Glass composition

Abstract: A glass composition comprises by weight, 50-60%, SiO₂; 5-13%, K₂0; 5-8%, Ti0₂; 10-15%, BaO; 5-10%, ZnO; 3-10%, Na₂0; 1-5%, CaO; and 0.3-0.8%, Sb₂0₃. The density, refractive index and dispersion value of light of the composition are equal to, or higher than, those of conventional lead-containing crystal glass, although the composition is entirely lead free.

Description: This invention relates to a glass composition which looks like, or can be regarded as, crystal glass, although it does not contain lead (Pb) and is suitable for use in producing tableware or like articles. Conventionally, lead-containing crystal glass is used popularly as crystal glass in producing tableware or like articles. The glass contains a large amount of lead, and such of its characteristics as that "it is massive"; that "it has a high light refraction index and exhibits a high dispersion value of light"; and that "it melts readily", are provided principally by PbO. While the content of PbO varies widely, it generally ranges from 24 to 26 percent by weight. However, it has recently been questioned whether lead, which is particularly injurious to the human body, can be dissolved out of lead-containing crystal glass. For example, in California, U.S.A., a complaint was filed asserting that the public organization "has not given a clear warning against exposure to lead" arising from lead crystal glass used to produce tableware, decanters and like articles. According to the FDA (Food and Drug Administration) standards of the U.S.A., the permitted level for the dissolution amount of lead has been revised to a rigorously low value. Meanwhile, in Japan, the dissolution amount of lead from lead-containing crystal glass is regulated by the "Official Announcement No. 84 of the Ministry of Health and Welfare Based on the Food Hygiene Law", and lead-containing crystal glassware makers manufacture lead-containing crystal glass so that the dissolution amount of lead may not exceed the permitted level even where the content of PbO in the lead-containing crystal glass is within 24 to 26 percent. However, it is forecast that the permitted levels may be progressively more restricted in Japan. Therefore, in order to suppress dissolution of lead from lead-containing crystal glass, Japanese Patent Laid-Open Application No. Heisi 3-205325 has proposed a technique wherein the surface of a piece of lead-containing crystal glass tableware is covered with a protective film which contains silicon oxide as a principal component. However, since the technique requires secondary working after making the glass, a rise in the production cost cannot be avoided. Another technique has been proposed and is disclosed in Japanese Patent Laid-Open Application No. Heisei 2-141434 wherein the surface of a crystal glass vessel is covered with a lead-free glass layer. With the technique, however, since two kinds of glass are melted simultaneously and sprayed on the crystal glass vessel to mold the lead-free glass layer, there are the problems that the molding process is inefficient, presswork cannot be employed, and so forth. A further technique is disclosed in Japanese Patent Laid-Open Application No. Heisei 4-50133, wherein the amount of an alkali metal or metals to be added to the total amount of PbO, an alkaline earth metal or metals and ZnO is limited, in order to reduce dissolution of lead. However, the reduction achieved is only about one half. It is an object of the present invention to provide a novel glass composition which exhibits such characteristics of lead-containing crystal glass as that "it is massive"; that "it has a high refractive index and high dispersion value"; and that "it melts readily" to a degree equal to or higher than that of conventional lead-containing crystal glass, while not containing lead at all. In order to attain the object described above, according to an aspect of the present invention, there is provided a glass composition having properties similar to those of crystal glass but containing no lead, comprising 50 to 60 percent by weight of SiO 2 , 5 to 13 percent by weight of K 2 O, 5 to 8 percent by weight of TiO 2 , 10 to 15 percent by