FI56517C - GLASKOMPOSITION FOER FRAMSTAELLNING AV GLASFIBRER - Google Patents

Description

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^ (11) UTLÄGGNI NGSSKRIFT 565 17

Patents granted II 02 1930 'Patent nseddelat' (51) Kv.lk. * / Lnt.CI. * 6 03 C 13/00 FINLAND — FINLAND <*> Pat «nttlhak * mui— Paten taruOknlng 1365/73 (22) HakemltpUvi - AnsOknlngadag 27 · 0¾. 73 '(23) AlkupUvi — Giltlghetsdag 27 · OU. 73 (41) Became Public - Bllvlt offentllg 29.10.73

National Board of Patents and Registration,,. ...., _ '(441 Date of publication | -

Patent · OCn registerstyrelsen Anafikan utlagd och utl.skrlften publlcarad 31.10.79 (32) (33) (31) Privilege claimed— Begird prlorltet 28.0U.72 28.OU.72, II.O9.72 USA (US) 2U8360, 2U8UUU , 288193 Proven-Styrkt (71) Owens-Coming 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) Glass alloy for the manufacture of glass fibers - Glass composition for glass fiber production

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, has a weight of 9-11% by weight 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, K 2 O and Li 2 O, must be less than 1% by weight, calculated as Na 2 O. Therefore, it is important to keep the alkali metal oxide level of glass alloys at or below one percent when developing new 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.

Boron is generally fed into the batch mixture as cholemanite, anhydrous boric acid or boric acid, while fluorine is added 66517

As CaF2 or as sodium silicofluoride (Na2SiFg). The melting of the raw materials of the glass charge, for example in gas burning furnaces, 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 Β20 ^ and F2 or the boron and fluorine'er compounds tend to evaporate from the molten glass and the gases can be drawn into the exhaust stacks 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 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 or more 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 often than bushings that come into contact with less viscous glasses.

3,56517 With these problems in mind, a boron and fluorine-free, fibrous glass mixture of the present invention was developed.

The glass composition of the present invention is boron and fluorine free and is characterized in that it contains essentially:

Ingredient Weight #

SiO 2 54-64 Al 2 O 3 9-19

CaO 9-25

Ti02 3-5

MgO 1.5-4.5

ZnO 0-6

SrO 0-6

BaO 0-6

Li 2 O 0-5

MnO 0-2.5

Na 2 O 0-2.5 K 2 O 0-2.5

ZrO2 0-2

Feo0,. 0-1 2 3> The glass compositions of this invention can be divided into low-alkali glass compositions having an alkali metal oxide concentration of less than one weight percent and glass compositions having an alkali metal oxide concentration of more than one percent. The low-alkali glasses of the present invention can directly replace E-glass, which is currently the most common glass alloy of textile fibers, as discussed above. Other glass alloys contain Li 2 O as a flux and thus contain more than one weight percent of alkali metal oxides.

Low alkali metal oxide glass alloys can be further divided into five and six component glass alloys.

The five-component glass mixture contains SiO 2, Al 2 O 3, CaO, 3-5% by weight of # TiO 2 and 1.5-4.5% by weight of # MgO. The addition of MgO and TiO 2 to the three-component masterbatch lowers the viscosity and liquefaction temperature of the glass to the defibering range and provides a glass blend suitable for defibering with conventional equipment and techniques.

All of the glass alloys described above are free of boron and fluorine and have a viscosity of log 2.5 poise or less at about 1340 ° C and a liquefaction temperature of about 1300 ° C or less. Glass alloys falling into the above range can be drawn into a fine continuous fiber with a diameter of 3.8 to 14 .mu.m.

As stated above, the glass composition of the present invention and the glass fibers made therefrom fall within the following wide range of ingredients: 4 S6517

Ingredient Weight #

SiO 2 54-64 Al 2 O 3 9-19

CaO 9-25

Ti02 3-5

MgO 1.5-4.5

ZnO 0-6

SrO 0-6

BaO 0-6

Li 2 O 0-5

MnO 0-2.5

Na 2 O 0-2.5 K 2 O 0-2.5

ZrO2 0-2

Pe203 0-1

The process for producing a boron- and fluorine-free textile fiber thus comprises adding 3-5 parts by weight of TiO 2 and 1.5-4.5% by weight of MgO to a glass mixture of three basic components, melting the charge to obtain a molten glass having a viscosity of log 2.5 poise at or below 1340 ° C and a liquefaction temperature of about 1200 ° C or below, and glass fiberization. Glass fiberization methods are described in prior art patents, which include U.S. Patent No. 2,908,036.

