WO2023190980A1 - Fibres de verre - Google Patents

Fibres de verre Download PDF

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Publication number
WO2023190980A1
WO2023190980A1 PCT/JP2023/013381 JP2023013381W WO2023190980A1 WO 2023190980 A1 WO2023190980 A1 WO 2023190980A1 JP 2023013381 W JP2023013381 W JP 2023013381W WO 2023190980 A1 WO2023190980 A1 WO 2023190980A1
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Prior art keywords
mass
less
glass
sio
glass fiber
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PCT/JP2023/013381
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English (en)
Japanese (ja)
Inventor
浩輔 藤原
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日本板硝子株式会社
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Publication of WO2023190980A1 publication Critical patent/WO2023190980A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/38—Fibrous materials; Whiskers
    • C04B14/42—Glass
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates

Definitions

  • the present invention relates to glass fibers for inorganic hardened products, specifically glass fibers suitable for blending into cement, mortar, concrete, calcium silicate plates, plaster, etc.
  • Glass fiber reinforced cement is a composite material of cement and glass fiber, and is intended to control the tensile strength and ductility of cement.
  • Mortar cement mortar
  • cement concrete cement concrete
  • coarse aggregate such as gravel and fine aggregate. It is solidified.
  • Cement mixed with water produces calcium hydroxide (Ca(OH) 2 ), etc., and therefore exhibits alkalinity.
  • alkali-resistant glass fibers are used for cement reinforcement.
  • AR glass is known as a composition of alkali-resistant glass fiber.
  • the AR glass contains 16.8% zirconium oxide (ZrO 2 ) and 14.5% alkali metal oxide in mass %.
  • Patent Document 1 discloses an improved composition of AR glass.
  • Glass fibers are widely used as fibers to reinforce not only cement-based hardened bodies such as cement and mortar, but also various inorganic hardened bodies including calcium silicate plates.
  • Demand for inorganic hardened materials reinforced with glass fibers is increasing, and the areas in which they are used are also becoming more diverse.
  • an object of the present invention is to provide a new glass fiber suitable for reinforcing an inorganic cured product.
  • the present invention is a glass fiber for an inorganic cured product, Displayed in mass%, 50 ⁇ SiO 2 ⁇ 65, 0 ⁇ B 2 O 3 ⁇ 2, 5 ⁇ Al 2 O 3 ⁇ 14, 10 ⁇ CaO ⁇ 30, 0 ⁇ ( Li2O + Na2O + K2O ) ⁇ 4, 0 ⁇ ZrO 2 ⁇ 7,
  • a glass fiber comprising a glass composition containing the following components is provided.
  • a new glass fiber suitable for reinforcing an inorganic cured product is provided.
  • not substantially containing and not substantially containing mean that the content is less than 0.1% by mass, less than 0.05% by mass, less than 0.01% by mass, and even 0. This means less than 0.005% by weight, in particular less than 0.003% by weight, and in some cases less than 0.001% by weight.
  • substantially means that the inclusion of trace amounts of impurities originating from glass raw materials, manufacturing equipment, molding equipment, etc. is allowed.
  • Mainn component means a component having the highest content on a mass basis.
  • T-Fe 2 O 3 means total iron oxide converted to diiron trioxide (Fe 2 O 3 ).
  • Alkali metal oxide means lithium oxide (Li 2 O), sodium oxide (Na 2 O) and potassium oxide (K 2 O). The upper and lower limits of the content described below can be arbitrarily combined.
  • a glass fiber suitable for reinforcing an inorganic cured product is provided.
  • each component constituting the glass composition in this embodiment will be explained.
  • SiO2 Silicon dioxide
  • SiO 2 is a component that forms the skeleton of glass and is the main component of the glass composition. Further, SiO 2 is a component that adjusts the devitrification temperature and viscosity during glass formation, and is a component that improves acid resistance.
  • the content of SiO 2 is 50% by mass or more and 65% by mass or less, an increase in the devitrification temperature of the glass, which would make glass production difficult, is suppressed, and the acid resistance and alkali resistance of the glass are increased. Further, within this range, the melting point of the glass will not become excessively high, and the uniformity of melting the raw materials will increase.
  • the lower limit of the content of SiO 2 may be 51% by mass or more, 52% by mass or more, 53% by mass or more, 54% by mass or more, 55% by mass or more, 56% by mass or more, 57% by mass or more, 58% by mass.
  • the content may be more than 59% by mass or more than 60% by mass.
