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WO1992006931A1 - Verre filable a resistance elevee aux alcalis - Google Patents

Verre filable a resistance elevee aux alcalis Download PDF

Info

Publication number
WO1992006931A1
WO1992006931A1 PCT/DE1991/000790 DE9100790W WO9206931A1 WO 1992006931 A1 WO1992006931 A1 WO 1992006931A1 DE 9100790 W DE9100790 W DE 9100790W WO 9206931 A1 WO9206931 A1 WO 9206931A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
cao
alkali
textile glass
resistant textile
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/DE1991/000790
Other languages
German (de)
English (en)
Inventor
Andreas Balzer
Klaus Forkel
Peter Felsberg
Jörg FRIEDRICH
Rolf Masthoff
Joachim Milbradt
Werner Riedel
Christian Schulze
Hannelore Triebel
Lothar Vonderlind
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Thueringer Glasfaser GmbH
Original Assignee
Thueringer Glasfaser GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Thueringer Glasfaser GmbH filed Critical Thueringer Glasfaser GmbH
Publication of WO1992006931A1 publication Critical patent/WO1992006931A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C03C13/001—Alkali-resistant fibres
    • C03C13/002—Alkali-resistant fibres containing zirconium

Definitions

  • the invention relates to a spinnable glass, in particular a high alkali resistance, which can be processed into threads / fibers by means of the technology available in the glass silk or glass fiber industry.
  • the threads and fibers thus produced can be used as fillers for preferably composite materials in the field of construction.
  • the main purpose of this known glass is to create a composition with low devitrification speed, a suitable viscosity at low melt temperatures, a low melting temperature, a wide processing range and high resistance of the glass and the fibers to the attack by water and acids.
  • the chemical composition of the E and C glass for glass fibers is known (Loewenstein, .L .: The Manufacturing Technology of Continuous Glass Fibers. Glass Science and Technology 6. Elsevier, Amsterdam / Oxford / New York 1983).
  • the patent DE-PS 1040444 describes the use of artificial mineral fibers for the production of moldings, plates, pipes and the like using cement as a binder, the weather-resistant, highly elastic silicate glass fibers or threads used as main components (mass fractions in %): 40 to 65 Si0 2 ; 5 to 24 A1-0-; 15 to 40 MgO with a total alkali content (Na-0 + K-0) less than 1.
  • DE-PS 2614395 describes an alkali-resistant glass which is characterized by the following chemical composition (mass fraction in%) istl 40 to 65 SiO-j 10 to 20 ZrO-j 0 to 5 Cr-O- j ⁇ 0 to 18
  • a glass with the chemical composition (mass fraction in%) 71.3 Si0 2 ; 11.5 Na 2 0 and 15.8 Zr0 2 and 0.8 i 2 0 describe next to.
  • Zr0 2 -free glasses FR BACON and RAGGON (J. Amer, Ceram.Soc. 42 (1959) 199 - 205) in connection with attack by citrates and other anions in neutral solution on glass and Si0 2 .
  • neutral solutions of sodium citrate in a similar way attack surfaces of silicate glasses and SiO-, as is known from al ⁇ -earth aqueous solutions * This effect is for both the so-called.
  • the Zr0 2 -containing glass called Zr-Erlenmeyer flask taken into account here is neither with regard to its resistance to basic aqueous media, which have an analogy to the pore liquid occurring in the cement paste, nor with regard to Applicability of a spinning process for the production of glass silk or glass fibers have been characterized, so that with the mention of the glass composition no ad hoc suitability for the areas of cement reinforcement mentioned here and technological assurance of the implementation of the spinning process must be given.
  • the object of the invention is to develop such a glass composition without fluoride-containing flux for a spinnable glass, in particular for glass fibers of high alkali resistance with low processing temperatures, with which the use of the existing spinning machines enables the glass fiber and glass fiber industry becomes.
