NO133269B - - Google Patents

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Publication number
NO133269B
NO133269B NO1755/73A NO175573A NO133269B NO 133269 B NO133269 B NO 133269B NO 1755/73 A NO1755/73 A NO 1755/73A NO 175573 A NO175573 A NO 175573A NO 133269 B NO133269 B NO 133269B
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NO
Norway
Prior art keywords
glass
fluorine
boron
composition
viscosity
Prior art date
Application number
NO1755/73A
Other languages
Norwegian (no)
Other versions
NO133269C (en
Inventor
T D Erickson
W W Wolf
R L Tiede
J A Williams
Original Assignee
Owens Corning Fiberglass Corp
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 Owens Corning Fiberglass Corp filed Critical Owens Corning Fiberglass Corp
Priority to NO750123A priority Critical patent/NO135060C/no
Priority to NO75752092A priority patent/NO135629C/no
Publication of NO133269B publication Critical patent/NO133269B/no
Publication of NO133269C publication Critical patent/NO133269C/no

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Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C13/00Fibre or filament compositions

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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)
  • Glass Compositions (AREA)

Description

Piberbare glass-sammensetninger omfatter idag bor-og fluorholdige forbindelser som flussmidler, hvilke reduserer viskositeten i satsen spesielt under de tidlige trinn av smel-tingen. Etter at man har erkjent bor og fluor som potensielt forurensende stoffer har problemet vært å fremstille en glass-sammensetning som (1) har de nødvendige fysikalske egenskaper for fiberdannelse, (2) som er akseptable for industrien og (3) som ikke omfatter fluor og bor. Piperable glass compositions today include boron- and fluorine-containing compounds as fluxes, which reduce the viscosity of the batch, especially during the early stages of melting. Having recognized boron and fluorine as potentially polluting substances, the problem has been to produce a glass composition which (1) has the necessary physical properties for fiber formation, (2) which are acceptable to industry and (3) which does not include fluorine and lives.

For eksempel har E-glass, som er den mest vanlige glass-sammensetning som idag benyttes for fremstilling av tekstilfibre fra 9 til 11 vekt-% B2°3 og kan innenolde fluor som flussmiddel. Spesifikasjonene for E-glassfibre krever også at prosentandelen av alkalimetalloksyder, nemlig Na20, K20 og LigO, er mindre enn 1 vekt-$, beregnet som Na20. Det er derfor viktig å holde alkalimetalloksydnivået for glass-sammensetningene på 1% eller mindre når det utvikles nye glass-sammensetninger som kan benyttes istedenfor E-glass. Sammensetningen for. E-glass er beskrevet i US-patent nr. 2.33^.961. For example, E-glass, which is the most common glass composition used today for the production of textile fibers, has from 9 to 11% by weight B2°3 and can contain fluorine as a flux. The specifications for E-glass fibers also require that the percentage of alkali metal oxides, namely Na 2 O, K 2 O and LigO, be less than 1 wt-$, calculated as Na 2 O. It is therefore important to keep the alkali metal oxide level for the glass compositions at 1% or less when developing new glass compositions that can be used instead of E-glass. The composition for. E-glass is described in US patent no. 2,33^,961.

Bor benyttes vanligvis i satssammensetningen som kolemanit, vannfri borsyre eller borsyre mens fluor tilsettes som CaF2 eller natriumsilicofluorid (Na2SiFg). Smelting av glassråstoffet i gassoppvarmede ovner, f.eks. for danning av smeltet glass, hvorfra fibrene kan trekkes og dannes, omfatter oppvarmingen av satsen og det smeltede glass til temperaturer på over 1204°C. Vanlige benyttede tekstilfibre smeltes i om-rådet 13l6-1510°C. Ved disse smeltingstemperaturer har B20^ og F^ heller forskjellige forbindelser av bor og fluor en tendens til å fordampe ut av det smeltede glass, og gassene kan trekkes opp gjennom avtrekkene og slippes ut til atmos-færen som omgir fabrikken. Boron is usually used in the batch composition as colemanite, anhydrous boric acid or boric acid, while fluorine is added as CaF2 or sodium silicofluoride (Na2SiFg). Melting of the glass raw material in gas-heated furnaces, e.g. for forming molten glass, from which the fibers can be drawn and formed, involves heating the batch and the molten glass to temperatures in excess of 1204°C. Commonly used textile fibers are melted in the range 1316-1510°C. At these melting temperatures, B20^ and F^, rather different compounds of boron and fluorine, tend to evaporate out of the molten glass, and the gases can be drawn up through the flues and released into the atmosphere surrounding the factory.

