WO2014115550A1 - Fibre inorganique biosoluble et composition de fibre inorganique biosoluble - Google Patents

Fibre inorganique biosoluble et composition de fibre inorganique biosoluble Download PDF

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Publication number
WO2014115550A1
WO2014115550A1 PCT/JP2014/000321 JP2014000321W WO2014115550A1 WO 2014115550 A1 WO2014115550 A1 WO 2014115550A1 JP 2014000321 W JP2014000321 W JP 2014000321W WO 2014115550 A1 WO2014115550 A1 WO 2014115550A1
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WO
WIPO (PCT)
Prior art keywords
mass
composition
mgo
cao
less
Prior art date
Application number
PCT/JP2014/000321
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English (en)
Japanese (ja)
Inventor
耕治 岩田
英樹 北原
持田　貴仁
賢 米内山
洋一 石川
達郎 三木
Original Assignee
ニチアス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by ニチアス株式会社 filed Critical ニチアス株式会社
Publication of WO2014115550A1 publication Critical patent/WO2014115550A1/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
    • C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
    • 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
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/125—Silica-free oxide glass compositions containing aluminium as glass former
    • 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
    • C03C2213/00—Glass fibres or filaments
    • C03C2213/02—Biodegradable glass fibres

Definitions

  • the present invention relates to a novel biosoluble inorganic fiber and a composition for obtaining the inorganic fiber.
  • conventional inorganic fibers are secondary-processed into shaped products and irregular shaped materials, together with various binders and additives, and joint materials in furnaces such as heat treatment equipment, industrial kilns and incinerators, It is used as a joint material, a sealing material, a packing material, a heat insulating material, and the like for filling gaps such as refractory tiles, heat insulating bricks, iron skin, and mortar refractories. Therefore, it is often exposed to high temperatures during use, and preferably has heat resistance. Further, alumina is often used for the wall surface in the furnace, and it is preferable that the fibers contained in the secondary processed product react with the alumina and the secondary processed product and the wall surface do not adhere or melt.
  • An object of the present invention is to provide a novel biosoluble inorganic fiber and a composition for obtaining the inorganic fiber.
  • the following inorganic fiber composition and inorganic fiber are provided.
  • the composition for inorganic fibers according to 1 or 2 having the following composition. Al 2 O 3 0.0-97.0 mass% CaO 0.0-97.0 mass% MgO 3.0-94.0% by mass 4).
  • the inorganic fiber composition according to any one of 1 to 4 having the following composition. Al 2 O 3 60.0-78.0 mass% CaO 12.0-30.0 mass% MgO more than 10.0% by mass and 20.0% by mass or less13.
  • 14 The composition for inorganic fibers according to any one of 1 to 6, wherein the total of Al 2 O 3 , CaO and MgO is 90.0% by mass or more.
  • the composition for inorganic fibers according to any one of 1 to 6, wherein the total of Al 2 O 3 , CaO and MgO is 95.0% by mass or more. 16.
  • a novel biosoluble inorganic fiber and a composition for obtaining the inorganic fiber can be provided.
  • the biological solubility in this invention says the solubility with respect to the physiological saline of pH4.5.
  • the fiber composition of the present invention contains one or two components selected from Al 2 O 3 and CaO, and MgO as main components.
  • the main component means that two or three components having the highest content (mass%) among all the components contained in the composition are 1 or 2 selected from Al 2 O 3 and CaO, and MgO. means.
  • Al 2 O 3 , CaO and MgO are included as main components.
  • 3.0% by mass or more of MgO is included as a viscosity modifier.
  • the fiber composition of the present invention preferably has the following composition from the viewpoint of biosolubility and heat resistance.
  • Al 2 O 3 0.0-97.0 mass% CaO 0.0-97.0 mass% MgO 3.0-94.0% by mass
  • the above composition can be further set as the following composition.
  • the above composition can be further set as the following composition. Al 2 O 3 16.0-93.0% by mass CaO 3.0-62.0 mass% MgO 4.0-55.0 mass%
  • the above composition can be further set as the following composition.
  • the above composition can be further set as the following composition.
  • the above composition can be further set as the following composition.
  • the above composition can be further set as the following composition. Al 2 O 3 64.0-93.0% by mass CaO 3.0-36.0 mass% MgO 4.0-28.0 mass%
  • the above composition can be further set as the following composition.
  • Al 2 O 3 60.0-84.0% by mass CaO 3.0-36.0 mass%
  • the above composition can be further set as the following composition.
  • the above composition can be further set as the following composition.
  • each component of said composition may be combined arbitrarily.
  • the total of the components to be specified is 80.0% by mass or more, 90.0% by mass or more, 95.0% by mass or more, 97.0% by mass or more, 98.0% by mass or more, 99. It is good also as 0 mass% or more or 100.0 mass%.
  • the rest other than the specified components is oxides or impurities of other elements.
  • the composition of the present invention comprises a respective oxide selected from Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or mixtures thereof. May or may not be included.
  • the amount of these oxides is 20.0% by mass or less, 10.0% by mass or less, 5.0% by mass or less, 3.0% by mass or less, 2.0% by mass or less, 1.0% by mass or less, respectively. 0.5% by mass or less, 0.2% by mass or less, or 0.1% by mass or less.
  • Each of the alkali metal oxides may or may not be contained, and the alkali metal oxides are each or 20.0% by mass or less in total. 0 mass% or less, 5.0 mass% or less, 3.0 mass% or less, 2.0 mass% or less, 1.0 mass% or less, 0.5 mass% or less, 0.2 mass% or less, or 0.1 It can be made into the mass% or less.
  • Each of ZrO 2 , ZnO, B 2 O 3 , P 2 O 5 , SrO, BaO, Cr 2 O 3 , SiO 2 , Fe 2 O 3 , and TiO 2 may or may not be included, each 20 0.0 mass% or less, 10.0 mass% or less, 5.0 mass% or less, 3.0 mass% or less, 2.0 mass% or less, 1.0 mass% or less, 0.5 mass% or less, It can be 2 mass% or less or 0.1 mass% or less.