weight of BaO, 5 to 10 percent by weight of ZnO, 3 to 10 percent by weight of Na 2 O, and 0.3 to 0.8 percent by weight of Sb 2 O 3 . The glass composition may also comprise 1 to 5 percent of CaO based on the whole weight of the composition. The glass composition may further comprise, based on the whole weight of the composition, 0 to 1.0 percent of Li 2 O, 0 to 2.0 percent of ZrO 2 , and 1.0 to 2.0% of B 2 0 3 . The contents of the components given above are listed in Table 1 below. It is to be noted that representations of % in the following description are all represented in percent by weight. Component Content wt% SiO 2 50.0 - 60.0 CaO 1.0 - 5.0 BaO 10.0 - 15.0 Na 2 O 3.0 - 10.0 K 2 O 5.0 - 13.0 Li 2 O 0 - 1.0 TiO 2 5.0 - 8.0 ZnO 5.0 - 10.0 ZrO 2 0 - 2.0 B 2 O 3 1.0 - 2.0 Sb 2 O 3 0.3 - 0.8 With the glass composition of the present invention, Ti0 2 and BaO are used as raw materials substituted for PbO, and the refractive index and the dispersion value of light are increased by TiO 2 , while the density and the refractive index are increased by BaO. TiO 2 is effective to increase the refractive index and increase the dispersion value (decrease the Abbe number) and is essential as a substitute for PbO in the present invention. Where TiO 2 is less than 5.0%, the target values of the refractive index and the dispersion value cannot be achieved. On the other hand, where TiO 2 exceeds 8.0%, the tendency that the color becomes yellowish increases significantly, and this is undesirable with crystal glass where importance is attached to transparency. If SiO 2 is less than 50.0%, then the glass composition is inferior in chemical durability, but if SiO 2 exceeds 60.0%, then it is necessary to raise the melting temperature of the glass composition and the density of the glass composition is decreased. While both of BaO and CaO can be employed as an alkaline earth metal, preferably BaO is used in order to assure a high density and a high refractive index. Where BaO is less than 10.0%, the target value of the high density of 2.90% or more cannot be achieved. Where BaO exceeds 15.0%, it is difficult to perform defoaming and the erosion of the furnace material is marked, and accordingly, it is difficult to melt the glass composition. While CaO is effective to lower the viscosity of the glass composition at a high temperature, it is suitably contained by 1.0 to 5.0% in order to assure a high solidifying rate in an operating temperature region. Alkali components, that is, K 2 0, Na 2 0 and Li 2 0 are used to lower the melting temperature. Particularly, K 2 0 is effective and important to suppress development of the color of Fe ions which are an impurity in the glass. The effect is low where K 2 0 is less than 5.0%, but where it exceeds 13.0%, the erosion of the refractory material is remarkable. Na 2 0 must necessarily be contained in an amount of at least 3.0% in order to make up for the effect of lowering the melting temperature. Where the total amount of K 2 0 and Na 2 0 exceeds 18.0%, the chemical durability of the glass is degraded, and accordingly, it must necessarily be restricted to 18.0% or less. Li 2 0 has a marked effect of lowering the melting temperature by addition of a small amount, and it is sufficient if it is contained in an amount of 1.0% or less. ZnO is effective to increase the chemical durability without increasing the hardness of the glass, moderate the viscosity-temperature curve and facilitate the molding operability. The amount of addition is sufficient if within the range of 5.0% to 10.0%. Since B 2 0 3 is effective to lower the melting temperature without increasing the coefficient of thermal expansion by addition of a small amount, it is added in an amount of 1.0 to 2.0%. Sb 2 0 3 has an effect as a defoaming agent in a composition melted at a low temperature, even in such a small amount as 0.3 to 0.8%. While ZrO 2 is added in order to raise the chemical durability, since it increases the hardness of the glass, it is not preferred with crystal glass, which is in most cases worked by cutting or polishing; and, accordingly, the amount of its addition must be restricted to a minimum. Due to such actions of the components as