  • the upper limit of the content of SiO 2 may be 64% by mass or less, or 63% by mass or less.
  • B 2 O 3 , Al 2 O 3 Diboron trioxide
  • B 2 O 3 is a component that forms the skeleton of glass.
  • B 2 O 3 is also a component that adjusts the devitrification temperature and viscosity during glass formation.
  • excessive content of B 2 O 3 lowers the acid resistance and alkali resistance of the glass.
  • the lower limit of the content of B 2 O 3 may be 0.1% by mass or more.
  • the upper limit of the content of B 2 O 3 may be less than 2% by mass, 1.5% by mass or less, 1% by mass or less, or 0.5% by mass or less.
  • the upper limit of the content of B 2 O 3 may be 0.1% by mass or less.
  • the glass composition may be substantially free of B 2 O 3 .
  • Aluminum oxide (Al 2 O 3 ) is a component that forms the skeleton of glass. Furthermore, Al 2 O 3 is a component that adjusts the devitrification temperature and viscosity during glass formation, and is a component that improves the water resistance of the glass. On the other hand, excessive content of Al 2 O 3 lowers the acid resistance and alkali resistance of the glass. When the Al 2 O 3 content is 5% by mass or more and 14% by mass or less, an increase in the devitrification temperature of the glass, which would make glass production difficult, is suppressed, and the acid resistance and alkali resistance of the glass are increased. Furthermore, the melting point of the glass does not become excessively high, and the uniformity of melting the raw materials increases.
  • the lower limit of the content of Al 2 O 3 may be 6% by mass or more, 7% by mass or more, 8% by mass or more, 8.5% by mass or more, 9% by mass or more, 9.5% by mass or more, 10% by mass % or more, 10.5% by mass or more, 11% by mass or more, and even 11.1% by mass or more.
  • the upper limit of the Al 2 O 3 content may be 13% by mass or less, 12.5% by mass or less, less than 12% by mass, or even 11.9% by mass.
  • the devitrification temperature increases while suppressing an excessive increase in the devitrification temperature.
  • the devitrification temperature and viscosity can be set within a range suitable for glass production. Further, within this range, it is also possible to improve the alkali resistance of the glass.
  • the lower limit of (B 2 O 3 +Al 2 O 3 ) may be 6% by mass or more, 7% by mass or more, 8% by mass or more, 9% by mass or more, and even 10% by mass or more.
  • the upper limit of (B 2 O 3 +Al 2 O 3 ) can be 15% by mass or less, 14% by mass or less, and even 13% by mass or less.
  • CaO Calcium oxide
  • CaO is a component that adjusts the devitrification temperature and viscosity during glass formation. Moreover, CaO is also a component that improves Young's modulus. When the CaO content is 10% by mass or more and 30% by mass or less, the Young's modulus is improved and the devitrification temperature and viscosity at the time of melting of the glass are controlled to be suitable for glass production while suppressing an excessive rise in the devitrification temperature.
  • the range can be within the specified range.
  • the lower limit of the content of CaO may be 12% by mass or more, 13% by mass or more, 14% by mass or more, 15% by mass or more, 16% by mass or more, 17% by mass or more, and even 18% by mass or more.
  • the upper limit of the content of CaO may be 28% by mass or less, 27% by mass or less, 26% by mass or less, further 25% by mass or less, particularly 24% by mass or less.
  • Alkali metal oxides (Li 2 O, Na 2 O, K 2 O) are components that adjust the devitrification temperature and viscosity during glass formation.
  • the devitrification temperature of the molten glass and the The viscosity can be in a range suitable for glass production. Further, while suppressing the increase in the melting point of the glass and achieving more uniform melting of the glass raw materials, high heat resistance of the glass can be ensured without excessively lowering the glass transition temperature. Furthermore, the acid resistance and alkali resistance of the glass are increased.
  • the lower limit of (Li 2 O+Na 2 O+K 2 O) may be greater than 0% by mass, or may be greater than or equal to 0.1% by mass.
  • the upper limit of (Li 2 O+Na 2 O+K 2 O) may be 3% by mass or less, 2% by mass or less, and less than 2% by mass. If the alkali resistance of the glass composition is particularly important, the value of (Li 2 O+Na 2 O+K 2 O) may be set to 0.1% by mass or less.
  • the glass composition may be substantially free of alkali metal oxides.
  • Each of Li 2 O, Na 2 O, and K 2 O is an optional component. In other words, the lower limit of the content of each of these components may be zero.
