CN103172267A - High-strength high-modulus glass fiber and preparation method thereof - Google Patents

High-strength high-modulus glass fiber and preparation method thereof Download PDF

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Publication number
CN103172267A
CN103172267A CN2013101218165A CN201310121816A CN103172267A CN 103172267 A CN103172267 A CN 103172267A CN 2013101218165 A CN2013101218165 A CN 2013101218165A CN 201310121816 A CN201310121816 A CN 201310121816A CN 103172267 A CN103172267 A CN 103172267A
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strength
modulus
glass
glass fiber
glass fibre
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徐时清
孙杏国
王焕平
赵士龙
李兵鹏
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China Jiliang University
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China Jiliang University
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    • 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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • 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
    • 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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Glass Compositions (AREA)

Abstract

The invention relates to high-strength high-modulus glass fiber. The high-strength high-modulus glass fiber is prepared from the following components: 53-57wt% of SiO2, 23-26wt% of Al2O3, 11.5-14.5wt% of MgO, 2-4wt% of B2O3, 0.2-1.0wt% of Fe2O3, 0.2-1.0wt% of CeO2, 0.2-0.8wt% of Li2O, 0-1wt% of TiO2, ZrO2, Y2O3 and other compounds, wherein the total weight of the ZrO2, Y2O3 and the other compounds is smaller than 1wt%. The high-strength high-modulus glass fiber has the advantages that the mechanical performance is good, i.e., the monofilament tensile strength reaches 4540-4720MPa, the modulus of elasticity for tension reaches 85-87MPa, the density of the glass fiber is equivalent to that of E glass, and compared with the traditional E glass fiber, the high-strength high-modulus glass fiber has the advantages that the monofilament tensile strength is improved by more than 30%, and the modulus of elasticity for tension is improved by more than 18%.