described above, a glass composition can be obtained which sufficiently satisfies such requirements for crystal glass that (1) the density as representative of massiveness is 2.90 g/cm 3 or more; (2) the refractive index Nd is 1.55 or more; (3) the Abbe number as representative of dispersion is 47 or less; (4) the glass composition can be melted readily at a low temperature of 1,370 to 1,380 °C; and (5) the coefficient of thermal expansion can be made lower than 100 x 10 7 /°C taking into consideration that the glass composition is used frequently for tableware. It is to be noted that it is of course possible to add a coloring agent such as chromium oxide by a small amount to produce colored crystal glass. As described above, according to the present invention, crystalline glass which has a density, a refractive index and a dispersion value equal to or higher than those of conventional lead-containing crystal glasses can be obtained, although the glass does not contain lead at all. Further, the raw materials are comparatively inexpensive and can be melted at a comparatively low temperature, and accordingly, the glass composition can be produced economically. When it is considered that the regulations regarding the use of lead are forecast to become progressively more severe, not only from the point of view of dissolution from glassware, but also of the production environment and of the environmental pollution caused by dust and fumes emitted at different stages of production, from the mixing of the raw materials to the blast furnace, the advantage of a glass composition that is entirely free of the highly toxic lead component is very great. Some non-limiting Examples are now presented to illustrate the invention. The glass compositions designated Example 1 to Example 7 in Table 2 were mixed, put into respective platinum pots, and melted for about 6 hours at a temperature of 1.375°C in an electric furnace. Thereafter, the pots were taken out, the molten glass materials flowed out onto a steel plate, and then cooled gradually in a lehr. Samples for measurement were then removed, and the density, refractive index, Abbe number and coefficient of thermal expansion of each of the samples were measured. Results of the measurements are listed in Table 2. It is to be noted that conventional exemplary lead-containing crystal glass has a density of 2.95 to 3.00 g/cm 3 , a refractive index Nd of 1.555 to 1.565, an Abbe number of 45 to 47 and a coefficient of thermal expansion of 96 to 100 x 10 7 /°C. Components & Physical Data Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 SiO 2 54.95 54.60 51.15 51.80 50.10 55.50 55.20 CaO 4.00 3.50 5.00 4.00 3.00 1.50 1.50 BaO 12.00 12.50 14.00 13.00 14.50 13.00 13.30 Na 2 O 3.00 3.50 3.00 5.00 3.00 6.00 9.50 K 2 O 9.00 10.00 11.00 8.00 12.50 7.00 5.00 Li 2 O 0.50 0.50 0.50 0.50 0.50 TiO 2 7.50 7.00 5.00 8.00 7.00 6.50 5.00 ZnO 7.50 8.00 7.50 8.00 7.00 9.00 9.00 ZrO 2 1.00 1.00 1.00 B 2 O 3 1.25 1.00 1.50 1.30 1.00 1.00 1.00 Sb 2 O 3 0.30 0.40 0.35 0.40 0.40 0.50 0.50 Density (g/cm 3 ) 2.885 2.908 2.951 2.940 2.955 2.902 2.906 Refraction Index Nd 1.589 1.590 1.588 1.600 1.601 1.582 1.577 Abbe Number 46.5 46.8 48.2 45.5 46.5 47.0 47.0 Coefficient of Thermal Expansion (x 10 -7 /°C) 92.6 97.0 101.4 98.3 105.5 94.3 99.5

Claims: A glass composition having properties similar to those of crystal glass but containing no lead, comprising 50 to 60 percent by weight of SiO 2 , 5 to 13 percent by weight of K 2 O, 5 to 8 percent by weight of TiO 2 , 10 to 15 percent by weight of BaO, 5 to 10 percent by weight of ZnO, 3 to 10 percent by weight of Na 2 O, and 0.3 to 0.8 percent by weight of Sb 2 O 3 . A glass composition as claimed in Claim 1, further comprising 1 to 5 percent by weight of CaO. A glass compostion as claimed in Claim 2, further comprising 0 to 1.0 percent by weight of Li 2 O, 0 to 2.0 percent by weight of ZrO 2 , and 1.0 to 2.0 percent by weight of B 2 O 3 .

Inventors: INABA SHIZUE, KOMIYA HIDETOSHI, OGATA HARUHIKO, INABA, SHIZUE, KOMIYA, HIDETOSHI, OGATA, HARUHIKO
Applicants: TOYO GLASS CO LTD, TOYO GLASS COMPANY LIMITED
Application year: 1993
Main classification: C03C3
IPC codes: A47G19, C03C4, C03C3