terephthalate, polycarbonate, thermoplastic polyurethane (TPU), polyphenylene sulfide and polyether-ether-ketone (PEEK).The example of useful commercial polymer resin indefiniteness comprises the EPIKOTE resin with Epikure MGS RIMH1366 solidifying agent in some embodiments of the present invention
Figure BDA00003039525600441
RIMR135 epoxy (available from Ohio Columbian Momentive Specialty Chemicals Inc.), Applied Poleramic MMFCS2 epoxy is (available from the Applied Poleramic of California Benicia, Inc.), with the EP255 modified epoxy (available from Barrday Composite Solutions, Millbury, MA).
Embodiment
Explanation exemplary more of the present invention in concrete, indefiniteness embodiment that now will be below.
Embodiment 1
Some performances of useful glass composition are to measure with conventionally test method well known by persons skilled in the art under controlled processing conditions in some embodiments of the present invention.The performance of some measurements is listed in table 1.Comprised the performance of the E-glass of standard and commercially available NE-glass as a reference.The performance of listed commercially available NE-glass comes from document.Data presentation in table 1 and E-glassy phase ratio are applicable to glass fibre of the present invention and show improved heat, chemistry and mechanical stability.With NE-Fiber Phase ratio, be applicable to glass fibre of the present invention and be 30% stronger and 25% harder.As measured by the x ray fluorescence spectra, the glass fibre of the sample 1 of table 1 comprises the glass composition that contains following component:
SiO 263.02 ± 0.25 % by weight;
B 2O 39.39 ± 0.15 % by weight;
Al 2O 311.60 ± 0.10 % by weight;
MgO 11.06 ± 0.15 % by weight;
CaO 2.54 ± 0.10 % by weight;
Na 2O 0.38 ± 0.02 % by weight;
K 2O 0.12 ± 0.01 % by weight;
Fe 2O 30.25 ± 0.05 % by weight;
F 20.72 ± 0.15 % by weight;
TiO 20.10 ± 0.01 % by weight;
Li 2O 0.81 ± 0.05; With
SO 30.02 % by weight.
Table 1. is applicable to the performance of glass composition of embodiments more of the present invention and the comparison of other glass combination physical performances.
Figure BDA00003039525600451
Embodiment 2
In this embodiment, will load and be compared by the made yarn of the 621 formed glass fiber precursors of glass composition of routine (" 621 yarn ") by the yarn breakage of the formed yarn of glass fiber precursor of the present invention (" sample yarn ").Each yarn is that single glass fiber precursor (having about 200 filaments, 7 microns of nominal diameters) forms.After formation, this glass fibre is applied with conventional starch-oily glueing composition.This glass fiber precursor is dry, and then twisting 1 circle/inch forms this yarn on the z direction, and then with its woven one-tenth plain weave style fabric, it has 60 parallel/inches and have 58 parallel/inches on weft direction on warp direction.
Then measure the breaking load of this fabric with ASTM5053.At 1 inch wide, install the paper label on 6 inches long fabric strips, and load on the universal test framework with the speed of 12 inch per minute clocks, until lost efficacy.Each fabric is carried out 12 breaking load measurements altogether.Average breaking load by the thread fabric strip of sample yarn is 197.5lb f, and are 181.7lb by the average breaking load of the 621 thread fabric strips of yarn fThen this fabric is come thermal cleaning and finishing with identical routine techniques.After thermal cleaning and finishing, use ASTM5035 again to measure the breaking load of fabric strip.12 breaking load measurements have altogether been carried out.The average breaking load of sample fabric is 119.5lb f, and the average breaking load of 621 fabrics is 85.1lb fThe breaking load retentivity of 621 fabrics (breaking load after thermal cleaning/finishing is divided by the breaking load X100 before the thermal cleaning finishing) is 46.8%.The breaking load retentivity of sample fabric (breaking load after thermal cleaning/finishing is divided by the breaking load before the thermal cleaning finishing) is 60.5%, and this has confirmed that the improvement in breaking load is better than 621 fabrics.
Embodiment 3
The stretching of laminate of the present invention and impact property and those laminaties of being made by the glass fibre that contains conventional glass composition are compared.In this embodiment, fabric is to use warp thread and the weft yarn made by the glass fiber precursor with glass composition of the present invention to come woven (" sample fabric ").The fabric of contrast is (" the E-glass fabric ") that the E-Glass yarn by standard forms.Be provided in table 2 about the other details of this fabric:
Table 2
? Sample fabric The E-glass fabric
Fabric pattern 7781 7781
Finishing 1383 497-A
Weaving pattern 8HS 8HS
The warp thread size DE79 DE75
The weft yarn size DE79 DE75
Counting 57x61 57x54
Basic weight 8.68oz/yd 2 8.73oz/yd 2
Thickness 0.008” 0.009”
Roller length 60yd 100yd
Then use the compression molded fabric with this preimpregnation of vacuum aided to be incorporated in laminate.Fluoropolymer resin used is from Barrday Composite Solutions, Millbury, the epoxy resin of the EP255 modification of MA.10 tissue layer are incorporated in each laminate.The processing conditions of table 3 is used for the compression molded device of this vacuum aided:
Table 3
Die temperature 255°F
The molded time 90 minutes
Die pressure 70psi
The abundant curing of resin is (the sample layer zoarium is 115.03 ℃, and E-glass coating zoarium is 116.57 ℃) verified by the second-order transition temperature (Tg) of measuring matrix material.The fiber weight fraction of sample layer zoarium is 65.72% glass, and the fiber weight fraction of E-glass coating zoarium is 67.39% glass.
The tensile property of laminate is measured according to ISO527-4.5 sample layers zoariums and 5 E-glass coatings have been analyzed fit.The initial evaluation data show that the average tension strain failure ratio E-glass coating zoarium of sample layer zoarium improves (2.15% pair 1.95%) a little.The tensile strength that also shows the sample layer zoarium is slightly high slightly low with tensile modulus.But, carrying out variance analysis (ANOVA) afterwards, it is significantly upper that these trend are not considered to statistics.