  • the glass used for the production of glass silk spun threads and fiberglass tape and the derived products made therefrom is characterized in that it contains as main components (mass fractions in%): 60 to 65 Si0 2 11 13 ZrO-
  • This glass developed according to the invention has a relatively high proportion of glass formers and intermediate oxides without the presence of fluoride-containing fluxes and shows similar processing properties to those skilled in the art of E-glass (aluminum borosilicate alkali content j L1%) and to a certain extent also of C-glass (alkali-lime glass with increased boron trioxide content) are known.
  • E-glass aluminum borosilicate alkali content j L1%
  • C-glass alkali-lime glass with increased boron trioxide content
  • the spinnable glass is also characterized in that up to 3 parts by mass in% CaO can be replaced by CaF 2 .
  • a type of the glass according to the invention is to be characterized in more detail below using an example.
  • composition of the glass according to the invention corresponds to the following:
  • Zirconium silicate 15.80% dolomite (moist) 8.05% lime powder 8.80% sand 47.29% sodium sulfate 0.42% soda 19.22% soda / coal mixture 0.42%
  • a normal glass melting port is used as the melting vessel
  • the melting temperature is 1480 C.
  • Devitrification cannot be determined during shaping.
  • the temperature in the upper furnace is approx. 1250 to 1300 ° C with a working fire.
  • REPLACEMENT LEAF 2 Processing of the glass to form filaments or fibers, the processing of the glass takes place in a known manner ent ⁇ speaking of the glass fiber spinning process at 1180 C, the DUsenziehvons at 1390 ° C and the rod drawing process at 1050 ° C.
  • the manufacture of the glass fiber filaments by the glass takes place are spinning process in accordance with the silk industry in the Glas ⁇ usual practice, where instead of the noble ⁇ metal bushing, a nozzle crucible having a capacity of one liter, and in the bottom of the crucible introduced precious metal nozzle is used, with a Medium-frequency system is heated inductively.
  • a 10% aqueous solution of dimethyldodecylbenzylammonium chloride is used as the size and the spinning bobbins are dried at 45 ° C. in a drying cabinet.
  • the fineness of the roving produced from the spinning bobbins is 2400 tex and 6 mm long fiber bundles are produced from the roving.
  • the fiber diameter is 13 to 25 / um.
  • the starting material for the production of the glass is utiliseba ⁇ des from pellets of the glass according to the invention, the one in a tub with an embedded as a trough base current-carrying and existing as a resistance nozzle bar of noble metal (Pt / Rh) in Temperature of 1390 C can be melted.
  • Glass droplets are formed at the nozzles, each of which draws a thread and are drawn out to the desired fiber thickness by deflection in the spinning device by means of water jets on the rotating spinning drum due to the high peripheral speed.
  • the fibers are lifted off by a scraper, swirled in a fiber sliver funnel after wetting with lubricating oil, drawn through the funnel opening and fed to a winding device.
  • E RSAT ZBLATT Diethylene glycol is used as an antistatic.
  • the sliver produced has a fineness of 720 tex.
  • rods of the glass according to the invention are guided to a burner flame system, so that the melted drops pull threads and are continuously wound onto a rotating take-off drum by deflection through a guide plate.
  • the melting temperature is approx. 1050 ° C.
  • the use of the glass silk threads or fiber ribbon produced by these known methods is used as reinforcement of a basic matrix, in particular for the consolidation of cement and concrete.
  • Fibers from the glass according to the invention are Fibers from the glass according to the invention.
  • the plates (30 cm x 30 cm) were drained in a laboratory casting press using PVC sieves with a mesh size of 0.3 mm.
  • the raw plates were autoclaved for 5.5 hours at a temperature of 181 ° C and then dried to constant weight at a temperature of 105 ° C.
  • a flexural strength of 4.8 MPa with a density of 0.565 g / cm was determined.
  • the plates are not flammable.

