FI56518C - BOR- OCH FLUORFRASE GLASKOMPOSITION FOER BILDNING AV GLASFIBRER - Google Patents

Description

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Β 11 UTLÄGC NIN CSSKRI FT 5 ^ 5 I 8 C .... Patent ray jnno tty li U2 1930 'Patent oeddelnt ^ (51) Kv.lk.' / Int.CI. * 0 03 C 13/00 (21) Pstenttlhakemus - Patentansöknlng 771877 (22) Hakemispilvi— Aniöknlngsdag 1 ^ .06.77 (FI) (23) Alkupilvl - Glltighetsdag 27 · 0¾. 73 (41) Become public - Bllvit offentllg li +. 06.77

Patent, and the National Board of Registration NihtSvikalpanon and heard | ulkal, un pvm. -

Patent and Registration Publications Ansökan utlagd och utl.skriften publicerad 31.10.79 (32) (33) (31) Privilege claimed — Begird prlorltet 28.0U.72 28.0U.72, 11.09.72 USA (US) 2U8360, 2U8UUU, 288193 ( 71) Owens-Corning Fiberglas Corporation, 608 Madison Avenue, Toledo,

Ohio, USA (72) Thomas David Erickson, Newark, Ohio, Warren Walter Wolf, Reynoldsburg, Ohio, Ralph Lester Science, Granville, Ohio, John Allen Williams,

Heath, Ohio, USA (US) (7U) Berggren Oy Ab (5U) Boron and fluorine-free glass alloy for forming glass fibers - Bor- och fluororfri glaskomposition för bildning av glasfibrer (62)

Avdelad frän ansökan 1365/73 (utläggningsskrift 56517)

Fibrous glass alloys currently contain boron- or fluorine-containing compounds as fluxes, which reduce the viscosity of the charge, especially during the early stages of melting. Since boron and fluorine have been found to be potent environmental toxins, the problem has been to produce a glass alloy that (1) has the physical properties required for defibering, (2) is acceptable to the industry, and (3) is free of fluorine and boron.

For example, E-glass, which is the most common of the glass alloys currently used to make textile fibers, contains 9-11% by weight of B 2 O 3 and may contain fluorine as a flux. The quality requirements for e-glass fibers also stipulate that the percentage of alkali metal oxides, namely Na 2 O, I 2 Or and I 2 Orn, must be less than 1% by weight, calculated as Na 2 O. Therefore, it is important to keep the glass alloys that can be used in place of E-glass. The composition of the e-glass is disclosed in U.S. Patent No. 2,334,961.

5651Θ

Boron is generally fed to the batch mixture as cholemanite, anhydrous boric acid or boric acid, while fluorine is added as CaF 2 or sodium silicofluoride (Na 2 SiFg). The melting of the raw materials of the glass charge, for example in gas kilns to form molten glass, from which the fibers can be drawn and formed, takes place by heating the charge and molten glass to temperatures above 1200 ° C. Commonly used textile fibers are melted between 1315-1510 ° C. At these melting temperatures B2C> 2 and F2 or various compounds of boron and fluorine tend to evaporate from the molten glass and the gases can be drawn into the exhaust pipes and escape into the air surrounding the glass fiber formation area.

The resulting air and potential water pollution can be reduced or eliminated in many different ways. Water washing or filtration of the exhaust gases can often clean the exhaust air. The use of electric furnaces instead of gas burners effectively eliminates the losses of volatile fluxes (e.g. boron and fluorine) commonly associated with gas burners at temperatures above 1200 ° C. However, these cleaning agents are often expensive and can be avoided if the source of environmental toxins can be removed from the glass mixtures. However, this solution is complicated by the fact that the removal of boron and fluorine removes the two flux components commonly used in fibrous textile glass compositions. Maintaining acceptable melting rates, melting and operating temperatures, liquid form, and viscosity without boron and fluorine has been found to be quite difficult.

The acceptable range for use in a commercial textile glass feed channel or passage is between 1230-1370 ° C. The glass mixture operating uniformly in this environment preferably has a liquefaction temperature of about 1200 ° C or lower and a viscosity of log 2.5 poise or less at 1315 ° C.