Description

High-strength and high-modulus glass fibre and preparation method thereof
Technical field
The present invention relates to a kind of high-strength and high-modulus glass fibre, be mainly used in wind electricity blade and long-distance transmission line field, also can be used for the defence and military fields such as Aeronautics and Astronautics, weapons.
Background technology
Development along with wind power technology; the low-coat scale development is inexorable trend; and the key of wind-powered electricity generation low-coat scale development is the technology that solves the large size wind electricity blade; due to the increase along with blade length; strength and stiffness to material propose requirements at the higher level; therefore, the strength and stiffness problems of solution blade material is to solve the key problem in technology that wind electricity blade maximizes.For this reason, wind-powered electricity generation developed country is all using the research and development of high-strength high-modulus glass fiber as a main direction that solves the wind electricity blade maximization.Abroad, the OCV corporation in 2006 is developed Hiper-tex tMglass, its strength and modulus improves respectively 30% and 17% than E glass; AGY company develops the S-1 glass in 2008, and its strength and modulus improves respectively 45% and 20% than E glass, with traditional high-strength glass fibre, compares, and these fibrous mechanical properties are suitable, but produce, stablizes, and price is low.The large glass giant of China three is in order to seize wind electricity blade market, and also emphasis drops into and researched and developed, between 2009～2010 years, successively developed the glass of the trades mark such as TM, Vipro, GMG, with the E glass fibre, compare, the intensity of these fibers improves 15～30%, and modulus improves 10～17%.
Summary of the invention
An object of the present invention is to solve the deficiency that existing glass fibre exists, disclose that a kind of to have good mechanical properties be that monofilament tensile strength and modulus in tension are good, as the high-strength and high-modulus glass fibre of enhancing base material; Another object of the present invention is to disclose a kind of preparation method who prepares above-mentioned high-strength and high-modulus glass fibre.
Technical scheme of the present invention is as follows:
The high-strength and high-modulus glass fibre, comprise that following component makes: SiO 260～66wt%, Al 2o 323～25.5wt%, MgO9～13.5wt%, CaO0～1.5wt%, CeO 20～1.6wt%, Y 2o 30～1.5wt%, ZrO 20～1.5wt%, TiO 20～1.5wt%, Nb 2o 30～1.5wt%, Fe 2o 3, WO 3, R 2o and other compound, Fe 2o 3, WO 3, R 2o and other total amount of compound are less than 1wt%.
As preferably, comprise that following component makes: SiO 261～64wt%, Al 2o 323.5～25wt%, MgO9.5～10.5wt%, CaO0～1.5wt%, CeO 20.2～1.0wt%, Y 2o 30～1.5wt%, ZrO 20～1.5wt%, TiO 20～1.5wt%, Nb 2o 30～1.5wt%, Fe 2o 3, WO 3, R 2o and other compound, Fe 2o 3, WO 3, R 2o and other total amount of compound are less than 1wt%.
The preparation method of high-strength and high-modulus glass fibre, make glass by each component claimed in claim 1 melting under 1500 ℃～1550 ℃ temperature condition, melting again under 1500 ℃, and melten glass is drawn into fiber under 1360～1380 ℃ of temperature condition.
As preferably, by each component under 1500 ℃～1550 ℃ temperature condition, melting while stirring, found and within 12 hours, make glass, melting more than 4 hours, after single hole wire-drawing crucible temperature is down to 1360～1380 ℃ again under 1500 ℃, start wire drawing, be drawn into the continuous fibre that diameter is 8～9 μ m.
Adopted the high-strength and high-modulus glass fibre of technique scheme, SiO 2as the glass network forming agent, its content directly affects strength of glass, modulus, recrystallization temperature, high temperature viscosity etc., along with SiO 2the increase of content, the raising of glass network structural integrity, fibre strength improves, high temperature viscosity improves, recrystallization temperature descends, but the Young's modulus reduction, glass melting temperature and wire-drawing temperature raising cause processing performance to descend; Otherwise, the strength decreased of fiber.SiO in glass fibre of the present invention 2the content optimum value is 61～64wt%.Al 2o 3as the glass network forming agent, its content directly affects strength of glass, modulus, recrystallization temperature, processing performance etc., along with Al 2o 3the increase of content, fibre strength raising, Young's modulus raising, recrystallization temperature raising, glass melting temperature, wire-drawing temperature raising cause processing performance to descend; Otherwise the strength and modulus of fiber reduces, and is difficult to obtain high strength glass fiber.Al in glass fibre of the present invention 2o 3the content optimum value is 23.5～25wt%.MgO is as the outer agent of glass network, and appropriate MgO has the effect that reduces the devitrification of glass temperature, improves processing performance and intensity, and too high levels improves on the contrary recrystallization temperature, reduces fibre strength; Too lowly be difficult to play due effect.MgO content optimum value in glass of the present invention is 9.5～10.5wt%.CaO, CeO 2, TiO 2mainly play and flux, clarify, reduce high-temperature viscosity, improve and to found and the fiber-forming process performance Deng metal oxide.In glass fibre of the present invention, the optimum value of these components is CaO0～1.5wt%, CeO 20～1.5wt%, TiO 20～1.5wt%.Y 2o 3, ZrO 2mainly play the effect that improves Young's modulus in this glass fibre, when content is too high, can improve recrystallization temperature, affect processing performance.Content optimum value in glass fibre of the present invention is Y 2o 30～1.5wt%, ZrO 20～1.5wt%.