Also according to ASTM3763, using 3/8 on the sample of equal thickness " the Impact Test machine of hemisphere knocker and instrumentation measured the impact property of this laminate.It is visibly different observing this sample layer impact property fit and E-glass coating zoarium.In whole situations, this sample layer zoarium has produced the obvious raising of impact property, and this shows as the high-energy at busy hour, and by the total energy of absorption of sample.The average energy of the maximum load of sample layer zoarium is 30.984 joules, and E-glass coating zoarium is 14.204 joules.The average absorption total energy of sample layer zoarium is 35.34 joules, and E-glass coating zoarium is 26.76 joules.Therefore, when being subject to identical impact velocity, the fit average specific E-of sample layer glass coating zoarium has absorbed 32% energy more.In addition, this sample layer zoarium shows much smaller than the damage of E-glass coating zoarium, and does not permeate.
Embodiment 4
The glass of this embodiment is by mixture melting in the 10%Rh/Pt crucible of 1500 ° of C-1550 ° of C (2732 °F-2822 °F) temperature of the chemical of the reaction reagent grade of powder type was made in 4 hours.Each batch is about 1200g.After the melting phase of 4 hours, the glass of this melting is poured into for the steel plate that quenches.In order to compensate B 2O 3Volatilization loss (in batch melting condition of laboratory, for batch scale of 1200g, typically lost general objective B 2O 3Concentration about 5%), the boron retention factors in charge calculation is set in 95%.Do not adjust other volatile matter for example fluorochemical and their emission loss of basic oxide in batch material, this is lower concentration in glass because of them.Composition in embodiment has represented class sets of batches compound.Because the reagent chemical is used to prepare the B with abundant adjustment 2O 3Glass, the class sets of batches compound shown in therefore is considered to close to measured composition.
Melt viscosity as the function of temperature and liquidus temperature uses respectively ASTM testing 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 " to measure.
The polishing disk of the glass sample of each 40mm diameter and 1-1.5mm thickness is used for electrical property and mechanical property is measured, it is made by annealed glass.Specific inductivity (the D of each glass k) and dissipation factor (D f) be from 1MHz to 1GHz, measure by ASTM testing method D150 " Standard Test Methods for A-C Loss Characteristics and Permittivity (Dielectric Constant) of Solid Electrical Insulating Materials ".According to this program, at 25 ℃, preconditioning is 40 hours under 50% humidity with whole samples.Use ASTM testing method C729 " Standard Test Method for Density of Glass by the Sink-Float Comparator ", glass density has been carried out selectivity test, for this test, all sample is all annealed.
For the selectivity composition, measured Young's modulus (in the not duty cycle of marking press with the micro-indentations method, and microhardness (from maximum impression load and maximum depth of indentation) curve initial slope from impression load-depth of indentation).For this test, used identical disk sample, its after tested D kAnd D fCarry out 5 impression measurements and obtained average Young's modulus and microhardness data.This micro-indentations equipment is to proofread and correct with reference to glass block with the commercial criterion that name of product is BK7.This Young's modulus with reference to glass is that 90.1GPa (standard deviation is 0.26GPa) and microhardness are 4.1GPa (standard deviation are 0.02GPa), and it is all based on 5 measurements.
Component values whole in embodiment represent with % by weight.In following table, " E " refers to Young's modulus; " H " refers to microhardness; σ fRefer to filament intensity; " Std " refers to standard deviation.
Table 4 composition
Sample 1-8 provides glass composition (table 4), and unit is weight %:SiO 262.5-67.5%, B 2O 38.4-9.4%, Al 2O 310.3-16.0%, MgO6.5-11.1%, CaO1.5-5.2%, Li 2O1.0%, Na 2O0.0%, K 2O0.8%, Fe 2O 30.2-0.8%, F 20.0%, TiO 20.0% and vitriol (be expressed as SO 3) 0.0%.
Have been found that described glass D when the 1MHz frequency kThat 5.44-5.67 and Df are 0.0006-0.0031, and when the 1GHz frequency D k5.47-6.67 and D f0.0048-0.0077.Electrical property at composition described in III series shows as the E-glass D that is starkly lower than (that is, improved) standard kAnd D f, the D of this standard E-glass when 1MHz k7.29 and D f0.003, and when 1GHz D k7.14 and D f0.0168.
At the fiberizing aspect of performance, the mold temperature (T of the composition of table 4 F) be 1300-1372 ℃ and moulding window (T F-T L) be 89-222 ℃.This can with E-glass (its T of standard FBe typically 1170-1215 ℃) quite.In order to be placed on glass devitrification in fiberizing, greater than the moulding window (T of 55 ℃ F-T L) make us expecting.In table 4, whole compositions table reveals gratifying moulding window.Although the composition of table 4 has the mold temperature higher than E-glass, they have the mold temperature that is starkly lower than D-glass (typical about 1410 ℃).
Table 4. is useful some glass compositions in some embodiments of the present invention.
Figure BDA00003039525600501
Figure BDA00003039525600511
Table 5 composition
Sample 9-15 provide glass composition: SiO 260.8-68.0%, B 2O 38.6 with 11.0%, Al 2O 38.7-12.2%, MgO9.5-12.5%, CaO1.0-3.0%, Li 2O0.5-1.5%, Na 2O0.5%, K 2O0.8%, Fe 2O 30.4%, F 20.3%, TiO 20.2% and vitriol (be expressed as SO 3) 0.0%.
Have been found that described glass D when the 1MHz frequency kThat 5.55-5.95 and Df are 0.0002-0.0013, and when the 1GHz frequency D k5.54-5.94 and D f0.0040-0.0058.In table 5, the electrical property of composition shows as E-glass (that is, the improved) D of the standard of being starkly lower than kAnd D f, the D of this standard E-glass when 1MHz k7.29 and D f0.003, and when 1GHz D k7.14 and D f0.0168.
In mechanical properties, the Young's modulus of the composition of table 5 is that 86.5-91.5GPa and microhardness are 4.0-4.2GPa, both all equal or higher than the Young's modulus of the composition of conventional E glass (its Young's modulus is that 85.9GPa and microhardness are 3.8GPa) table 5 also apparently higher than D-glass (it is about 55GPa based on data in literature).