  • the lower limit of the content of lithium oxide (Li 2 O) may be 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, and even 0.4% by mass or more.
  • the upper limit of the content of Li 2 O may be 4% by mass or less, 3% by mass or less, 2% by mass or less, 1.5% by mass or less, and even 1% by mass or less.
  • the lower limit of the content of sodium oxide (Na 2 O) may be 0.1% by mass or more, or 0.2% by mass or more.
  • the upper limit of the content of Li 2 O may be 4% by mass or less, 3% by mass or less, 2% by mass or less, 1.5% by mass or less, and even 1% by mass or less.
  • the lower limit of the potassium oxide (K 2 O) content may be 0.1% by mass or more, or 0.2% by mass or more.
  • the upper limit of the content of K 2 O may be 4% by mass or less, 3% by mass or less, 2% by mass or less, 1.5% by mass or less, or even 1% by mass or less.
  • the lower limit of the value obtained by subtracting the Al 2 O 3 content from the SiO 2 content is 40% by mass or more, 41% by mass or more , 42% by mass or more, 43% by mass or more, 44% by mass or more, 45% by mass or more, 46% by mass or more, 47% by mass or more, more than 48% by mass, 48.5% by mass or more, and more than 49% by mass. , or even 49.5% or more.
  • the upper limit of (SiO 2 -Al 2 O 3 ) may be 57% by mass or less, 56% by mass or less, 55% by mass or less, 54% by mass or less, 53% by mass or less, and even 52% by mass or less. It's possible.
  • the upper limit of (SiO 2 -B 2 O 3 -Al 2 O 3 ) may be 56% by mass or less, 55% by mass or less, 54% by mass or less, 53% by mass or less, 52% by mass or less, and even It may be 51% by mass or less.
  • the value of the sum of the contents of SiO 2 and Al 2 O 3 (SiO 2 +Al 2 O 3 ) is important.
  • the lower limit of (SiO 2 +Al 2 O 3 ) is preferably 55% by mass or more, 58% by mass or more, 60% by mass or more, 62% by mass or more, 64% by mass or more, It may be 65% by mass or more, or 66% by mass or more.
  • the upper limit of (SiO 2 +Al 2 O 3 ) is preferably 80% by mass or less, and may be 78% by mass or less, 76% by mass or less, 75% by mass or less, 74% by mass or less, or 73% by mass or less. .
  • the value of the total content of SiO 2 , B 2 O 3 and Al 2 O 3 (SiO 2 +B 2 O 3 +Al 2 O 3 ) is important.
  • the lower limit of (SiO 2 +B 2 O 3 +Al 2 O 3 ) is preferably 55% by mass or more, 58% by mass or more, 60% by mass or more, 62% by mass or more, 64% by mass or more. It may be at least 65% by mass, or at least 66% by mass.
  • the upper limit of (SiO 2 +B 2 O 3 +Al 2 O 3 ) is preferably 80% by mass or less, 78% by mass or less, 76% by mass or less, 75% by mass or less, 74% by mass or less, and 73% by mass or less. There may be.
  • the glass composition may further contain magnesium oxide (MgO).
  • MgO is a component that adjusts the devitrification temperature and viscosity during glass formation. Moreover, MgO is also a component that improves Young's modulus. On the other hand, excessive MgO content reduces the alkali resistance of the glass.
  • the lower limit of the MgO content may be 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, or even 2% by mass or more.
  • the upper limit of the content of MgO may be 10% by mass or less, 8% by mass or less, 6% by mass or less, 5% by mass or less, 4.5% by mass or less, or 4% by mass or less.
  • the value of the sum of the contents of MgO and CaO is important.
  • the lower limit of (MgO+CaO) is preferably 15% by mass or more, 16% by mass or more, 17% by mass or more, 18% by mass or more, 19% by mass or more. , 20% by mass or more, 21% by mass or more, and 22% by mass or more, in this order.
  • the upper limit of (MgO+CaO) is preferably 40% by mass or less, more preferably 35% by mass or less, 32% by mass or less, 30% by mass or less, 29% by mass or less, and 28% by mass or less.
  • the glass composition may further contain strontium oxide (SrO).
  • SrO is a component that adjusts the devitrification temperature and viscosity during glass formation.
  • excessive SrO content reduces the acid resistance of the glass.
  • the lower limit of the content of SrO may be 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, It may be 6% by mass or more, 7% by mass or more, or even 8% by mass or more.