The glass mixture may also contain small amounts up to one weight percent of certain additions or impurities, including Fe 2 O 3, Na 2 O, K 2 <0 and Li 2 O, and MgO. Typical compositions that include the preferred composition of the five-component, low-alkali glass composition of this invention are shown in Table 1 below, Examples .1-17.

The five-component, low-alkali glass composition of the present invention contains substantially 54.5-60 # SiO 2, 9-14.5 # Al 2 O 3, 17-24 # CaO, 3-5 # TiO 2 and 1.5-4 # MgO: a. As indicated above, the preferred mixture also contains less than 1% by weight of alkali metal oxides and the mixture also contains certain additions or impurities up to one% by weight. Typical examples of the five-component, low-alkali glass alloy of this invention are shown in Table 1, Examples 1-17 ·

Table 2, Examples 1-8, shows glass compositions according to the invention in which LiO 2 and TiO 2 together replace boron and fluorine as flux.

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56517 8

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. k2, No. 11, November 1959, pages 537-5 ^ 1. 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 using the equipment and methods described in the Tiede article.

The glass compositions of this invention, some of which are described in the tables above, preferably have liquefaction temperatures of 1200 ° C or lower and a viscosity of log 2.50 poise (i.e., 10 poise) or less at 13 → 0 ° C. Glass containing less than 1% by weight of alkali metal oxides is therefore suitable for fiber formation, and direct replacement of E-glass and the corresponding boron- and fluorine-containing textile glass-forming glass with boron- and fluorine-free glass is therefore possible.

All of the glass alloys in Tables 1-2 contain one weight percent or less of the alkali metal oxides described above, and thus these glasses in their fibrous form are acceptable to consumers who require low alkali metal oxide contents, such as E-glass. The primary glass-forming components in the glass compositions of this invention are SiO 2 and Al 2 O 2. The three basic oxides of glass alloys are SiO 2, Al 2 O 2 and CaO.

Titanium dioxide (TiO 2) is used in the glass compositions of this invention as a flux instead of boron and fluorine. TiO 2 is sold as a fine white powder with extensive use in paints to impart opacity to enamels, etc. It is also used in glass decoration, however, the use of TiO 2 as a substitute for B 2 O 2 and F 2 to reduce the viscosity of defibering glass without adversely affected the temperature of the liquid form, was quite surprising. TiO 2 should be used in these mixtures in amounts of 5% by weight or less, preferably less than 3-3.5%. Concentrations of more than * 1% TiO2 may cause a brownish or yellowish color in the glass fibers. This can be a problem when the fibers are combined with a clear base material and are visible in the final product. Clear plastic sheets or clear plastic fishing rods are examples of products that may be less desirable if dyed fibers are used.

9,56517

The concentration of MgO in the five-component glass mixture is preferably less than 4% by weight. Concentrations of MgO above 4 # raise the temperature of the liquid form above the recommended limit for defibering.

MgO can be added to the glass mixture with the raw materials and is known to have an effect on e.g. the melting temperature of E-glass and is added to E-glass to control the crystallization of diopsides (Ca0Mg0SiO2). It has now been found that 1.5-4.5 wt.% MgO lowers the liquefaction temperature and adjusts it to the defibering range and, as discussed above, reduces the amount of TiO 2 required in the mixture, which improves the color of the fibers. It can be seen from the examples in the table that MgO mainly replaces CaO.

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% by weight. 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 viscosity in the desired range.

Pe 2 O 2 may be present in all of the glass compositions of this invention as an impurity in the feedstock or may be intentionally added in up to one weight percent. However, Pe 2 O 2 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 · ^), 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 (1)

56517 Claim A mixture of boron and fluorine-free glass which is defiberable to form glass fibers and has a viscosity of log 2.5 poise at a temperature of 1345 ° C or less, characterized in that it contains mainly Ingredient Weight% SiO 2 54-64 Al 2 O 3 9-19 CaO 9-25 TiO2 3-5 MgO 1.5-4.5 ZnO 0-6 SrO 0-6 BaO 0-6 Li 2 O 0-5 MnO 0-2.5 Na 2 O 0-2.5 K 2 O 0-2.5 ZrO 2 0-2 FegO ^ 0-1 Bor- and fluorofru glaskomposition, som är fibrerbar account bild-Ning av glasfibrer och har har viscositet av log 2,5 pois vid 1345 ° C eller mindre, kännetecknad av att den i interesudsak bestär av Beständsdel Viktprocent Si02 ' 54-64 Al 2 O 3 9-19 CaO 9-25 TiO 2 3-5 MgO 1.5-4.5 ZnO 0-6 SrO 0-6 BaO 0-6 Li 2 O 0-5 MnO 0-2.5 Na 2 O 0-2, 5 K 2 O 0-2.5 ZrO 2 0-2 Fe 2 O 3 0-1