At the fiberizing aspect of performance, the mold temperature (T of the composition of table 5 F) be 1224-1365 ℃ and moulding window (T F-T L) be 6-105 ℃, by comparison, the T of standard E-glass FScope is at 1170-1215 ℃.Some but the composition of not all table 5 has the moulding window (T greater than 55 ℃ F-T L), in this some situation in the commercial fibres forming operation for avoiding devitrification to be regarded as preferably.The composition of table 5 has low but higher than the E-glass mold temperature of mold temperature (1410 ℃) than D-glass.
Table 5. is useful some glass compositions in some embodiments of the present invention.
Figure BDA00003039525600521
Table 6. is useful some glass compositions in some embodiments of the present invention.
Sample: 16 17 18 19 20
Al 2O 3 10.37 11.58 8.41 11.58 12.05
B 2O 3 8.71 10.93 10.66 8.98 8.69
CaO 2.01 2.63 3.02 1.78 2.12
F 2 0.32 0.30 0.30 0.30 0.30
Fe 2O 3 0.40 0.27 0.27 0.27 0.27
K 2O 0.79 0.25 0.25 0.16 0.10
Li 2O 0.50 1.21 1.53 0.59 1.40
MgO 11.06 10.04 9.65 11.65 10.57
Na 2O 0.52 0.25 0.57 0.35 0.15
SiO 2 65.13 62.55 65.35 64.35 64.35
TiO 2 0.20 0.00 0.00 0.00 0.00
Amount to 100.00 100.00 100.00 100.00 100.00
D k，1MHz 5.43 5.57 ? 5.30 5.42
D k，1GHz 5.33 5.48 ? 5.22 5.33
D f，1MHz 0.0057 0.0033 ? 0.0031 0.0051
D f，1GHz 0.0003 0.0001 ? 0.0008 0.0014
T L(℃) 1231 1161 1196 1254 1193
T F(℃) 1327 1262 1254 1312 1299
T F-T L(℃) 96 101 58 58 106
T M(℃) 1703 1592 1641 1634 1633
E(GPa) 85.3 86.1 85.7 91.8 89.5
Std?E(GPa) 0.4 0.6 2.5 1.7 1.5
H(GPa) 3.99 4.00 4.03 4.22 4.13
Std?H(GPa) 0.01 0.02 0.09 0.08 0.05
Table 6 (continuing).
Table 7. is useful some glass compositions in some embodiments of the present invention.
Sample: 27 28 E-glass
Al 2O 3 12.42 12.57 13.98
B 2O 3 9.59 8.59 5.91
CaO 0.11 0.10 22.95
F 2 0.35 0.26 0.71
Fe 2O 3 0.21 0.21 0.36
K 2O 0.18 0.18 0.11
Li 2O 0.80 1.01 0
MgO 10.25 10.41 0.74
Na 2O 0.15 0.18 0.89
SiO 2 65.47 65.96 54.15
TiO 2 0.17 0.17 0.07
D k，1MHz 5.3 5.4 7.3
D k，1GHz 5.3 5.4 7.1
D f，1MHz 0.003 0.008 ?
D f，1GHz 0.011 0.012 0.0168
T L(℃) 1184 1201 1079
T F(℃) 1269 1282 1173
TF-TL(℃) 85 81 94
E(GPa) ? ? ?
H(GPa) 3.195 3.694 ?
Sample 29-62 provides glass composition (table 8), % by weight: SiO 253.74-76.97%, B 2O 34.47-14.28%, Al 2O 34.63-15.44%, MgO4.20-12.16%, CaO1.04-10.15%, Li 2O0.0-3.2%, Na 2O0.0-1.61%, K 2O0.01-0.05%, Fe 2O 30.06-0.35%, F 20.49-1.48%, TiO 20.05-0.65% and vitriol (are expressed as SO 3) 0.0-0.16%.
Sample 29-62 provides glass composition (table 8), % by weight, and wherein (MgO+CaO) content is 7.81-16.00%, the CaO/MgO ratio is 0.09-1.74%, (SiO 2+ B 2O 3) content is 67.68-81.44%, Al 2O 3/ B 2O 3Ratio is 0.90-1.71%, (Li 2O+Na 2O+K 2O) content is 0.03-3.38%, and Li 2O/ (Li 2O+Na 2O+K 2O) ratio is 0.00-0.95%.
In mechanical properties, the fibre density of the composition of table 8 is 2.331-2.416g/cm 3And average fiber tensile strength (perhaps fibre strength) is 3050-3578MPa.
In order to measure tensile strength of fiber, produce from 10Rh/90Pt unicuspid fiber draw unit from the fiber sample of glass composition.The glass cullet of the given composition of about 85g are supplied in the axle bush melting plant, and in the temperature regulation 2 hours that approaches or equal 100 pool melt viscosities.This melt is reduced to the temperature that approaches or equal 1000 pool melt viscosities subsequently, and stablizes before tensile fiber 1 hour.Control by the speed of controlling the tensile fiber spooler diameter fibers that Fibre diameter is produced about 10 μ m.All fiber sample is captured in air, and does not contact with any of exterior object.Tensile fiber is to complete in the room of the humidity RH that is controlled at 40-45%.
Tensile strength of fiber is to use Kawabata KES-G1 (Ka-Tech Co.Ltd., Japan) the Analysis of tensile strength instrument that is equipped with Kawabata type C load cell to measure.Using resin adhesive that fiber sample is installed to paper becomes on frame bar.Drawing force is applied on fiber until inefficacy is measured fibre strength based on Fibre diameter and rupture stress thus.This test is to carry out under the controlled humidity of the RH of room temperature and 40-45%.For each composition, come calculating mean value and standard deviation based on the sample size of 65-72 fiber.
Have been found that the D at the described glass of 1GHz k4.83-5.67 and D f0.003-0.007.In table 8, the electrical property of composition shows as the E-glass D that is starkly lower than (that is, improved) standard kAnd D f, this standard E-glass D when 1GHz k7.14 and D f0.0168.