  • the upper limit of the content of SrO can be 25% by mass or less, 20% by mass or less, 15% by mass or less, 12% by mass or less, 10% by mass or less, 8% by mass or less, 6% by mass or less, 5% by mass or less It can be.
  • the upper limit of the SrO content may be 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.5% by mass or less, or even 0.1% by mass or less.
  • the glass composition may be substantially free of SrO.
  • the value of the total content of MgO, CaO and SrO (MgO+CaO+SrO) is important.
  • the lower limit of (MgO + CaO + SrO) is preferably 15% by mass or more, 18% by mass or more, 20% by mass or more, 21% by mass or more, 22% by mass or more. , 23% by mass or more, 24% by mass or more, 25% by mass or more, 26% by mass or more, 27% by mass or more, and 28% by mass or more.
  • the upper limit of (MgO+CaO+SrO) is preferably 40% by mass or less, more preferably 38% by mass or less, 36% by mass or less, 35% by mass or less, and 34% by mass or less.
  • the glass composition may further contain barium oxide (BaO).
  • BaO is a component that adjusts the devitrification temperature and viscosity during glass formation.
  • excessive BaO content reduces the acid resistance of the glass.
  • the upper limit of the BaO content may be 10% by mass or less, 5% by mass or less, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.5% by mass or less, and even 0.1% by mass or less. % by mass or less.
  • the glass composition may be substantially free of BaO.
  • the value of the total content of MgO, CaO, SrO and BaO is important.
  • the lower limit of (MgO+CaO+SrO+BaO) is preferably 15% by mass or more, 18% by mass or more, 20% by mass or more, 21% by mass or more, 22% by mass or more. , 23% by mass or more, 24% by mass or more, 25% by mass or more, 26% by mass or more, 27% by mass or more, and 28% by mass or more.
  • the upper limit of (MgO+CaO+SrO+BaO) is preferably 40% by mass or less, more preferably 38% by mass or less, 36% by mass or less, 35% by mass or less, and 34% by mass or less.
  • the glass composition may further contain zinc oxide (ZnO).
  • ZnO is a component that adjusts the devitrification temperature and viscosity during glass formation.
  • the upper limit of the content of ZnO may be 10% by mass or less, 5% by mass or less, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.5% by mass or less, and even 0.1% by mass or less. % by mass or less.
  • the glass composition may be substantially free of ZnO.
  • the glass composition may further contain titanium dioxide ( TiO2 ).
  • TiO 2 is a component that improves the meltability and chemical durability of glass, and improves the ultraviolet absorption characteristics of glass. Furthermore, a suitable amount of TiO 2 improves the acid resistance and water resistance of the glass. However, since TiO 2 is a relatively expensive raw material, if it is contained in a large amount, the raw material cost will increase. The lower limit of the content of TiO 2 may be 0.1% by mass or more.
  • the upper limit of the content of TiO 2 can be 10% by mass or less, 8% by mass or less, 7% by mass or less, 6% by mass or less, 5% by mass or less, less than 2% by mass, 1% by mass or less, 0.5 The amount may be less than or equal to 0.3% by mass, or even less than 0.2% by mass.
  • the glass composition may be substantially free of TiO2 .
  • the lower limit of the content of TiO2 may be 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, 1.6% by mass or more, 2% by mass or more, 3% by mass or more, It may be 4% by mass or more, 5% by mass or more, more than 5% by mass, or even 5.1% by mass or more.
  • ZrO2 Zirconium oxide
  • ZrO 2 Zirconium oxide
  • ZrO 2 Zirconium oxide
  • ZrO 2 is a component that adjusts the devitrification temperature and viscosity during glass formation. Furthermore, ZrO 2 is a component that improves the acid resistance and alkali resistance of glass.
  • ZrO 2 is a relatively expensive raw material, if it is contained in a large amount, the raw material cost will increase. A high content of ZrO 2 also increases the working temperature. Further, the lower limit of the content of ZrO 2 may be 0.1% by mass or more.
  • the upper limit of the content of ZrO2 may be less than 6% by mass, and may be 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, and may be 0.1% by mass or less.
  • the glass composition may be substantially free of ZrO2 .
  • the lower limit of the content of ZrO 2 may be 0.5% by mass or more, 1% by mass or more, 2% by mass or more, or even 3% by mass or more.
  • the glass composition may further contain iron oxide.
  • Iron (Fe) usually exists in the Fe 2+ or Fe 3+ state.