Den resulterende luft- og mulige vannforurensning kan reduseres eller elimineres på flere måter. Vannvasking eller filtrering av utslippsgassene kan ofte rense utslipps-luften. Bruken av elektriske ovner istedenfor gassfyrte ovner vil vesentlig eliminere tapet av flyktige flussmidler (f.eks. bor og fluor) som vanligvis forbindes med gassfyrte ovner ved temperaturer over 1204°C. Disse rensingstiltak er imidlertid ofte kostbare og kan unngås hvis forurensningskilden kan fjernes fra giass-sammensetningene. Noe som imidlertid kompli-serer dette er det faktum at man ved å fjerne bor og fluor fjernes to vanligvis benyttede flussmidler i fibrerbare glass-sammensetninger. Det har vist seg å være vanskelig å oppnå akseptable smeltehastigheter, smelting- og driftstemperaturer, likvidus og viskositet i fravær av bor og fluor. The resulting air and possible water pollution can be reduced or eliminated in several ways. Water washing or filtering the exhaust gases can often clean the exhaust air. The use of electric furnaces instead of gas-fired furnaces will substantially eliminate the loss of volatile fluxes (eg boron and fluorine) usually associated with gas-fired furnaces at temperatures above 1204°C. However, these cleaning measures are often expensive and can be avoided if the source of contamination can be removed from the giass compositions. Something that complicates this, however, is the fact that by removing boron and fluorine, two commonly used fluxes in fibrable glass compositions are removed. It has proven difficult to achieve acceptable melting rates, melting and operating temperatures, liquidus and viscosity in the absence of boron and fluorine.

Et akseptabelt driftsområde i en kommersiell tek-stilglassmater er mellom 1232 og 1371°C. En glass-sammensetning som oppfører seg godt i denne omgivelse bør helst ha en likvidustemperatur på omtrent 120<i>}°C eller mindre og en viskositet på log 2,5 poise ved 13l6°C eller mindre. An acceptable operating range in a commercial tek style glass feeder is between 1232 and 1371°C. A glass composition that behaves well in this environment should preferably have a liquidus temperature of about 120<i>}°C or less and a viscosity of log 2.5 poise at 1316°C or less.

Fiberfremstillingstemperaturen er helst omkring 55°C over likvidustemperaturen for å unngå devitrifisering (krystallvekst) i glasset når fibrene dannes. Fordi devitrifisering forårsaker uregelmessigheter eller kjerner i glasset som hemmer eller som kan stoppe fiberfremstillingen, bør likvidustemperaturen for et kommersielt tekstilglass helst være mindre enn omkring 1204°C. Glassets viskositet er også en nøkkel for effektiv og økonomisk fiberfremstilling. Glass-viskositeter på log 2,5 poises ved 1343°C eller mer krever så høye temperaturer for å smelte glasset, for å gi det flyt-egenskaper og gjøre det formbart til fibre at de metalliske bøssinger eller matere kan. bli ubrukbare eller må erstattes eller repareres hyppigere enn bøssinger som kommer i kontakt med mindre viskøse glasstyper. The fiber production temperature is preferably around 55°C above the liquidus temperature to avoid devitrification (crystal growth) in the glass when the fibers are formed. Because devitrification causes irregularities or nuclei in the glass that inhibit or may stop fiber production, the liquidus temperature of a commercial textile glass should ideally be less than about 1204°C. The viscosity of the glass is also a key to efficient and economical fiber production. Glass viscosities of log 2.5 poise at 1343°C or more require such high temperatures to melt the glass, to give it flow properties and make it formable into fibers that the metallic bushings or feeders can. become unusable or need to be replaced or repaired more frequently than bushings that come into contact with less viscous types of glass.

Foreliggende oppfinnelse angår således bor- og fluorfri glass-sammensetning til fremstilling.av glassfibre og med en viskositet på log 2,5 pois ved 13^3°C. eller mindre, og sammensetningen karakteriseres ved åt den i det vesentlige består av The present invention thus relates to a boron- and fluorine-free glass composition for the production of glass fibers and with a viscosity of log 2.5 pois at 13^3°C. or less, and the composition is characterized by what it essentially consists of

Si02 54 64 vekt-#, Si02 54 64 weight #,

A1203 9-19 A1203 9-19

CaO 9-25 vekt-55 CaO 9-25 wt-55

Ti02 3-5 " Ti02 3-5"

MgO 1,5 - 4,5 " MgO 1.5 - 4.5"

Slik det fremgår av det ovenforstående er dette i det vesentlige en 5-komponentsammenseting. I den grad de ifølge oppfinnelsen angitte glass-sammensetninger inneholder ytterligere oksyder foruten de 5 ovenfor angitte oksyder Si02, Al20j, CaO, Ti02 og MgO er det kun snakk som tilfeldige foru-rensninger. As can be seen from the above, this is essentially a 5-component composition. To the extent that the glass compositions according to the invention contain further oxides in addition to the 5 above-mentioned oxides SiO 2 , Al 2 O 2 , CaO, TiO 2 and MgO, it is only a question of accidental contamination.