At the fiberizing aspect of performance, the mold temperature (T of the composition of table 8 F) be 1247-1439 ℃ and moulding window (T F-T L) be 53-243 ℃.Liquidus temperature (the T of the composition of table 8 L) be 1058-1279 ° of C.This can with E-glass (its T of standard FBe typically 1170-1215 ℃) quite.In order to prevent glass devitrification in fiberizing, sometimes expectation be moulding window (T greater than 55 ℃ F-T L).In table 8, whole compositions table reveals gratifying moulding window.
Table 8. is useful some glass compositions in some embodiments of the present invention.
wt% 29 30 31 32 33
SiO 2 64.24 58.62 57.83 61.00 61.56
Al 2O 3 11.54 12.90 12.86 12.87 12.82
Fe 2O 3 0.28 0.33 0.33 0.33 0.32
CaO 1.70 1.04 2.48 2.48 1.08
MgO 11.69 11.63 12.16 9.31 10.69
Na 2O 0.01 0.00 0.00 0.00 0.00
K 2O 0.03 0.03 0.03 0.03 0.03
B 2O 3 8.96 14.28 13.15 12.81 12.30
F 2 0.53 0.62 0.61 0.61 0.65
TiO 2 0.40 0.54 0.54 0.54 0.54
Li 2O 0.60 0.00 0.00 0.00 0.00
SO 3 0.01 0.01 0.01 0.01 0.01
Amount to 100.00 100.00 100.00 100.00 100.00
? ? ? ? ? ?
(MgO+CaO) 13.39 12.67 14.64 11.79 11.77
CaO/Mg 0.15 0.09 0.20 0.27 0.10
MgO/(MgO+CaO) 0.87 0.92 0.83 0.79 0.91
SiO 2+B 2O 3 73.20 72.90 70.98 73.81 73.86
Al 2O 3/B 2O 3 1.29 0.90 0.98 1.00 1.04
(Li 2O+Na 2O+K 2O) 0.64 0.03 0.03 0.03 0.03
Li 2O/(Li 2O+Na 2O+K 2O) 0.94 0.00 0.00 0.00 0.00
? ? ? ? ? ?
T L(°C) 1196 1228 1205 1180 1249
T F(°C) 1331 1300 1258 1334 1332
T F-T L(°C) 135 72 53 154 83
D k@1GHz 5.26 *** *** 5.30 ***
D f@1GHz 0.0017 *** *** 0.001 ***
? ? ? ? ? ?
Fibre density (g/cm 3) *** *** *** *** ***
Fibre strength (MPa) *** *** *** *** ***
Table 8 (continuing)
wt% 34 35 36 37 38
SiO 2 63.83 65.21 66.70 60.02 53.74
Al 2O 3 10.97 10.56 10.11 12.32 15.44
Fe 2O 3 0.26 0.25 0.24 0.29 0.24
CaO 2.38 2.29 2.19 4.01 3.83
MgO 10.64 10.23 9.79 9.95 10.53
Na 2O 0.29 0.28 0.27 0.33 0.09
K 2O 0.03 0.03 0.03 0.03 0.03
B 2O 3 9.32 8.96 8.57 10.48 13.94
F 2 1.20 1.16 1.11 1.35 1.48
TiO 2 0.36 0.35 0.33 0.41 0.65
Li 2O 0.70 0.67 0.64 0.79 0.02
SO 3 0.14 0.14 0.13 0.16 0.14
Amount to 100.13 100.13 100.12 100.15 100.13
? ? ? ? ? ?
(MgO+CaO) 13.02 12.52 11.98 13.96 14.36
CaO/MgO 0.22 0.22 0.22 0.40 0.36
MgO/(MgO+CaO) 0.82 0.82 0.82 0.71 0.73
SiO 2+B 2O 3 73.15 74.17 75.27 70.50 67.68
Al 2O 3/B 2O 3 1.18 1.18 1.18 1.18 1.11
(Li 2O+Na 2O+K 2O) 1.02 0.98 0.94 1.15 0.14
Li 2O/(Li 2O+Na 2O+K 2O) 0.69 0.68 0.68 0.69 0.16
? ? ? ? ? ?
T L(°C) 1255 1267 1279 1058 1175
T F(°C) 1313 1320 1333 1266 1247
T F-T L(°C) 58 53 54 208 72
D k@1GHz *** 5.46 5.43 5.56 5.57
D f@1GHz *** 0.0036 0.0020 0.0025 0.00437
? ? ? ? ? ?
Fibre density (g/cm 3) 2.402 2.408 2.352 2.416 ***
Fibre strength (MPa) 3310 3354 3369 3413 ***
Table 8 (continuing)
wt% 39 40 41 42 43
SiO 2 62.54 63.83 65.21 66.70 59.60
Al 2O 3 11.36 10.97 10.56 10.11 13.52
Fe 2O 3 0.27 0.26 0.25 0.24 0.33
CaO 2.47 2.38 2.29 2.19 1.80
MgO 11.02 10.64 10.23 9.79 9.77
Na 2O 0.31 0.29 0.28 0.27 0.10
K 2O 0.03 0.03 0.03 0.03 0.03
B 2O 3 9.65 9.32 8.96 8.57 12.70
F 2 1.25 1.20 1.16 1.11 1.21
TiO 2 0.37 0.36 0.35 0.33 0.51
Li 2O 0.73 0.70 0.67 0.64 0.41
SO 3 0.15 0.14 0.14 0.13 0.15
Amount to 100.14 100.13 100.13 100.12 100.14
? ? ? ? ? ?
(MgO+CaO) 13.49 13.02 12.52 11.98 11.57
CaO/MgO 0.22 0.22 0.22 0.22 0.18
MgO/(MgO+CaO) 0.82 0.82 0.82 0.82 0.84
SiO 2+B 2O 3 72.19 73.15 74.17 75.27 72.30
Al 2O 3/B 2O 3 1.18 1.18 1.18 1.18 1.06
(Li 2O+Na 2O+K 2O) 1.07 1.02 0.98 0.94 0.54
Li 2O/(Li 2O+Na 2O+K 2O) 0.68 0.69 0.68 0.68 0.76
? ? ? ? ? ?