The fiber formation temperature is preferably about 55 ° C higher than the liquefaction temperature to prevent devitrification (growth of crystals) in the glass when the fibers are formed. Because devitrification causes irregularities or beads in the glass that interfere with or can stop fiber production, the liquefaction temperature of commercial textile glass should preferably be below about 1200 ° C.

The viscosity of glass is also the key to efficient and economical fiber formation. Glass viscosities of log 2.50 poise at 3,56518 or above at 1340 ° C require such high temperatures to melt the glass and make it a flowable and malleable fiber that metal bushings or feed openings can collapse and become unusable or need to be replaced. or repaired more frequently than bushings that come into contact with less viscous glasses.

With these problems in mind, a boron and fluorine free, fibrous glass mixture of the present invention was developed.

The glass mixture according to the invention is a boron- and fluorine-free glass mixture which can be defibered to form glass fibers and has a viscosity of log 2.5 poise at 1345 ° C or less and is mainly characterized in that it contains mainly Ingredient.

SiC> 2 55-65 A1203 11-18

CaO 9-25

Li 2 O 0.3-2.5

TiO2 2-5

MgO 0-10

MnO 0-1.5

Na 2 O, K 2 O 0-2.5

BaO 0-2.5

SrO 0-1.5

ZnO 0-4

ZrO2 0-2

The amount of Fe 2 O 3 0-1 in the amount of Li 2 O + TiO 2 is 3.5-6.5% by weight.

The glass alloy of the present invention has an alkali metal oxide content of more than 1%, lithium oxide (Li 2 O) as the primary flux, and lithium oxide and titanium dioxide (TiO 2) together replace boron and fluorine as flux. Preferably, the mixture contains 0.3-2.5% by weight of Li 2 O and 2-5% of TiO 2, wherein the total percentage of Li 2 O and TiO 2 is 3.5-6.5%. This mixture may also contain 0-10% MgO and other ingredients, as shown below.

It has been found that Li 2 O and TiO 2 together have a synergistic effect on the preferred glass alloys. When Li 2 O is added as the primary flux, the mixture contains 1.5-4% Li 2 O and 0-10% MgO.

4,56518

The glass composition of the invention is boron and fluorine free and has a viscosity of log 2.5 poise or less at a temperature of about 1340 ° C and a liquefaction temperature of about 1300 ° C or less. The glass mixture falling in the above range can be drawn into a fine continuous fiber with a diameter of 3.8-14 μm.

The mixture according to the invention is preferably as follows:

Ingredient Weight%

SiO 2 56.7-59 Al 2 O 3 12.2-14.6

CaO 16-23

Li 2 O 0.4-2.5

TiO2 0.4-2.5

MgO 2-3.5 R 2 O (Na 2 O, K 2 O) 0-0.8

BaO 0-2.5

ZrO2 0-2

Fe 2 O 3 0-1

The total weight percentage of Li 2 O and TiCl 2 ranges from 3.5 to 6.5%.

Typical mixtures included within the above limits are shown in Table 1 below, Examples 1-16.

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The viscosity determinations of the above examples were performed using the equipment and methods disclosed in U.S. Patent No. 3,056,283 and in The Journal of the American Ceramic Society, Vol. 42, No. 11, November 1959, pages 537-541. The article is entitled "Improved Apparatus for Rapid Measurement of Viscosity of Glass at High Temperatures" and was written by Ralph L. Science. Other separate viscosity determinations referred to herein may be measured with the equipment and methods described in the Tiede article.

Lithium oxide (LiO 2) and titanium dioxide (TiO 2) are used together in the glass alloys shown in Table 1 as fluxes instead of boron and fluorine. The synergistic, viscosity-lowering effect of the combination of Li 2 O and TiO 2 without the detrimental effect on liquefaction is an important step in the preparation of fibrous glass alloys that are free of strong environmental toxins, boron and fluorine. MgO can also be added to this glass mixture, if necessary, to lower the liquefaction temperature to the fiberization zone.