  • composition of the present invention usually does not contain the following substances, or even if contained, it is 0.2% by mass or less or 0.1% by mass or less, respectively.
  • Inorganic fibers can be obtained from the composition of the present invention.
  • the fiber of the present invention can be produced by a known method such as a melting method or a sol-gel method, but the melting method is preferred because of low cost.
  • a raw material melt is produced by a normal method, and the melt is made into a fiber.
  • it can be manufactured by a spinning method in which a melted raw material is poured onto a wheel rotating at high speed, and a blow method in which the melted raw material is fiberized by applying compressed air.
  • the fiber of the present invention may or may not be coated with a known coating material.
  • the solubility during storage and use can be adjusted by coating.
  • the fiber of the present invention is the same as the composition of the raw material composition, and has solubility (biological solubility) in physiological saline having a pH of 4.5 by having the above composition.
  • the solubility in physiological saline of pH 4.5 is preferably 1.0 mg / g or more, more preferably 1.5 mg / g or more, and further preferably 3.0 mg / g or more, according to the measurement method of the example.
  • solubility biological solubility
  • physiological saline having a pH of 7.4 has solubility (biological solubility) in physiological saline having a pH of 7.4.
  • the solubility in physiological saline at pH 7.4 is preferably 1.0 mg / g or more, more preferably 1.5 mg / g or more, and even more preferably 3.0 mg / g or more, according to the measurement method of the example.
  • the dissolution rate constant is preferably 10 ng / cm 2 ⁇ h or more, more preferably 50 ng / cm 2 ⁇ h or more, still more preferably 100 ng / cm 2 ⁇ h or more, and particularly preferably 200 ng / cm by the measurement method of the example. 2 ⁇ h or more.
  • the fibers of the present invention preferably have low alumina reactivity.
  • the alumina reactivity is preferably not adhered or does not react with the measurement method of the examples.
  • the fibers of the present invention preferably have heat resistance at 800 ° C or higher, 1000 ° C or higher, 1100 ° C or higher, 1200 ° C or higher, 1300 ° C or higher, 1400 ° C or higher.
  • the volume shrinkage (%) is 40% or less, preferably 30% or less at 1400 ° C. for 8 hours by the measurement method of the example. It is 40% or less, preferably 30% or less, more preferably 23% or less, and most preferably 15% or less at 1300 ° C. for 8 hours. It is 40% or less, preferably 30% or less, more preferably 23% or less, and most preferably 15% or less at 1200 ° C. for 8 hours.
  • the fiber of the present invention is preferably measured by the measurement method of the Examples, and the linear shrinkage rate is determined at each temperature (600 ° C, 800 ° C, 1000 ° C, 1100 ° C, 1200 ° C, 1300 ° C, 1400 ° C, 1500 ° C, 1600 ° C). ), Preferably 30% or less, more preferably 20% or less, still more preferably 10% or less, and most preferably 5% or less.
  • the heat shrinkage rate of the fiber can be measured before and after producing a blanket from the fiber and firing it at 1100 ° C. and 1260 ° C. for 24 hours.
  • the tensile strength can be measured with a universal testing machine.
  • the fiber of the present invention can reduce the types of essential components, the number of man-hours for the blending process is reduced and the cost is reduced. In addition, the fact that there are few kinds of components for adjusting delicate blending amounts reduces the difficulty of production.
  • Examples 1-18 The fiber composition shown in Table 1 was examined as follows. First, the raw materials were mixed so as to have the composition shown in Table 1, and pressed to obtain a molded body. The molded product was melted by heating and rapidly cooled to obtain a sample. Using this sample, the following method was used for evaluation. The results are shown in Table 1.
  • Biosolubility 1 g of a sample was placed in an Erlenmeyer flask (volume: 300 mL) containing 150 mL of physiological saline having a pH of 4.5 or pH 7.4. This flask was placed in an incubator at 37 ° C., and horizontal vibration at 120 revolutions per minute was continued for 2.5 hours. Thereafter, the amount (mg) of each element contained in the filtrate obtained by filtration was measured with an ICP emission spectrometer, and the total was taken as the elution amount (mg / sample 1 g).
  • volume shrinkage The sample was molded to obtain a cylindrical sample having a diameter of about 7 mm and a height of about 15 mm. This columnar sample was heated at 1400 ° C. for 8 hours to determine the volume shrinkage (%).
  • Alumina reaction resistance A sample was molded to obtain a cylindrical sample having a diameter of about 7 mm and a thickness of about 5 mm. This cylindrical sample was placed on an alumina plate and heated at 1400 ° C. for 8 hours to observe the presence or absence of adhesion or melting. It was 4 when the cylindrical sample was melted, 3 when it was adhered, 2 when it was not adhered but remained, and 1 when it was not adhered and remained.
  • Comparative Example 1 A ceramic fiber (conventional heat-resistant inorganic fiber) (Comparative Example 1) containing 47.2% by mass of SiO 2 and 52.7% by mass of Al 2 O 3 was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Examples 19-31 Fibers having the compositions shown in Table 2 were produced by a melting method. The obtained fiber was evaluated by the following method. The results are shown in Table 2.
  • Dissolution rate constant The fiber was placed on a membrane filter, physiological saline of pH 4.5 or pH 7.4 was dropped on the fiber with a micropump, and the filtrate passing through the fiber and filter was stored in a container. The accumulated filtrate was taken out after 24 hours, and the eluted components were quantified with an ICP emission spectrometer.
  • the measurement elements were three elements of Mg, Al and Ca which are main elements.
  • the fiber diameter was measured and converted to a dissolution rate constant k (unit: ng / cm 2 ⁇ h) which is the amount of elution per unit surface area / unit time.
  • the inorganic fiber of the present invention can be used for various purposes as a heat insulating material or as a substitute for asbestos.