T L(°C) 1238 1249 1266 1276 1083
T F(°C) 1293 1313 1342 1368 1310
T F-T L(°C) 55 64 76 92 227
D k@1GHz 5.45 5.31 5.39 5.25 5.20
D f@1GHz 0.00531 0.00579 0.00525 0.00491 0.00302
? ? ? ? ? ?
Fibre density (g/cm 3) 2.403 *** *** *** ***
Fibre strength (MPa) 3467 *** *** *** ***
Table 8 (continuing)
wt% 44 45 46 47 48
SiO 2 59.90 60.45 62.68 65.30 65.06
Al 2O 3 13.23 13.06 12.28 11.51 12.58
Fe 2O 3 0.34 0.35 0.20 0.19 0.25
CaO 1.86 1.58 1.65 1.39 1.25
MgO 10.14 10.50 8.74 8.18 6.56
Na 2O 0.10 0.10 0.10 0.09 0.13
K 2O 0.03 0.03 0.02 0.02 0.05
B 2O 3 12.40 12.29 12.69 11.89 10.03
F 2 1.26 1.07 1.11 0.94 0.82
TiO 2 0.53 0.55 0.51 0.48 0.07
Li 2O 0.20 0.00 0.00 0.00 3.20
SO 3 0.15 0.16 0.15 0.14 0.11
Amount to 100.14 100.15 100.14 100.13 100.10
? ? ? ? ? ?
RO(MgO+CaO) 12.00 12.08 10.39 9.57 7.81
CaO/Mg 0.18 0.15 0.19 0.17 0.19
MgO/(MgO+CaO) 0.85 0.87 0.84 0.85 0.84
SiO 2+B 2O 3 72.30 72.74 75.37 77.19 75.09
Al 2O 3/B 2O 3 1.07 1.06 0.97 0.97 1.25
(Li 2O+Na 2O+K 2O) 0.33 0.13 0.12 0.11 3.38
Li 2O/(Li 2O+Na 2O+K 2O) 0.61 0.00 0.00 0.00 0.95
? ? ? ? ? ?
T L(°C) 1129 1211 1201 1196 ***
T F(°C) 1303 1378 1378 1439 ***
T F-T L(°C) 174 167 177 243 ***
Dk@1GHz 5.24 5.05 4.94 4.83 5.67
Df@1GHz 0.00473 0.00449 0.00508 0.00254 0.007
? ? ? ? ? ?
Fibre density (g/cm 3) 2.387 2.385 2.354 2.34 2.345
Fibre strength (MPa) 3483 3362 3166 3050 3578
Table 8 (continuing)
wt% 49 50 51 52 53
SiO 2 61.14 60.83 62.45 61.88 66.25
Al 2O 3 12.90 13.02 12.52 12.72 10.60
Fe 2O 3 0.27 0.28 0.26 0.28 0.18
CaO 1.72 1.74 1.59 1.63 3.33
MgO 9.25 9.36 8.98 9.13 5.98
Na 2O 0.10 0.10 0.10 0.10 0.86
K 2O 0.03 0.03 0.03 0.03 0.02
B 2O 3 12.70 12.70 12.29 12.38 11.44
F 2 1.16 1.17 1.08 1.10 0.90
TiO 2 0.51 0.51 0.50 0.50 0.44
Li 2O 0.21 0.25 0.21 0.25 0.00
SO 3 0.15 0.15 0.14 0.14 0.00
Amount to 100.14 100.14 100.13 100.13 100.00
? ? ? ? ? ?
(MgO+CaO) 10.97 11.10 10.57 10.76 9.31
CaO/Mg 0.19 0.19 0.18 0.18 0.56
MgO/(MgO+CaO) 0.84 0.84 0.85 0.85 0.64
SiO 2+B 2O 3 73.84 73.53 74.74 74.26 77.69
Al 2O 3/B 2O 3 1.02 1.03 1.02 1.03 0.93
(Li 2O+Na 2O+K 2O) 0.34 0.38 0.34 0.38 0.88
Li 2O/(Li 2O+Na 2O+K 2O) 0.62 0.66 0.62 0.66 0.00
? ? ? ? ? ?
T L(°C) 1179 1179 1186 1191 ***
T F(°C) 1342 1340 1374 1366 ***
T F-T L(°C) 163 161 188 175 ***
D k@1GHz *** 5.24 4.96 5.06 5.03
D f@1GHz *** 0.0018 0.0015 0.0014 0.0027
? ? ? ? ? ?
Fibre density (g/cm 3) 2.358 2.362 2.338 *** 2.331
Fibre strength (MPa) 3545 3530 3234 *** 3161
Table 8 (continuing)
wt% 54 55 56 57 58
SiO 2 66.11 69.19 70.68 69.44 69.40
Al 2O 3 10.58 10.37 8.87 7.20 7.21
Fe 2O 3 0.18 0.18 0.16 0.13 0.14
CaO 5.31 5.20 5.50 5.57 10.15
MgO 4.20 7.13 7.54 10.39 5.85
Na 2O 0.86 0.55 0.59 0.59 0.59
K 2O 0.02 0.02 0.02 0.02 0.02
B 2O 3 11.41 6.39 5.72 5.80 5.79
F 2 0.90 0.53 0.55 0.55 0.55
TiO 2 0.44 0.43 0.37 0.30 0.30
Li 2O 0.00 0.00 0.00 0.00 0.00
SO 3 0.00 0.00 0.00 0.00 0.00
Amount to 100.00 100.00 100.00 100.00 100.00
? ? ? ? ? ?