  • Fe 3+ is a component that enhances the ultraviolet absorption properties of glass
  • Fe 2+ is a component that enhances heat ray absorption properties of glass. Even if Fe is not intentionally included, it may be unavoidably mixed in with industrial raw materials. If the content of Fe is small, coloring of the glass can be prevented.
  • the upper limit of the content of Fe expressed by T-Fe 2 O 3 may be 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass % or less, 0.4 mass% or less, 0.3 mass% or less, 0.2 mass% or less, further 0.1 mass% or less, less than 0.1 mass%, 0.08 mass% or less, 0.05 The amount may be less than or equal to 0.04% by mass, or even less than 0.03% by mass.
  • the lower limit of the content of Fe expressed by T-Fe 2 O 3 may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, and further 0.2% by mass or more. Particularly in glass compositions with a low content of alkali metal oxides, trace amounts of iron oxide can contribute to promoting glass fining.
  • the glass composition may further contain fluorine (F 2 ) and chlorine (Cl 2 ). Since F 2 easily volatizes, there is a possibility of it scattering during melting, and there is also the problem that it is difficult to control the content in the glass.
  • the upper limit of the content of F2 can be 5% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.2% by mass or less, and even 0.1% by mass or less. It's possible.
  • the glass composition may be substantially free of F2 .
  • the upper limit of the content of Cl 2 may be 5% by mass or less, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.2% by mass or less, and even less than 0.1% by mass. It's possible.
  • the glass composition may be substantially free of Cl2 .
  • Glass composition include P 2 O 5 , Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , CeO 2 , Pr 2 O 3 , Nd 2 O 3 , Pm 2 O 3 and Sm 2 O3 , Eu2O3 , Gd2O3 , Tb2O3 , Dy2O3 , Ho2O3 , Er2O3 , Tm2O3 , Yb2O3 , Lu2O3 , WO3 , Nb 2 O 5 , Y 2 O 3 , MoO 3 , Ta 2 O 5 , MnO 2 and Cr 2 O 3 at a content of 0% by mass or more and 5% by mass or less, respectively. .
  • the permissible content of these components may be less than 2% by weight each, less than 1% by weight, less than 0.5% by weight, or even less than 0.1% by weight.
  • the total allowable content of these components may be 5% by weight or less, less than 2% by weight, less than 1% by weight, less than 0.5% by weight, or even less than 0.1% by weight.
  • oxides of litanoid La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
  • the glass composition contains at least one selected from SO 3 , Br 2 , I 2 , SnO 2 , As 2 O 3 and Sb 2 O 3 as an additive in an amount of 0% by mass or more and 1% by mass or less, respectively. It can be contained at a certain content rate.
  • the permissible content of these components can be less than 0.5% by weight, less than 0.2% by weight, or even less than 0.1% by weight for each.
  • the total allowable content of these components may be 1% by weight or less, less than 0.5% by weight, less than 0.2% by weight, or even less than 0.1% by weight.
  • the other components mentioned above may not be substantially contained.
  • the glass composition may contain H 2 O, OH, H 2 , CO 2 , CO, He, Ne, Ar, and N 2 at a content of 0% by mass or more and 0.1% by mass or less, respectively.
  • the permissible content of these components can be less than 0.05% by weight, less than 0.03% by weight, or even less than 0.01% by weight for each.
  • the total allowable content of these components can be 0.1% by weight or less, less than 0.05% by weight, less than 0.03% by weight, and even less than 0.01% by weight.
  • the other components mentioned above may not be substantially contained.
  • the glass composition may contain trace amounts of noble metal elements.
  • noble metal elements such as Pt, Rh, Au, and Os can be included at a content of 0% by mass or more and 0.1% by mass or less, respectively.
  • the permissible content of these components may be less than 0.1% by weight each, less than 0.05% by weight, less than 0.03% by weight, or even less than 0.01% by weight.
  • the total allowable content of these components can be 0.1% by weight or less, less than 0.05% by weight, less than 0.03% by weight, and even less than 0.01% by weight.
  • the other components mentioned above may not be substantially contained.
  • the glass composition may have a composition that does not substantially contain CuO. Further, the glass composition may have a composition that does not substantially contain CoO. Further, the glass composition can be substantially free of PbO. Further, the glass composition may have a composition that does not substantially contain NiO.