Glass-sammensetningene som faller innenfor den ovenfor angitte definisjon kan trekkes til fine, kontinuerlige fibre med en diamter på omkring 3,7 x 10 ^ til 14 x 10 ^. The glass compositions falling within the above definition can be drawn into fine, continuous fibers having a diameter of about 3.7 x 10 2 to 14 x 10 2 .

Noen eksempler på glass-sammensetninger ifølge oppfinnelsen angis i følgende tabell: Some examples of glass compositions according to the invention are given in the following table:

Viskositetsbestemmelsene i eksemplene ovenfor ble oppnådd ved bruk av den apparatur og fremgangsmåte som er beskrevet i US-patent nr. 3.056.283 og i en artikkel i "The Journal of the American Ceramic Society", vol. 42, nr. 11, november 1959j sidene 537-541. Artikkelen har titlen "Improved Apparatus for Rapid Measurement of Viscosity of Glass at High Temperatures" og er skrevet av Ralph L. Tiede. The viscosity determinations in the above examples were obtained using the apparatus and method described in US Patent No. 3,056,283 and in an article in "The Journal of the American Ceramic Society", Vol. 42, No. 11, November 1959j pages 537-541. The article is entitled "Improved Apparatus for Rapid Measurement of Viscosity of Glass at High Temperatures" and is written by Ralph L. Tiede.

Alle glass-sammensetningene i tabellen inneholder 1 vekt-% eller mindre av alkalimetalloksydene og således vil disse glasstyper i fiberform være akseptable for forbrukere som krever lavere nivåer av alkalimetalloksydene slik som hos E-glass. All the glass compositions in the table contain 1% by weight or less of the alkali metal oxides and thus these types of glass in fiber form will be acceptable to consumers who require lower levels of the alkali metal oxides such as with E-glass.

Titaniumoksyd (Ti02) benyttes i glass-sammensetningene ifølge oppfinnelsen som et flussmiddel istedenfor bor og fluor. TiO^ markedsføres som et fint, hvitt pulver, som finner utstrakt bruk i malinger for å gi emaljer og lignende opasitet. Det benyttes også ved glassdekorasjon, imidlertid var bruken av Ti02 som erstatning for B20^ og F2 for å redus-ere viskositeten i fibrerbare glass uten ugunstig å påvirke likvidustemperaturen heller uventet. Titanium oxide (Ti02) is used in the glass compositions according to the invention as a flux instead of boron and fluorine. TiO^ is marketed as a fine, white powder, which finds extensive use in paints to give enamels and similar opacity. It is also used in glass decoration, however the use of Ti02 as a substitute for B20^ and F2 to reduce the viscosity in fibrable glasses without adversely affecting the liquidus temperature was rather unexpected.

Konsentrasjonen av MgO i 5-komponent glass-sammensetningen er helst mindre enn 4 vekt-$L Konsentrasjoner for MgO på over 4$ øker likvidustemperaturen over den foretrukkede grense for fibrering. MgO kan tilsettes til glass-sammensetningen sammen med råstoffene og er kjent å ha en virkning på -smeltetemperaturen for E-glass og tilsettes f.eks. til E-glass for å regulere devitrifiseringen av diopsider (CaOMg02Si02). Det er nå oppdaget at 1,5<- 4,5 vekt-# MgO reduserer og regul-erer likvidustemperaturen til innenfor fibreringsområdet og reduserer den mengde Ti02 som er nødvendig i sammensetningen, noe som forbedrer fibrenes farge. The concentration of MgO in the 5-component glass composition is preferably less than 4 wt-$L Concentrations of MgO in excess of 4$ increase the liquidus temperature above the preferred limit for fiberization. MgO can be added to the glass composition together with the raw materials and is known to have an effect on the melting temperature of E-glass and is added e.g. to E-glass to regulate the devitrification of diopsides (CaOMg02Si02). It has now been discovered that 1.5<-4.5 wt-# MgO reduces and regulates the liquidus temperature to within the fiberization range and reduces the amount of TiO 2 required in the composition, which improves the color of the fibers.