(MgO+CaO) 9.51 12.33 13.04 15.96 16.00
CaO/Mg 1.26 0.73 0.73 0.54 1.74
MgO/(MgO+CaO) 0.44 0.58 0.58 0.65 0.37
SiO 2+B 2O 3 77.52 75.58 76.40 75.24 75.19
Al 2O 3/B 2O 3 0.93 1.62 1.55 1.24 1.25
(Li 2O+Na 2O+K 2O) 0.88 0.57 0.61 0.61 0.61
Li 2O/(Li 2O+Na 2O+K 2O) 0.00 0.00 0.00 0.00 0.00
? ? ? ? ? ?
T L(°C) *** *** *** *** ***
T F(°C) *** *** *** *** ***
T F-T L(°C) *** *** *** *** ***
D k@1GHz *** *** *** *** ***
D f@1GHz *** *** *** *** ***
? ? ? ? ? ?
Fibre density (g/cm 3) 2.341 *** *** *** ***
Fibre strength (MPa) 3372 *** *** *** ***
Table 8 (continuing)
wt% 59 60 61 62
SiO 2 69.26 71.45 74.07 76.97
Al 2O 3 8.72 5.30 7.27 4.63
Fe 2O 3 0.13 0.06 0.09 0.10
CaO 4.89 5.24 4.88 5.69
MgO 9.92 10.63 4.77 5.56
Na 2O 0.53 0.58 0.73 1.61
K 2O 0.03 0.02 0.03 0.01
B 2O 3 5.09 4.96 6.39 4.47
F 2 0.49 0.50 0.66 0.77
TiO 2 0.27 0.05 0.17 0.19
Li 2O 0.69 1.20 0.95 0.00
SO 3 0.00 0.00 0.00 0.00
Amount to 100.00 100.00 100.00 100.00
? ? ? ? ?
(MgO+CaO) 14.81 15.87 9.65 11.25
CaO/Mg 0.49 0.49 1.02 1.02
MgO/(MgO+CaO) 0.67 0.67 0.49 0.49
SiO 2+B 2O 3 74.35 76.41 80.46 81.44
Al 2O 3/B 2O 3 1.71 1.07 1.14 1.04
(Li 2O+Na 2O+K 2O) 1.25 1.80 1.71 1.62
Li 2O/(Li 2O+Na 2O+K 2O) 0.55 0.67 0.56 0.00
? ? ? ? ?
T L(°C) *** *** *** ***
T F(°C) 1358/1355 1331/1333 1493/1484 ***
T F-T L(°C) *** *** *** ***
D k@1GHz *** *** *** ***
D f@1GHz *** *** *** ***
? ? ? ? ?
Fibre density (g/cm 3) *** *** *** ***
Fibre strength (MPa) *** *** *** ***
Sample 63-73 provides glass composition (table 9), % by weight: SiO 262.35-68.35%, B 2O 36.72-8.67%, Al 2O 310.53-18.04%, MgO8.14-11.44%, CaO1.67-2.12%, Li 2O1.07-1.38%, Na 2O0.02%, K 2O0.03-0.04%, Fe 2O 30.23-0.33%, F 20.49-0.60%, TiO 20.26-0.61% and vitriol (are expressed as SO 3) 0.0%.
Sample 63-73 provides glass composition (table 9), % by weight, and wherein (MgO+CaO) content is 9.81-13.34%, the CaO/MgO ratio is 0.16-0.20, (SiO 2+ B 2O 3) content is 69.59-76.02%, Al 2O 3/ B 2O 3Ratio is 1.37-2.69, (Li 2O+Na 2O+K 2O) content is 1.09-1.40%, and Li 2O/ (Li 2O+Na 2O+K 2O) ratio is 0.98.
In mechanical properties, the fibre density of the composition of table 9 is 2.371-2.407g/cm 3And average fiber tensile strength (perhaps fibre strength) is 3730-4076MPa.Tensile strength of fiber by the made fiber of the composition of table 9 is to measure with the same way as of the measurement tensile strength of fiber relevant with the composition of table 8.
Young's modulus (E) value that has been found that the fiber that is formed by said composition is 73.84-81.80GPa.The Young's modulus of this fiber (E) value uses sound modulus method to measure on fiber.The elastic mould value of the fiber that stretches from the glass melt with described composition is to use ultrasonic wave sound pulsed technique from Panametrics, and Inc.of Waltham measures on the Panatherm5010 instrument of Massachusetts.The expansion wave reflection time is to use for 20 microsecond extended periods, and the 200kHz pulse obtains.Measure sample length, and calculated expansion wave velocity (V separately E).Fibre density (ρ) is measured with Micromeritics AccuPyc1330 specific gravity flask.Usually, each composition has been carried out 20 measurements, and according to formula E=V E 2* ρ has calculated average Young's modulus (E).The fiber failure strain is to use the Hooke rule, calculates based on known fibre strength and Young's modulus value.
Have been found that the D at the described glass of 1GHz kThat 5.20-5.54 and Df are 0.0010-0.0020.The electrical property of the composition of table 9 shows as E-glass (that is, the improved) D of the standard of being starkly lower than kAnd D f, this standard E-glass D when 1GHz k7.14 and D f0.0168.
At the fiberizing aspect of performance, the mold temperature (T of the composition of table 9 F) be 1303-1388 ℃ and moulding window (T F-T L) be 51-144 ℃.
Table 9. useful some glass compositions in some embodiments of the present invention.
wt% 63 64 65 66 67
SiO 2 64.25 65.35 66.38 67.35 68.35
Al 2O 3 11.88 11.52 11.18 10.86 10.53
Fe 2O 3 0.26 0.25 0.24 0.24 0.23
CaO 2.12 2.05 1.99 1.93 1.87
MgO 10.50 10.17 9.87 9.58 9.29
Na 2O 0.02 0.02 0.02 0.02 0.02
K 2O 0.04 0.03 0.03 0.03 0.03
B 2O 3 8.67 8.40 8.15 7.91 7.67
F 2 0.60 0.58 0.56 0.54 0.53
TiO 2 0.30 0.29 0.28 0.27 0.26
Li 2O 1.38 1.33 1.29 1.26 1.22
SO 3 0.00 0.00 0.00 0.00 0.00
Amount to 100.00 100.00 100.00 100.00 100.00
? ? ? ? ? ?