Landscapes

  • 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)
  • Glass Compositions (AREA)

Abstract

Un verre filable à résistance élevée aux alcalis peut être traité ultérieurement par des techniques connues de transformation en fibres ou en fils, ces fibres étant particulièrement utiles pour des matériaux composites dans le domaine de la construction. Le but de l'invention est de développer une composition de verre filable à des températures réduites ne contenant pas de fondants fluorés. Le verre filable décrit à résistance élevée aux alcalis se caractérise par le fait qu'il contient en tant que composants principaux (en pourcentage en poids): 60 à 65 % de SiO2; 11 à 13 % de ZrO2; 0,1 à 5 % de TiO2; 0,4 à 4 % de Al2O3; 0,1 à 2 % de B2O3; 6 à 10 % de CaO; 1 à 4 % de MgO; 10 à 15 % de Na2O; 0,1 à 2 % de K2O. Ce verre se caractérise en outre par le fait que jusqu'à 3 % en poids de CaO sont substitués par du CaF2.
PCT/DE1991/000790 1990-10-10 1991-10-09 Verre filable a resistance elevee aux alcalis Ceased WO1992006931A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4032460.5 1990-10-10
DE19904032460 DE4032460A1 (de) 1990-10-10 1990-10-10 Spinnfaehiges glas hoher alkaliresistenz

Publications (1)

Publication Number Publication Date
WO1992006931A1 true WO1992006931A1 (fr) 1992-04-30

Family

ID=6416183

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1991/000790 Ceased WO1992006931A1 (fr) 1990-10-10 1991-10-09 Verre filable a resistance elevee aux alcalis

Country Status (2)

Country Link
DE (1) DE4032460A1 (fr)
WO (1) WO1992006931A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009056768A3 (fr) * 2007-10-31 2009-06-25 Saint Gobain Technical Fabrics Fils de verre a faible teneur en alumine aptes a renforcer des matieres organiques et/ou inorganiques
US9212086B2 (en) 2006-10-25 2015-12-15 Owens Corning Intellectual Capital, Llc Chemically resistant glass composition for the manufacture of glass reinforcing strands
US9790122B2 (en) 2005-10-28 2017-10-17 Ocv Intellectual Capital, Llc Alkali-and acid-resistant glass composition for the manufacture of glass strands
CN109982982A (zh) * 2016-12-27 2019-07-05 日本电气硝子株式会社 玻璃纤维用玻璃组合物、玻璃纤维和玻璃纤维的制造方法

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19945517B4 (de) * 1999-02-15 2005-03-17 Schott Ag Hochzirconiumoxidhaltiges Glas und seine Verwendungen
AU764593B2 (en) 1999-02-15 2003-08-21 Carl-Zeiss-Stiftung Trading As Schott Glaswerke Glass with high proportion of zirconium-oxide and its uses
DE19906240A1 (de) 1999-02-15 2000-08-17 Schott Glas Hochzirkoniumoxidhaltiges Glas und dessen Verwendungen
EP1630144A1 (fr) * 2004-08-31 2006-03-01 Saint-Gobain Revetex S.r.l. Additif en fil de verre résistant aux alkalis pour béton perméable et béton perméable obtenu avec tel additif
EP1630145A1 (fr) * 2004-08-31 2006-03-01 Saint-Gobain Revetex S.r.l. Additif en fil de verre résistant aux alkalis pour matrices en béton, procédé de fabrication de tel additif et matrices de béton le contenant
US9593038B2 (en) 2009-08-03 2017-03-14 Ppg Industries Ohio, Inc. Glass compositions and fibers made therefrom
US9446983B2 (en) 2009-08-03 2016-09-20 Ppg Industries Ohio, Inc. Glass compositions and fibers made therefrom
US9556059B2 (en) 2009-08-03 2017-01-31 Hong Li Glass compositions and fibers made therefrom