  • the glass composition of this embodiment contains the following components expressed in mass %, and may further have a preferable composition similarly described in mass % in the following paragraphs and subsequent paragraphs. 50 ⁇ SiO 2 ⁇ 65, 0 ⁇ B 2 O 3 ⁇ 2, 5 ⁇ Al 2 O 3 ⁇ 14, 10 ⁇ CaO ⁇ 30, 0 ⁇ ( Li2O + Na2O + K2O ) ⁇ 4, 0 ⁇ ZrO 2 ⁇ 7
  • a composition containing the following components and substantially free of alkali metal oxides A composition containing the following components and substantially free of alkali metal oxides.
  • the content of the alkali metal oxide is determined by the sum of the contents of Li 2 O, Na 2 O, and K 2 O.
  • composition containing the following ingredients 50 ⁇ SiO 2 ⁇ 65, 0 ⁇ B 2 O 3 ⁇ 2, 5 ⁇ Al 2 O 3 ⁇ 14, 1 ⁇ MgO ⁇ 10, 15 ⁇ CaO ⁇ 30, 0 ⁇ ( Li2O + Na2O + K2O ) ⁇ 4, 0 ⁇ ZrO 2 ⁇ 7, 0 ⁇ T-Fe 2 O 3 ⁇ 5, A composition containing the following ingredients.
  • composition containing the following ingredients.
  • the composition does not substantially contain B 2 O 3 .
  • composition containing the following ingredients 50 ⁇ SiO 2 ⁇ 65, 0.1 ⁇ B 2 O 3 ⁇ 2, 5 ⁇ Al 2 O 3 ⁇ 14, 0.1 ⁇ MgO ⁇ 10, 15 ⁇ CaO ⁇ 30, 0 ⁇ ( Li2O + Na2O + K2O ) ⁇ 4, 0 ⁇ ZrO 2 ⁇ 7, 0 ⁇ T-Fe 2 O 3 ⁇ 5, A composition containing the following ingredients.
  • (SiO 2 -Al 2 O 3 ) is the value obtained by subtracting the content of Al 2 O 3 from the content of SiO 2 on a mass basis.
  • the lower limit of (SiO 2 -Al 2 O 3 ) may be 49, and the upper limit may be 55.
  • compositions excluding compositions that do not substantially contain TiO 2 ), a composition further satisfies 0.1 ⁇ TiO 2 ⁇ 2.
  • the characteristics that the glass composition of this embodiment can have will be explained below.
  • the temperature at which the viscosity of the molten glass becomes 1000 dPa ⁇ sec (1000 poise) is called the working temperature of the glass, and is the most suitable temperature for forming the glass.
  • the working temperature is 1100° C. or higher, variations in glass fiber diameter can be reduced. If the working temperature is 1290° C. or lower, the fuel cost for melting glass can be reduced, the glass manufacturing equipment will be less susceptible to corrosion due to heat, and the life of the equipment will be extended.
  • the lower limit of the working temperature may be 1100°C or higher, 1120°C or higher, 1140°C or higher, 1150°C or higher, 1160°C or higher, 1170°C or higher, 1180°C or higher, or even 1200°C or higher.
  • the upper limit of the working temperature may be 1290°C or less, 1270°C or less, 1260°C or less, or even 1250°C or less.
  • ⁇ T may be 0°C or higher, 10°C or higher, 20°C or higher, 30°C or higher, 40°C or higher, or even 50°C or higher.
  • ⁇ T may be 200° C. or less, the glass composition can be easily adjusted.
  • ⁇ T may be 200°C or less, 180°C or less, or even 160°C or less.
  • the devitrification temperature is the temperature at which crystals are generated in the molten glass base and begin to grow.
  • long glass fibers are manufactured by, for example, pulling out a molten glass base through a nozzle of a bushing provided at the bottom of a kiln tank, continuously winding it up with a winder, and spinning it into a fiber.
  • Short glass fibers can be produced, for example, by pouring a molten glass base from the bottom of a kiln tank into a spinner that rotates at high speed, and by centrifugal force, the fibrous glass that pops out of a hole on the side of the spinner is further processed using the pressure of a gas jet or the like. Manufactured by stretching into thin pieces. Considering these manufacturing processes, it is desirable that the glass composition has excellent meltability and good moldability, has appropriate temperature-viscosity characteristics, and has a devitrification temperature lower than the working temperature. .
  • Young's modulus The higher the Young's modulus of the glass composition forming the glass fiber, the better the elasticity of the glass fiber, which improves the mechanical properties of an inorganic cured product reinforced with glass fiber, such as glass fiber reinforced cement.