(MgO+CaO) 12.61 12.22 11.86 11.51 11.16
CaO/MgO 0.20 0.20 0.20 0.20 0.20
MgO/(MgO+CaO) 0.83 0.83 0.83 0.83 0.83
SiO 2+B 2O 3 72.92 73.75 74.53 75.26 76.02
Al 2O 3/B 2O 3 1.37 1.37 1.37 1.37 1.37
(Li 2O+Na 2O+K 2O) 1.40 1.36 1.32 1.28 1.24
Li 2O/(Li 2O+Na 2O+K 2O) 0.98 0.98 0.98 0.98 0.98
? ? ? ? ? ?
T L(°C) 1241 1259 1266 1268 1287
T F(°C) 1306 1329 1349 1374 1388
T F-T L(°C) 65 70 83 106 101
D k@1GHz 5.44 5.35 5.29 5.31 5.2
D f@1GHz 0.0013 0.0016 0.001 0.002 0.0013
? ? ? ? ? ?
Fibre density (g/cm 3) 2.395 2.385 2.384 2.375 2.371
Fibre strength (MPa) 3730 3759 3813 3743 3738
Young's modulus (GPa) *** *** *** 74.25 ***
Fiber failure strain (%) *** *** *** 5.04 ***
Table 9 (continuing)
wt% 68 69 70 71 72 73
SiO 2 64.39 63.63 62.87 65.45 65.61 62.35
Al 2O 3 14.05 16.04 18.04 11.05 14.29 14.74
Fe 2O 3 0.28 0.30 0.33 0.24 0.28 0.29
CaO 1.90 1.79 1.67 1.91 1.77 1.79
MgO 9.39 8.77 8.14 11.44 8.72 11.37
Na 2O 0.02 0.02 0.02 0.02 0.02 0.02
K 2O 0.04 0.04 0.04 0.03 0.04 0.04
B 2O 3 7.75 7.23 6.72 7.80 7.19 7.28
F 2 0.54 0.51 0.49 0.54 0.51 0.51
TiO 2 0.41 0.51 0.61 0.28 0.43 0.45
Li 2O 1.23 1.15 1.07 1.24 1.14 1.16
SO 3 0.00 0.00 0.00 0.00 0.00 0.00
Amount to 100.00 100.00 100.00 100.00 100.00 100.00
? ? ? ? ? ? ?
(MgO+CaO) 11.29 10.55 9.81 13.34 10.49 13.16
CaO/MgO 0.20 0.20 0.20 0.17 0.20 0.16
MgO/(MgO+CaO) 0.83 0.83 0.83 0.86 0.83 0.86
SiO 2+B 2O 3 72.14 70.87 69.59 73.25 72.80 69.63
Al 2O 3/B 2O 3 1.81 2.22 2.69 1.42 1.99 2.02
(Li 2O+Na 2O+K 2O) 1.25 1.17 1.09 1.26 1.16 1.18
Li 2O/(Li 2O+Na 2O+K 2O) 0.98 0.98 0.98 0.98 0.98 0.98
? ? ? ? ? ? ?
T L(°C) 1231 1219 1236 1266 1235 1220
T F(°C) 1349 1362 1368 1317 1379 1303
T F-T L(°C) 118 143 132 51 144 83
Dk@1GHz 5.4 5.38 5.39 5.54 5.52 5.58
Df@1GHz 0.0016 0.0013 0.002 0.0015 0.0016 0.0015
? ? ? ? ? ? ?
Fibre density (g/cm 3) 2.393 2.398 2.407 *** *** ***
Fibre strength (MPa) 3954 3977 4076 *** *** ***
Young's modulus (GPa) 73.84 80.34 81.57 80.69 81.80 ***
Fiber failure strain (%) 5.36 4.95 5.00 4.68 4.72 ***
The characteristic of making us expecting (it can show by different but nonessential whole embodiments of the present invention) can include but not limited to following: glass fibre, glass fiber precursor, glasscloth, matrix material and laminate (having relative low density) are provided; Glass fibre, glass fiber precursor, glasscloth, matrix material and laminate (it has relative high modulus) are provided; Glass fibre, glass fiber precursor, glasscloth, matrix material and laminate (it has relative high strain and lost efficacy) are provided; Glass fibre, glass fiber precursor, glasscloth, matrix material, laminate and prepreg (being useful for strengthening application) are provided; With glass fibre, glass fiber precursor, glasscloth, matrix material, laminate and prepreg are provided, it has than the relative low cost of other glass fibre, glass fiber precursor, glasscloth, matrix material, laminate and prepreg of be used for to strengthen using.
The different embodiment of the present invention has been described in realizing the different target of the present invention.Should be recognized that these embodiments are only the signals of the principle of the invention.Its numerous improvement and change will be easily apparent for a person skilled in the art, and not break away from the spirit and scope of the invention.

Claims (37)

1. glass fiber precursor, it comprises a plurality of glass fibre, and this glass fibre comprises the glass composition that contains following component:
SiO 2The 60-68 % by weight;
B 2O 3The 7-12 % by weight;
Al 2O 3The 9-15 % by weight;
MgO 8-15 % by weight;
CaO 0-4 % by weight;
Li 2O 0-2 % by weight;
Na 2O 0-1 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-1 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions are the 0-5 % by weight altogether;
(Li wherein 2O+Na 2O+K 2O) content is less than 2 % by weight, and wherein MgO content is the twice at least of CaO content based on % by weight.
2. yarn, it comprises at least a glass fiber precursor according to claim 1.
3. the yarn of claim 2, wherein this at least a glass fiber precursor is coated with glueing composition at least in part.
4. the yarn of claim 2, wherein the diameter of these a plurality of glass fibre is the about 13 μ m of about 5-.
5. fabric, it is to be formed by according to claim 1 at least a glass fiber precursor.
6. fabric, it comprises at least one weft yarn, and this weft yarn comprises at least a glass fiber precursor according to claim 1.
7. fabric, it comprises at least one warp thread, and this warp thread comprises at least a glass fiber precursor according to claim 1.