Claims (1)

Bor- og fluorfri glass-sammensetning til fremstilling av glassfibre og med en viskositet på log 2,5 poise ved 1343°C eller mindre, karakterisert ved at den i det vesentlige består av:Boron- and fluorine-free glass composition for the production of glass fibers and with a viscosity of log 2.5 poise at 1343°C or less, characterized in that it essentially consists of:
NO1755/73A 1972-04-28 1973-04-27 NO133269C (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
NO750123A NO135060C (en) 1972-04-28 1975-01-16
NO75752092A NO135629C (en) 1972-04-28 1975-06-12

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US24844472A 1972-04-28 1972-04-28
US24836072A 1972-04-28 1972-04-28
US28819372A 1972-09-11 1972-09-11

Publications (2)

Publication Number Publication Date
NO133269B true NO133269B (en) 1975-12-29
NO133269C NO133269C (en) 1976-04-07

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Family Applications (3)

Application Number Title Priority Date Filing Date
NO1755/73A NO133269C (en) 1972-04-28 1973-04-27
NO750123A NO135060C (en) 1972-04-28 1975-01-16
NO75752092A NO135629C (en) 1972-04-28 1975-06-12

Family Applications After (2)

Application Number Title Priority Date Filing Date
NO750123A NO135060C (en) 1972-04-28 1975-01-16
NO75752092A NO135629C (en) 1972-04-28 1975-06-12

Country Status (18)

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JP (1) JPS577089B2 (en)
AR (1) AR198215A1 (en)
BE (1) BE798819A (en)
CA (1) CA975386A (en)
CH (1) CH602503A5 (en)
DD (1) DD107005A5 (en)
DE (1) DE2320720C2 (en)
ES (1) ES414161A1 (en)
FI (3) FI56517C (en)
FR (1) FR2182184B1 (en)
GB (1) GB1391384A (en)
IL (1) IL42018A (en)
IN (1) IN139472B (en)
IT (1) IT986640B (en)
NL (1) NL180655C (en)
NO (3) NO133269C (en)
PL (1) PL87767B1 (en)
SE (2) SE386156C (en)

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2407538B2 (en) * 1974-02-16 1976-04-01 Jenaer Glaswerk Schott & Gen., 6500 Mainz GLASSES BASED ON SIO TIEF 2 - ZNO AS A REINFORCEMENT AGENT IN CONCRETE AND FOR INSTALLATION IN LIGHTWEIGHT CONCRETE
JPS524519A (en) * 1975-06-30 1977-01-13 Fuji Fibre Glass Co Ltd Composite of alkaliiproof glass
JP2587708Y2 (en) * 1990-11-15 1998-12-24 セイコーインスツルメンツ株式会社 Small motor
WO1996039362A1 (en) * 1995-06-06 1996-12-12 Owens Corning Boron-free glass fibers
CA2375719C (en) * 1999-05-28 2007-01-09 Ppg Industries Ohio, Inc. Glass fiber composition
US6962886B2 (en) * 1999-05-28 2005-11-08 Ppg Industries Ohio, Inc. Glass Fiber forming compositions
FR2800730B1 (en) * 1999-11-04 2001-12-07 Vetrotex France Sa GLASS YARNS CAPABLE OF REINFORCING ORGANIC AND / OR INORGANIC MATERIALS, PROCESS FOR PRODUCING GLASS YARNS, COMPOSITION USED
MXPA03001996A (en) 2000-09-06 2004-08-12 Ppg Ind Ohio Inc Glass fiber forming compositions.
DE10161791A1 (en) 2001-12-07 2003-06-26 Dbw Fiber Neuhaus Gmbh Continuous glass fiber with improved thermal resistance
CN101514080B (en) * 2004-05-13 2011-02-02 旭玻璃纤维股份有限公司 Glass fiber for reinforcing polycarbonate resin and polycarbonate resin molded product
BRPI0518202B1 (en) * 2004-11-01 2017-05-30 The Morgan Crucible Company Plc refractory earth alkaline metal silicate fibers
US7875566B2 (en) 2004-11-01 2011-01-25 The Morgan Crucible Company Plc Modification of alkaline earth silicate fibres
KR100676167B1 (en) 2006-01-25 2007-02-01 주식회사 케이씨씨 A biodegradable ceramic fiber composition for a heat insulating material
FR2910462B1 (en) * 2006-12-22 2010-04-23 Saint Gobain Vetrotex GLASS YARNS FOR REINFORCING ORGANIC AND / OR INORGANIC MATERIALS
WO2008156090A1 (en) 2007-06-18 2008-12-24 Nippon Sheet Glass Company, Limited Glass composition
DE102008037955B3 (en) 2008-08-14 2010-04-15 Bürger, Gerhard High temperature and chemically resistant glass with improved UV light transmission and its use
CN101503279B (en) * 2009-03-02 2012-04-11 巨石集团有限公司 Novel glass fibre composition
CN101597140B (en) * 2009-07-02 2011-01-05 重庆国际复合材料有限公司 High-strength high-modulus glass fiber
EP2354104A1 (en) 2010-02-05 2011-08-10 3B Glass fibre composition and composite material reinforced therewith
EP2354106A1 (en) 2010-02-05 2011-08-10 3B Glass fibre composition and composite material reinforced therewith
EP2354105A1 (en) 2010-02-05 2011-08-10 3B Glass fibre composition and composite material reinforced therewith
CN102173594B (en) * 2011-02-14 2012-05-23 重庆国际复合材料有限公司 Boron-free fluorine-free glass fiber composition
US20140357143A1 (en) * 2011-12-06 2014-12-04 Nitto Boseki Co., Ltd. Glass fabric and glass fiber sheet material using same
US9499432B2 (en) 2012-04-18 2016-11-22 3B-Fibreglass Sprl Glass fibre composition and composite material reinforced therewith
RS57931B1 (en) * 2013-02-18 2019-01-31 As Valmieras Stikla Skiedra Temperature-resistant aluminosilicate glass fibers and method for the production thereof and use thereof
CN103145341B (en) * 2013-03-22 2016-06-08 内江华原电子材料有限公司 A kind of floride-free boron-free and alkali-free glass fiber and preparation method thereof
CN103332866B (en) * 2013-07-19 2016-07-06 重庆国际复合材料有限公司 A kind of glass fibre
KR20210101269A (en) 2018-12-12 2021-08-18 코닝 인코포레이티드 Ion-exchangeable lithium-containing aluminosilicate glass
EP4249445A4 (en) * 2021-06-29 2024-06-19 Nitto Boseki Co., Ltd. Glass composition for glass fibers, glass fiber, and glass fiber-reinforced resin molded product
CN118495821A (en) * 2024-07-19 2024-08-16 淄博卓意玻纤材料有限公司 Compression-resistant high-strength high-modulus glass fiber, production method and system

