WO1991016273A1

WO1991016273A1 - Calcia-aluminoborosilicate glass compositions

Info

Publication number: WO1991016273A1
Application number: PCT/US1991/002334
Authority: WO
Inventors: John Paul Stevenson; John F. Collins
Original assignee: United States Borax & Chemical Corporation
Priority date: 1990-04-25
Filing date: 1991-04-04
Publication date: 1991-10-31

Abstract

Glass compositions for use in the preparation of glass microspheres and having reduced 2 Pas (20 poise) temperatures comprise 38 to 44 % SiO2, 14 to 22 % B2O3, 9 to 16 % Al2O3, 22 to 26 % CaO and optionally MgO, 0 to 8 % Na2O, 0 to 2 % Li2O, 0 to 2 % K2O and 0 to 1 % Fe2O3, the sum of B2O3 and Na2O being at least 19 %, said percentage by weight.

Description

CALCIA - ALUMINOBOROSILICATE GLASS COMPOSITIONS

The invention relates to glass compositions for use in the preparation of glass microspheres.

Background of the Invention Hollow glass microspheres (e.g. 0.5 mm) are used, for example, as bulk, lightweight fillers for reinforced plastic components for the motor industry. They find use also as hollow microbubbles for adhesives. They can be prepared, for example, by pulsing an inert gas, such as argon into a continuous stream of molten glass in order to produce individual microspheres. For best results, the molten glass should be at a temperature such that the melt has a viscosity of about 2 Pas (20 poise). This temperature is known as the 20 poise temperature (20 PT). The glass compositions previously proposed for use in the preparation of hollow glass microspheres in this way have had 20 PT values in the region of 1440° to 1450°C. For example, a standard E- Glass composition (analyzing 53.4 wt % SiO₂, 13.9 wt % Al₂O₃, 8.9 wt % B₂O₃, 21.7 wt % CaO, 0.3 wt % Na₂O and 0.7 wt % K₂O), such as is used in providing glass fibers for reinforcing plastics, has a 20 PT of 1447°C. A borosilicate glass composition used in the preparation of glass microspheres (analyzing 44.7 wt % SiO₂, 12.5 wt %

Al₂O₃, 14.1 wt % B₂O₃, 26.3 wt % CaO, 0.6 wt % Na₂O and

0.7 wt % K₂O) has a PT of 1444°C. Such high 20 PT values can cause a reduced service life for metal parts, such as platinum bushings, employed in the manufacture of microspheres and are of course associated with high energy requirements. Accordingly it is desired to provide glass compositions suitable for use in the preparation of glass microspheres but having lower 20 PT values than the glass compositions hitherto used.

Description of the Invention

This invention provides glass compositions for use in the preparation of glass microspheres comprising 38 to 44% SiO₂, 14 to 22% B₂O₃, 9 to 16% Al₂O₃, 22 to 26% CaO, 0 to 8% Na₂O, 0 to 2 % Li₂O, 0 to 2% K₂O and 0 to 1% Fe₂O₃, the sum of B₂O₃ and Na₂O being at least 19%, said percentages being by weight. Optionally, a portion of the CaO in the composition, such as up about 50%, may be substituted by MgO.

Preferably the glass composition comprises 39 to 43% SiO₂, 19 to 22% B₂O₃, 9 to 13% Al₂O₃, 22 to 26% CaO and optionally MgO, 4 to 6% Na₂O, 0 to 1% K₂O and 0.2 to 0.4% Fe₂O₃. A particularly preferred composition is one which consists essentially of about 40% SiO₂, about

11% Al₂O₃, about 20% B₂O₃, about 23% CaO, about 5% Na₂O, about 1% K₂O, and about 0.3% Fe₂O₃, said percentages by weight. The glass compositions provided in accordance with this invention preferably have 20 PT values below about 1350°C, especially below 1300°C.

The B₂O₃ content, either alone or combined with the Na₂O content, has an important effect in reducing the 20 PT value. When the B₂O₃ content is too high, say 25 to 30 wt %, the glass becomes opalescent and its viscosity is undesirably increased. The optimum B₂O₃ content is from 20 to 21% when the glass composition contains 0 to 5% Na₂O.