8. fabric, it comprises:
At least one weft yarn, this weft yarn comprise at least a glass fiber precursor according to claim 1, and
At least one warp thread, this warp thread comprise at least a glass fiber precursor according to claim 1.
9. the fabric of claim 8, wherein this fabric comprises plain weave fabric, twilled fabric, woven fabric, satin woven fabric, stitch bonded fabric or 3D woven fabric.
10. matrix material, it comprises:
Fluoropolymer resin; With
Be arranged in the glass fibre from according to claim 1 glass fiber precursor in this fluoropolymer resin.
11. a matrix material, it comprises:
Fluoropolymer resin; With
At least a fabric that is formed by at least a glass fiber precursor according to claim 1.
12. the matrix material of claim 11, wherein this fluoropolymer resin comprises epoxy resin.
13. the matrix material of claim 11, wherein this fluoropolymer resin comprises following at least a: polyvinyl resin, acrylic resin, polyamide resin, polyimide resin, polybutylene terephthalate resin, polycarbonate resin, TPU(Thermoplastic polyurethanes), phenolic resin, vibrin, vinyl ester resin, polydicyclopentadiene resins, polyphenylene sulfide resin, polyether-ether-ketone resin, cyanate ester resin, bimaleimide resin and thermosetting polyurethane resin.
14. the matrix material of claim 11, wherein this fabric comprises plain weave fabric, twilled fabric, woven fabric, satin woven fabric, stitch bonded fabric or 3D woven fabric.
15. an aerospace matrix material, it comprises matrix material according to claim 11.
16. an aviation matrix material, it comprises matrix material according to claim 11.
17. a radome, it comprises matrix material according to claim 11.
18. a prepreg, it comprises:
Fluoropolymer resin; With
At least a glass fiber precursor according to claim 1.
19. fiber-metal level is fit, it comprises:
Prepreg according to claim 20;
Be adhesively secured to lip-deep first tinsel of this prepreg; With
Be adhesively secured to the second tinsel on the second surface of this prepreg, make this prepreg between two tinsels.
20. fiber according to claim 19-metal level is fit, it further comprises according to claim 20 the second prepreg and the 3rd tinsel, and wherein this second prepreg is between the second tinsel and the 3rd tinsel.
21. the fiber of claim 19-metal level is fit, wherein this tinsel comprises aluminium.
22. the fiber of claim 19-metal level is fit, wherein this fluoropolymer resin comprises epoxy resin.
23. a laminate, it comprises:
Fluoropolymer resin; With
A plurality of glasscloths, wherein at least one fabric is to be formed by at least a glass fiber precursor according to claim 1.
24. a matrix material, it comprises:
Fluoropolymer resin; With
Be arranged in a plurality of glass fibre in this fluoropolymer resin, wherein at least one in these a plurality of glass fibre comprises the glass composition that contains following component:
SiO 253.5-77 % by weight;
B 2O 34.5-14.5 % by weight;
Al 2O 34.5-18.5 % by weight;
MgO 4-12.5 % by weight;
CaO 0-10.5 % by weight;
Li 2O 0-4 % by weight;
Na 2O 0-2 % by weight;
K 2O 0-1 % by weight;
Fe 2O 3The 0-1 % by weight;
F 2The 0-2 % by weight;
TiO 2The 0-2 % by weight; With
Other compositions are the 0-5 % by weight altogether.
25. the matrix material of claim 24, wherein these a plurality of glass fibre are arranged and form fabric.
26. the matrix material of claim 24, wherein this fabric comprises plain weave fabric, twilled fabric, woven fabric, satin woven fabric, stitch bonded fabric or 3D woven fabric.
27. the matrix material of claim 24, wherein this fluoropolymer resin comprises epoxy resin.
28. the matrix material of claim 24, wherein this fluoropolymer resin comprises following at least a: polyvinyl resin, acrylic resin, polyamide resin, polyimide resin, polybutylene terephthalate resin, polycarbonate resin, TPU(Thermoplastic polyurethanes), phenol tree lipoid, vibrin, vinyl ester resin, polydicyclopentadiene resins, polyphenylene sulfide, polyether-ether-ketone resin, cyanate ester resin, bimaleimide resin and thermosetting polyurethane resin.
29. an aerospace matrix material, it comprises matrix material according to claim 24.
30. an aviation matrix material, it comprises matrix material according to claim 24.
31. a radome, it comprises matrix material according to claim 24.
32. a prepreg, it comprises matrix material according to claim 24.
33. fiber-metal level is fit, it comprises:
Prepreg according to claim 32;
Be adhesively secured to lip-deep first tinsel of this prepreg; With
Be adhesively secured to the second tinsel on the second surface of this prepreg, make this prepreg between two tinsels.
34. fiber according to claim 33-metal level is fit, it further comprises according to claim 32 the second prepreg and the 3rd tinsel, and wherein this second prepreg is between the second tinsel and the 3rd tinsel.
35. the fiber of claim 33-metal level is fit, wherein this tinsel comprises aluminium.
36. the fiber of claim 33-metal level is fit, wherein this fluoropolymer resin comprises epoxy resin.
37. a laminate, it comprises the prepreg of claim 32.
CN2011800492867A 2010-09-14 2011-09-14 Low density and high strength fiber glass for reinforcement applications Pending CN103153896A (en)

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US38273810P 2010-09-14 2010-09-14
US61/382,738 2010-09-14
US12/940,764 US8697590B2 (en) 2006-12-14 2010-11-05 Low dielectric glass and fiber glass for electronic applications
US12/940,764 2010-11-05
US13/229,012 2011-09-09
US13/229,012 US8697591B2 (en) 2006-12-14 2011-09-09 Low dielectric glass and fiber glass
PCT/US2011/051555 WO2012037219A1 (en) 2010-09-14 2011-09-14 Low density and high strength fiber glass for reinforcement applications

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CN107759095A (en) * 2017-10-30 2018-03-06 安徽丹凤集团桐城玻璃纤维有限公司 A kind of high strength glass fiber
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MX2013002777A (en) 2013-10-28
TW201217295A (en) 2012-05-01

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