Nb 2o 3effect be even more important, its effect is effectively to reduce high alumina devitrification of glass temperature and glass metal high temperature viscosity, is conducive to improve the processing performance of glass, too high levels, cost improves, and is unfavorable for low-coat scale production.Nb in glass fibre of the present invention 2o 3optimum content is 0～1.5wt%.Add Nb in high lead glass 2o 3can greatly reduce recrystallization temperature and the high temperature viscosity of high lead glass, improve processing performance, and, fiber isotropic modulus can effectively be improved.Contain a small amount of Fe in glass fibre 2o 3, WO 3, R 2other compound such as O, its total amount is less than 1wt%, plays fluxing action, improves and founds and the drawing process performance, and R refers to the alkali metals such as K, Na.High-strength and high-modulus glass fibre of the present invention can 1500～1550 ℃ under temperature condition, and the pre-assigned glass batch of electricity consumption heating and melting obtains high-strength and high-modulus glass.Then glass melting again under 1500 ℃, it is 8～9 μ m continuous fibres that melten glass is drawn into diameter by leting slip a remark of platinum bushing plate under 1360～1380 ℃ of temperature condition.The fiber drawn can need to be made the various glass fiber products such as glasscloth, yarn, band according to the user.
In sum, the advantage of this high-strength and high-modulus glass fibre is to have good mechanical property, be monofilament tensile strength 4600～4820MPa, modulus in tension>90GPa, compare with traditional E glass fibre, monofilament tensile strength improves more than 33%, modulus in tension improves more than 27%.The preparation method's of this high-strength and high-modulus glass fibre advantage is 1360～1380 ℃ of forming temperatures, 1300～1320 ℃ of liquidus temperatures, and production cost is low, is applicable to scale operation.
Embodiment
The embodiment that table 1 is high-strength and high-modulus glass fibre of the present invention.
Press the high-strength and high-modulus glass fibre shown in table 1, comprise that following component makes: SiO 260～66wt%, Al 2o 323～25.5wt%, MgO9～13.5wt%, CaO0～1.5wt%, CeO 20～1.6wt%, Y 2o 30～1.5wt%, ZrO 20～1.5wt%, TiO 20～1.5wt%, Nb 2o 30～1.5wt%, more than the total content of these oxide compounds in glass fibre reaches 99wt%, contain a small amount of Fe in glass of the present invention 2o 3, WO 3, R 2o and other compound, Fe 2o 3, WO 3, R 2o and other total amount of compound are less than 1wt%, and R refers to the alkali metals such as K, Na.
Embodiment:
Table 1
Figure BDA00003025268500041
The preparation method of high-strength and high-modulus glass fibre, be hybridly prepared into admixtion by each above-mentioned component, is contained in platinum material crucible, except SiO 2adopting quartz sand is beyond raw mineral materials, all other adopts the oxide compound industrial chemicals, under 1500 ℃～1550 ℃ temperature condition, melting while stirring, found 12 hours, the glass melted is flow on heat-resisting steel sheet and plate, make frit block, get part material piece and put into the single hole wire-drawing crucible, melting more than 4 hours again under 1500 ℃, after single hole wire-drawing crucible temperature is down to 1360～1380 ℃, start wire drawing, adjust drawing speed, making the continuous fibre diameter be drawn into is 8～9 μ m, get the monofilament between small opening and drawing wire machine with special sampler and testing bar, for the monofilament tensile strength test, getting a part of frit block measures for glass density, in addition the material of platinum material crucible is joined in the 100 full platinum wire-drawing crucibles in hole, adjustment crucible bushing temperature to 1360～1380 ℃, adjust drawing speed, draws the precursor of 12Tex left and right, for measuring Young's modulus.Glass density testing method: adopt suspension method, the weight before and after claiming to be immersed in the water with special balance.Glass fiber single filament strength detection method: with sampler and testing bar get between small opening and bobbins without frayed single fiber, automatically record strength machine with UTM-11-20 and survey brute force, with measuring microscope, under the condition of 800 x magnifications, measure Fibre diameter.Test condition: strength test, selected staple length 10mm, rate of extension 8mm/min, 22～25 ℃ of envrionment temperatures, humidity 40～55%; Fibre diameter 8～9 μ m.Glass fibre Young's modulus testing method: adopt sonic approach, precursor one end of the 12Tex left and right full platinum wire-drawing crucible drawn is welded on copper core loudspeaker with rosin, the other end is fixed with clip, two point of fixity distances are 100cm, loudspeaker are connected on audio signal generator, measure audio signal generator emission and the frequency that receives signal and reach hour, according to the frequency computation part Young's modulus.