Additions of Li₂O and/or Na₂O have been found to be effective in lowering 20 PT values. However, the durability of glasses containing too much of these ingredients can be adversely affected. Durability is measured as the amount of sodium (or alkali equivalent) leached from a glass after treatment in water for 1 hour at 98°C. (See ISO-719-1985 "Glass-Hydrolytic Resistance of Glass Grains at 98°C, Materials for Test and Classification"). Sodium loss provides an inverse measure of durability, i.e. more durable glasses have low sodium losses. A balance should therefore be sought between improving (lowering) the 20 PT value and worsening the durability. A particularly preferred Na₂O content is about 5 wt % since it has been found that this amount of Na₂O can be more effective in lowering the 20 PT value than a lower amount (e.g. 2.5 wt %) or higher amount (e.g. about 7.5 wt %). Weight for weight Li₂O is more effective in reducing the viscosity of a glass (i.e. is a better flux) than Na₂O, but is more expensive.

Al₂O₃ is a refractory material and increases the viscosity of most glasses. It is generally added to glasses to improve their aqueous durability. The optimum amount is from 9 to 14%, especially 9 to 11%, Al₂O₃.

Preferably the glass compositions contain CaO rather than both CaO and MgO . Nevertheless mixtures of CaO and MgO can be used if desired, the amount of MgO suitably being up to about half the total amount of CaO and MgO.

Fe₂O₃ is normally present in E-type glasses to improve radiation heat transfer into the glass during gas firing and heat radiation from fibers during cooling. It can be present, for example in amounts of up to 1 wt %, preferably 0.2 to 0.4 wt %, especially about 0.3 wt %, in the glass compositions of this invention to improve heat transfer. Fe₂O₃ also contributes to the fluxing action.

This invention also relates to the use of the glass compositions in the preparation of glass microspheres. This can suitably be done by pulsing an inert gas, preferably argon, into a continuous melt of said glass compositions to produce individual microspheres. The melt will preferably have a viscosity of about 2 Pas (20 poise).

EXAMPLES The invention is illustrated by reference to the following Examples and comparative Examples.

Glass formulations were melted. The viscosity: temperature relationships were measured and the temperature at which the viscosity was 2 Pas (20 poise) was extrapolated (above 1400°C) or interpolated (below 1400°C). Details of the target compositions and of the results of analysis are given in the following Table, together with the 20 PT values. For some of the glasses durability was measured in accordance with the method referred to above and the results also appear in the Table. Examples 13-21 are comparative examples. G

I

A comparison of the properties of Examples 1-12 with examples 13-21 shows the significant improvement in viscosity obtained with the compositions of this invention while retaining their aqueous durability and other desirable properties.

Various changes and modifications of the invention can be made and, to the extent that such variations incorporate the spirit of this invention, they are intended to be included within the scope of the appended claims.

Claims

1. A glass composition for use in the preparation of glass microspheres comprising 38 to 44% SiO₂, 14 to 22% B₂O₃, 9 to 16% Al₂O₃, 22 to 26% CaO, 0 to 8% Na₂O, 0 to 2% Li₂O, 0 to 2% K₂O and 0 to 1% Fe₂O₃, the sum of B₂O₃ and Na₂O being at least 19%, said percentages by weight.

2. A glass composition according to claim 1 which comprises 39 to 43% SiO₂, 19 to 22% B₂O₃, 9 to 13% Al₂O₃, 22 to 26% CaO, 4 to 6% Na₂O and 0 to 1% K₂O.

3. A glass composition according to claim 1 which contains 20 to 21% B₂O₃ and 0 to 5% Na₂O.

4. A glass composition according to claim 1 consisting essentially of about 40% SiO₂, about 11% Al₂O₃, about 20% B₂O₃, about 23% CaO, about 5% Na₂O and about 1% K₂O.

5. A glass composition according to claim 1 in which up to about 50% of said CaO is replaced by MgO.

6. A glass composition according to claim 2 in which up to about 50% of said CaO is replaced by MgO.

A glass composition according to claim 2 in which 0.2 to 0.4% Fe₂O₃ is included.

8. A glass composition according to claim 2 which contains 20 to 21% B₂O₃.

9. A glass composition according to claim 4 in which about 0.3% Fe₂O₃ is included.

10. In the production of hollow glass microspheres by pulsing an inert gas into a continuous stream of molten glass, thereby forming individual microspheres of said glass, the improvement which comprises employing as said glass a composition according to claim 1.

11. The process according to claim 10 in which said molten glass has a viscosity of about 2 Pas (20 poise).

12. The process according to claim 10 in which said inert gas is argon.