  • the Young's modulus GPa
  • the lower limit of Young's modulus may be 85 GPa or more, 86 GPa or more, 87 GPa or more, 88 GPa or more, or even 89 GPa or more.
  • the upper limit of Young's modulus may preferably be 100 GPa or less, 99 GPa or less, 98 GPa or less, 97 GPa or less, 96 GPa or less, or even 95 GPa or less.
  • the glass composition of the present embodiment can have a higher Young's modulus than E glass or AR glass.
  • ⁇ W 1 of the glass fiber is 5.0% by mass or less.
  • ⁇ W 1 of the glass composition of the present embodiment may be 5.0% by mass or less, 4.5% by mass or less, 4.0% by mass or less, 3.5% by mass or less, and even 3.0% by mass It can be:
  • the ⁇ W 1 that can be achieved by this embodiment is, for example, 0.01 to 5.0% by mass.
  • ⁇ W 2 of the glass fiber is 10.0% by mass or less.
  • ⁇ W 2 of the glass composition of the present embodiment may be 10.0% by mass or less, 9.0% by mass or less, 8.0% by mass or less, 7.0% by mass or less, or even 6.0% by mass It can be:
  • the ⁇ W 2 that can be achieved by this embodiment is, for example, 0.1 to 10.0% by mass.
  • Glass fibers made of such a glass composition with excellent chemical durability can be suitably used for reinforcing materials such as cement, mortar, concrete, and calcium silicate plates.
  • emphasis has been placed on alkali resistance, but considering use in highly acidic environments such as chemical factories and sewage-related facilities, and exposure to acid rain, it is also desirable to place emphasis on acid resistance.
  • the glass fiber of this embodiment is made of the glass composition described above.
  • the glass fibers of this embodiment may be long glass fibers or short glass fibers.
  • Long glass fibers are produced by flowing a viscosity-controlled glass melt through a nozzle and winding it up with a winder. This continuous fiber is cut to an appropriate length at the time of use.
  • Short glass fibers are manufactured by blowing away glass melt using high-pressure air, centrifugal force, or the like. Short glass fibers are sometimes called glass wool because they have a cotton-like morphology.
  • the average fiber diameter of the glass fibers is, for example, 0.1 to 50 ⁇ m.
  • the average fiber diameter of the glass fibers may be 0.1 ⁇ m or more, 0.2 ⁇ m or more, 0.3 ⁇ m or more, 0.4 ⁇ m or more, and even 0.5 ⁇ m or more, 50 ⁇ m or less, 40 ⁇ m or less, It may be 30 ⁇ m or less, or 25 ⁇ m or less.
  • the average fiber diameter may be 1 ⁇ m or more, 2 ⁇ m or more, 3 ⁇ m or more, 4 ⁇ m or more, or even 5 ⁇ m or more.
  • the average fiber diameter may be 10 ⁇ m or less, 5 ⁇ m or less, 4 ⁇ m or less, 3 ⁇ m or less, 2 ⁇ m or less, or even 1 ⁇ m or less.
  • the inorganic cured body of this embodiment includes the glass fibers described above. That is, the inorganic cured body of this embodiment is reinforced with glass fiber.
  • the inorganic hardened material include cement, mortar, concrete, calcium silicate board, and plaster.
  • the inorganic cured product may be other than those mentioned above as long as it can be manufactured by a manufacturing method that involves curing. Curing is carried out, for example, by kneading a slurry prepared by adding water to raw materials or using an autoclave.
  • the inorganic cured product may contain an organic substance as long as the remainder excluding the glass fibers is mainly composed of an inorganic substance.
  • Example and comparative example Ordinary glass raw materials such as silica sand were prepared to have the compositions shown in Tables 1 to 4, and batches of glass raw materials were prepared for each of Examples and Comparative Examples. Using an electric furnace, each batch was heated to 1500-1600° C. to melt it and maintained there for about 4 hours until the composition became uniform. Thereafter, a part of the molten glass (glass melt) was poured out onto an iron plate and slowly cooled to room temperature in an electric furnace to obtain a bulk glass composition (plate-like material, glass sample).
  • the platinum ball pulling method refers to the relationship between the load (resistance) applied when a platinum ball is immersed in molten glass and pulled up with uniform motion, and the gravity and buoyancy force acting on the platinum ball. This is a method of measuring viscosity by applying Stokes' law, which describes the relationship between viscosity and falling speed when minute particles settle in a fluid.