Lithium oxide is the only one of the three commonly used alkali metal oxides (Li 2 O, K 2 O and Na 2 O) that can be used in amounts of up to 4% by weight to adjust the viscosity without adversely affecting liquefaction. In the preferred glass mixture shown in Table 1, the Li 2 O range is between 0.5-2.5% by weight. Concentrations of lithium oxide in excess of 2.5% by weight in combination with TiO 2 can cause the liquefaction temperature to rise to undesired levels. Titanium dioxide should be used in these glass alloys in amounts of 5% by weight or less. When used in amounts above 5%, the liquefaction temperature may rise above the recommended limit for defibering.

Alkali metal oxides Na 2 O and K 2 O can be used separately or together to adjust the viscosity. In either case, the total amount of Na 2 O and K 2 O should not exceed about 2.5% by weight when the total amount of alkali metal oxide may exceed 1% and preferably does not exceed one weight percent. Amounts in excess of 2.5% by weight cause an undesirable increase in the liquefaction temperature, which outweighs the importance of these oxides in maintaining the viscosity in the desired range.

8 66516

In Examples 1-5, 8, 9 and 16 of Table 1, Na 2 O was added as a feedstock. In the other examples in Table 1, Na 2 O was not intentionally added but entered the glass mixtures as an impurity with one feedstock.

K20 was included in all the examples in Table 1 as a feed impurity. Glass alloys free of K 2 O or Na 2 O are also within the scope of this invention.

Certain oxides from the group BaO, CaO, MgO and MnO are preferred additives in the glass mixture of Table 1. SrO should be equally useful. This group of oxides is useful in controlling the liquefaction temperature and does not adversely affect viscosity. The best results have been observed when these oxides are used together in amounts of 27% by weight and the best results are generally obtained when MgO and CaO are used either separately or together. MnO is preferably used in amounts of 0.5% or less. When MnO is used in amounts above 0.5%, it can cause a brown or purple color in the glass mixture and fabrics.

Fe 2 O 2 may be incorporated into the glass compositions of this invention as an impurity in the feedstock or may be intentionally added up to one weight percent. However, Fe 2 O 3 can stain the glass and the fibers drawn therefrom, as described above, and therefore its amount should be kept as low as possible when clear glass fibers are required for some application, especially when TiO 2 is present. Various other impurities or adventitious materials may also be present in the glass compositions in amounts of about 0.3% by weight or less without adversely affecting the glasses or fibers. These impurities include chromium oxide (Cr 2 O 3), vanadium oxides and phosphates. These substances may enter the glass as impurities in the raw materials or they may be products formed by a chemical reaction between the components of the molten glass and the furnace. Sulfur oxides may also be present in very small amounts, either as feed impurities or as deliberate additions of sulfates as finishing agents.

Claims (4)

9,56518 A mixture of hoorj and fluorine-free glass which is heat-shrinkable to form glass fibers and has a viscosity at a temperature of 1345 ° C or less, characterized in that it contains mainly Ingredient Weight% SiO 2 55-63 Al 2 O 3 11- 18 CaO 9-25 Li 2 <3 0.3—2.5 TiO 2 2-5 MgO 0-10 MnO 0-1.5 Na 2 O, K 2 O 0-2.5 BaO 0-2.5 SrO 0-1.5 ZnO 0-4 ZrO 2 0-2 Fe 2 O 3 0-1 in the sum of Li 2 O + TiO 2 in an amount of 3.5-6.5% by weight. Glass mixture according to Claim 1, characterized in that the amount of MgO is 2.5 to 3.5% by weight. 1. Bor- and fluorofre glasompositiön, som är fibrerbar account bild-Ning av glasfibrer och som har en visositet av log 2,5 pois vid 1345 ° C eller mindre, kännetecknad av att den i huvudsak bestär av Bestandsdel Vikt-% Si02 55- 63 Al 2 O 11-18 CaO 9-25 Li 2 O 0.3-2.5 TiO 2 2-5 MgO 0-10 MnO 0-1.5 Na 2 O, K 2 O 0-2.5 BaO 0-2.5 SrO 0-1, 5 ZnO 0-4 ZrO2 0-2 Fe2Ö3 0-1