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Publication number Priority date Publication date Assignee Title
FR1356354A (en) * 1963-02-12 1964-03-27 Compositions of glass and fiberglass or other articles formed therewith
DE1496662A1 (en) * 1964-06-12 1969-07-03 Sued Chemie Ag High melting point fiberglass
GB1200732A (en) * 1966-07-11 1970-07-29 Nat Res Dev Improvements in or relating to glass fibres and compositions containing glass fibres
GB1209244A (en) * 1967-04-05 1970-10-21 Owens Corning Fiberglass Corp Glass composition

Also Published As

Publication number Publication date
JPS4947408A (en) 1974-05-08
FI56518C (en) 1980-02-11
FI56518B (en) 1979-10-31
NO133269C (en) 1976-04-07
SE386156B (en) 1976-08-02
AR198215A1 (en) 1974-06-07
FR2182184B1 (en) 1977-12-30
IT986640B (en) 1975-01-30
IL42018A (en) 1977-10-31
NL180655C (en) 1987-04-01
FI771877A (en) 1977-06-14
PL87767B1 (en) 1976-07-31
SE7513371L (en) 1975-11-27
NO752092L (en) 1973-10-30
FR2182184A1 (en) 1973-12-07
SE410730B (en) 1979-10-29
FI56519C (en) 1980-02-11
FI56519B (en) 1979-10-31
JPS577089B2 (en) 1982-02-08
CA975386A (en) 1975-09-30
NO135060C (en) 1977-02-02
NL180655B (en) 1986-11-03
BE798819A (en) 1973-08-16
FI56517B (en) 1979-10-31
NO135060B (en) 1976-10-25
NL7305629A (en) 1973-10-30
ES414161A1 (en) 1976-06-01
IL42018A0 (en) 1973-06-29
SE386156C (en) 1984-07-16
FI56517C (en) 1980-02-11
NO135629B (en) 1977-01-24
DD107005A5 (en) 1974-07-12
FI771878A (en) 1977-06-14
CH602503A5 (en) 1978-07-31
DE2320720A1 (en) 1973-11-08
AU5450673A (en) 1974-10-17
NO750123L (en) 1973-10-30
GB1391384A (en) 1975-04-23
IN139472B (en) 1976-06-26
NO135629C (en) 1977-05-04
DE2320720C2 (en) 1983-06-16

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