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5059528A (fr) * 1973-09-28 1975-05-22
US4014705A (en) * 1971-11-03 1977-03-29 Pilkington Brothers Limited Glass compositions
DE2656002A1 (de) * 1976-12-10 1978-06-15 Inst De Cercetari Proiectari Glas hoher alkalibestaendigkeit, aus ihm hergestellte glasfasern, verfahren zu ihrer herstellung und mit glasfasern bewehrtes zementerzeugnis
GB2071081A (en) * 1980-02-27 1981-09-16 Pilkington Brothers Ltd Alkali resistant glass fibres and cementitious products reinforced with such glass fibres
SU1366488A1 (ru) * 1986-05-13 1988-01-15 Государственный научно-исследовательский институт стекла Стекло

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD97192A5 (fr) * 1971-02-15 1973-04-20
GB1459385A (en) * 1973-02-14 1976-12-22 Turner Newall Ltd Glass fibres
IE49426B1 (en) * 1980-03-18 1985-10-02 Tegral Technology Ltd Method of making asbestos-free,glass fibre reinforced,cement composite products and the products of such method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014705A (en) * 1971-11-03 1977-03-29 Pilkington Brothers Limited Glass compositions
JPS5059528A (fr) * 1973-09-28 1975-05-22
DE2656002A1 (de) * 1976-12-10 1978-06-15 Inst De Cercetari Proiectari Glas hoher alkalibestaendigkeit, aus ihm hergestellte glasfasern, verfahren zu ihrer herstellung und mit glasfasern bewehrtes zementerzeugnis
GB2071081A (en) * 1980-02-27 1981-09-16 Pilkington Brothers Ltd Alkali resistant glass fibres and cementitious products reinforced with such glass fibres
SU1366488A1 (ru) * 1986-05-13 1988-01-15 Государственный научно-исследовательский институт стекла Стекло

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
15TH INTERNATIONAL CONGRESS ON GLASS, LENINGRAD,1989, PROCEEDINGS VOL. 2B, seiten 117-119. A.PLSKO ET AL: "The Research of Glasses Suitable for Alkali-Resistant Fibers Production." siehe Tabelle 1 *
CHEMICAL ABSTRACTS, vol. 108, no. 14, 4. April 1988, Columbus, Ohio, US; abstract no. 117560X, Seite 331 ; siehe Zusammenfassung & SU,A,1 366 488 (D.L.ORLOV) 15. Januar 1988 *
CHEMICAL ABSTRACTS, vol. 84, no. 12, 22. M{rz 1976, Columbus, Ohio, US; abstract no. 78599F, Seite 306 ; siehe Zusammenfassung & JP,A,50 059 528 (ASAHI GLASS CO.) 22. Mai 1975 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9790122B2 (en) 2005-10-28 2017-10-17 Ocv Intellectual Capital, Llc Alkali-and acid-resistant glass composition for the manufacture of glass strands
US9212086B2 (en) 2006-10-25 2015-12-15 Owens Corning Intellectual Capital, Llc Chemically resistant glass composition for the manufacture of glass reinforcing strands
US9932263B2 (en) 2006-10-25 2018-04-03 Ocv Intellectual Capital, Llc Glass composition having improved hydraulic resistance for the manufacture of glass reinforcing strands
WO2009056768A3 (fr) * 2007-10-31 2009-06-25 Saint Gobain Technical Fabrics Fils de verre a faible teneur en alumine aptes a renforcer des matieres organiques et/ou inorganiques
US8367571B2 (en) 2007-10-31 2013-02-05 Saint-Gobain Technical Fabrics Europe Glass strands with low alumina content capable of reinforcing organic and/or inorganic materials
CN109982982A (zh) * 2016-12-27 2019-07-05 日本电气硝子株式会社 玻璃纤维用玻璃组合物、玻璃纤维和玻璃纤维的制造方法

Also Published As

Publication number Publication date
DE4032460A1 (de) 1992-06-11

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