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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)
  • General Life Sciences & Earth Sciences (AREA)
  • Glass Compositions (AREA)
  • Inorganic Fibers (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

L'invention concerne une composition de fibre inorganique contenant, en tant que principaux composants, du MgO et un ou plusieurs composants choisis dans le groupe comprenant Al2O3 et CaO.
PCT/JP2014/000321 2013-01-23 2014-01-23 Fibre inorganique biosoluble et composition de fibre inorganique biosoluble WO2014115550A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-010217 2013-01-23
JP2013010217A JP2014141367A (ja) 2013-01-23 2013-01-23 生体溶解性無機繊維及びその組成物

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WO2014115550A1 true WO2014115550A1 (fr) 2014-07-31

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WO (1) WO2014115550A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016065333A (ja) * 2014-09-24 2016-04-28 三菱樹脂株式会社 無機繊維、無機繊維集合体及び無機繊維成形体

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108368277A (zh) * 2015-12-25 2018-08-03 日本制纸株式会社 母料、橡胶组合物和它们的制造方法
DE102016121699A1 (de) * 2016-11-11 2018-05-17 Schwartz Gmbh Temperierstation zur partiellen Wärmebehandlung eines metallischen Bauteils
JP6432616B2 (ja) * 2017-02-09 2018-12-05 品川リフラクトリーズ株式会社 鋼の連続鋳造用ノズルへの断熱材の貼り付け方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS506823A (fr) * 1973-06-02 1975-01-24
JPH06272116A (ja) * 1992-08-26 1994-09-27 Didier Werke Ag 無機繊維
JP2009542927A (ja) * 2006-06-30 2009-12-03 ユニフラックス Ｉ リミテッド ライアビリティ カンパニー 無機繊維
US20120119133A1 (en) * 2010-11-16 2012-05-17 Zoitos Bruce Kendall Inorganic fiber
WO2012073989A1 (fr) * 2010-11-30 2012-06-07 ニチアス株式会社 Fibres inorganiques et leur procédé de fabrication
WO2012114565A1 (fr) * 2011-02-24 2012-08-30 ニチアス株式会社 Fibres inorganiques

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS506823A (fr) * 1973-06-02 1975-01-24
JPH06272116A (ja) * 1992-08-26 1994-09-27 Didier Werke Ag 無機繊維
JP2009542927A (ja) * 2006-06-30 2009-12-03 ユニフラックス Ｉ リミテッド ライアビリティ カンパニー 無機繊維
US20120119133A1 (en) * 2010-11-16 2012-05-17 Zoitos Bruce Kendall Inorganic fiber
WO2012073989A1 (fr) * 2010-11-30 2012-06-07 ニチアス株式会社 Fibres inorganiques et leur procédé de fabrication
WO2012114565A1 (fr) * 2011-02-24 2012-08-30 ニチアス株式会社 Fibres inorganiques

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016065333A (ja) * 2014-09-24 2016-04-28 三菱樹脂株式会社 無機繊維、無機繊維集合体及び無機繊維成形体

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