Claims (4)

1. high-strength and high-modulus glass fibre, is characterized in that comprising that following component makes: SiO 260～66wt%, Al 2o 323～25.5wt%, MgO9～13.5wt%, CaO0～1.5wt%, CeO 20～1.6wt%, Y 2o 30～1.5wt%, ZrO 20～1.5wt%, TiO 20～1.5wt%, Nb 2o 30～1.5wt%, Fe 2o 3, WO 3, R 2o and other compound, Fe 2o 3, WO 3, R 2o and other total amount of compound are less than 1wt%.
2. high-strength and high-modulus glass fibre according to claim 1, is characterized in that comprising that following component makes: SiO 261～64wt%, Al 2o 323.5～25wt%, MgO9.5～10.5wt%, CaO0～1.5wt%, CeO 20.2～1.0wt%, Y 2o 30～1.5wt%, ZrO 20～1.5wt%, TiO 20～1.5wt%, Nb 2o 30～1.5wt%, Fe 2o 3, WO 3, R 2o and other compound, Fe 2o 3, WO 3, R 2o and other total amount of compound are less than 1wt%.
3. the preparation method of high-strength and high-modulus glass fibre, it is characterized in that each component claimed in claim 1 melting under 1500 ℃～1550 ℃ temperature condition is made to glass, melting again under 1500 ℃, melten glass is drawn into fiber under 1360～1380 ℃ of temperature condition.
4. the preparation method of high-strength and high-modulus glass fibre according to claim 3, it is characterized in that each component under 1500 ℃～1550 ℃ temperature condition, melting while stirring, found and within 12 hours, make glass, melting more than 4 hours again under 1500 ℃, after single hole wire-drawing crucible temperature is down to 1360～1380 ℃, start wire drawing, be drawn into the continuous fibre that diameter is 8～9 μ m.
CN2013101218165A 2013-04-09 2013-04-09 High-strength high-modulus glass fiber and preparation method thereof Pending CN103172267A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107337350A (en) * 2017-07-20 2017-11-10 太仓市格雷得五金有限公司 A kind of high strength glass fiber and preparation method thereof
US11306021B2 (en) 2018-11-26 2022-04-19 Owens Coming Intellectual Capital, LLC High performance fiberglass composition with improved elastic modulus
US11524918B2 (en) 2018-11-26 2022-12-13 Owens Corning Intellectual Capital, Llc High performance fiberglass composition with improved specific modulus

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08231240A (en) * 1995-02-28 1996-09-10 Nitto Boseki Co Ltd Composition for high strength glass fiber
JP2004115368A (en) * 2003-10-31 2004-04-15 Nitto Boseki Co Ltd Method for manufacturing glass fiber, glass fiber, glass fiber braid, glass fiber reinforced resin and printed wiring board
CN101300199A (en) * 2005-11-04 2008-11-05 Ocv智识资本有限责任公司 Composition for high performance glass, high performance glass fibers and articles therefrom
CN101549958A (en) * 2009-05-05 2009-10-07 中材科技股份有限公司 Composition for high-performance glass fiber
CN102317224A (en) * 2008-12-24 2012-01-11 Ocv智识资本有限责任公司 Composition for high performance glass fibers and fibers formed therewith
US20120177870A1 (en) * 2007-03-05 2012-07-12 Phra Douglas Lyle Ballistic materials

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08231240A (en) * 1995-02-28 1996-09-10 Nitto Boseki Co Ltd Composition for high strength glass fiber
JP2004115368A (en) * 2003-10-31 2004-04-15 Nitto Boseki Co Ltd Method for manufacturing glass fiber, glass fiber, glass fiber braid, glass fiber reinforced resin and printed wiring board
CN101300199A (en) * 2005-11-04 2008-11-05 Ocv智识资本有限责任公司 Composition for high performance glass, high performance glass fibers and articles therefrom
US20120177870A1 (en) * 2007-03-05 2012-07-12 Phra Douglas Lyle Ballistic materials
CN102317224A (en) * 2008-12-24 2012-01-11 Ocv智识资本有限责任公司 Composition for high performance glass fibers and fibers formed therewith
CN101549958A (en) * 2009-05-05 2009-10-07 中材科技股份有限公司 Composition for high-performance glass fiber

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107337350A (en) * 2017-07-20 2017-11-10 太仓市格雷得五金有限公司 A kind of high strength glass fiber and preparation method thereof
US11306021B2 (en) 2018-11-26 2022-04-19 Owens Coming Intellectual Capital, LLC High performance fiberglass composition with improved elastic modulus
US11524918B2 (en) 2018-11-26 2022-12-13 Owens Corning Intellectual Capital, Llc High performance fiberglass composition with improved specific modulus

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Application publication date: 20130626