  • devitrification temperature A glass composition pulverized to a particle size of 1.0 to 2.8 mm was placed in a platinum boat, held in an electric furnace with a temperature gradient (800 to 1400°C) for 2 hours, and placed at the position where crystals appeared.
  • the devitrification temperature was determined from the maximum temperature of the corresponding electric furnace. When the glass became cloudy and crystals could not be observed, the maximum temperature of the electric furnace corresponding to the position where the cloudiness appeared was taken as the devitrification temperature.
  • the particle size is a value measured by a sieving method.
  • the temperature difference ⁇ T is the temperature difference obtained by subtracting the devitrification temperature from the working temperature.
  • Glass single fibers (filaments) were produced using the obtained glass composition (bulk). That is, the glass composition (bulk) was remelted in an electric furnace and then molded into pellets while being cooled. Using this pellet, a single glass fiber having a diameter of 15 ⁇ m was produced.
  • the tensile modulus of the obtained glass fiber was measured in accordance with the Japanese Industrial Standards (JIS) "Testing method for tensile properties of carbon fibers - monofilament R7606:2000".
  • JIS Japanese Industrial Standards
  • Mass reduction rate (%) ⁇ (Wa-Wb)/Wa ⁇ 100
  • Young's modulus is 88 to 95 GPa
  • tensile modulus is 76 to 87 GPa
  • working temperature is 1210 to 1283°C
  • ⁇ T working temperature - devitrification temperature
  • ⁇ W 1 is 0.26 to 3. Results of 48% by mass and ⁇ W 2 of 1.66 to 5.35% by mass were obtained.
  • the glass composition of Comparative Example 1 has an E glass composition.
  • E glass has poor acid resistance ( ⁇ W 1 ) and is also slightly inferior in Young's modulus and tensile modulus.
  • the glass composition of Comparative Example 2 has an AR glass (alkali-resistant glass) composition. Since AR glass requires a large amount of ZrO 2 , the raw material cost is high and the working temperature is also high.However, results superior to those of the Examples in terms of Young's modulus and tensile modulus could not be obtained.

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Abstract

L'invention fournit de nouvelles fibres de verre qui sont adaptées au renforcement d'un corps durci inorganique tel qu'un ciment, un mortier, un béton, des plaques silicocalcaires, un gypse, ou similaire. Plus précisément, l'invention concerne des fibres de verre pour corps durci inorganique qui contient une composition de verre comprenant, en % en masse, des composants satisfaisant ５０≦ＳｉＯ2≦６５, ０≦Ｂ2Ｏ3＜２, ５≦Ａｌ2Ｏ3≦１４, １０≦ＣａＯ≦３０, ０≦（Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏ）≦４ et ０≦ＺｒＯ2≦７.
PCT/JP2023/013381 2022-03-30 2023-03-30 Fibres de verre WO2023190980A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000247684A (ja) * 1999-03-03 2000-09-12 Nippon Sheet Glass Co Ltd ガラス繊維
JP2003500330A (ja) * 1999-05-28 2003-01-07 ピーピージー インダストリーズ オハイオ， インコーポレイテッド ガラスファイバー組成物
JP2020504067A (ja) * 2018-06-22 2020-02-06 ジュシ グループ カンパニー リミテッド ガラス繊維組成物及びそのガラス繊維、並びに複合材料
WO2020230550A1 (fr) * 2019-05-10 2020-11-19 日本電気硝子株式会社 Composition de verre pour fibres de verre
CN114014601A (zh) * 2021-12-06 2022-02-08 深圳市纳路特建材科技有限公司 耐碱隔热水泥砂浆及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000247684A (ja) * 1999-03-03 2000-09-12 Nippon Sheet Glass Co Ltd ガラス繊維
JP2003500330A (ja) * 1999-05-28 2003-01-07 ピーピージー インダストリーズ オハイオ， インコーポレイテッド ガラスファイバー組成物
JP2020504067A (ja) * 2018-06-22 2020-02-06 ジュシ グループ カンパニー リミテッド ガラス繊維組成物及びそのガラス繊維、並びに複合材料
WO2020230550A1 (fr) * 2019-05-10 2020-11-19 日本電気硝子株式会社 Composition de verre pour fibres de verre
CN114014601A (zh) * 2021-12-06 2022-02-08 深圳市纳路特建材科技有限公司 耐碱隔热水泥砂浆及其制备方法

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