JPH0324433B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for manufacturing a composite of crystallized glass and ceramic, and its purpose is to provide a composite of crystallized glass and ceramic, which has the beauty of natural stone and has physical and chemical properties. The object of the present invention is to provide a crystallized glass composite that has excellent workability and is inexpensive.

[Conventional technology]

In the past, there were some methods, such as Japanese Patent Application Laid-open No. 11312/1983, in which a substrate and a plate glass were fused together. In this method, a plate glass is stacked on a substrate, and the plate glass is fused to the substrate by firing, thereby obtaining a substrate-glass composite.

[Problem to be solved by the invention]

However, this conventional glass composite had several drawbacks. First, since glass that has been fired and hardened is used, the substrate and glass do not fit well, and when fired on the substrate, the substrate and glass cannot be completely integrated, so it is difficult to break when used as a building material. There was a risk of peeling off, falling, etc. For this reason, glass composites have been considered unsuitable as building materials due to safety concerns. It has also become necessary to use a frit or the like to increase the adhesion between the substrate and the glass. Ordinary glass such as plate glass is transparent, but unlike crystallized glass, it does not have the texture of natural stone, and it is also weak against impact, which is one of the reasons why it is not suitable as a building material. . Furthermore, it has been difficult to create a wide variety of glass composites due to the manufacturing method. In other words, because the color, pattern, and shape of the plate glass are the same as those of the glass composite, the resulting composite is monochromatic and flat, with no variations in color, pattern, or shape.

[Means to solve the problem]

The present invention was devised to eliminate the above-mentioned drawbacks, and its structure consists of a glass raw material having a composition that melts and vitrifies at a lower temperature than that of the ceramic substrate formed into an arbitrary shape. Place the
By firing at a temperature where the ceramic substrate does not melt and the glass raw materials melt to form a uniform glass, the temperature is then lowered to an appropriate temperature higher than the glass strain point of the glass, maintained at that temperature, and then cooled. , a method for manufacturing a crystallized glass composite, characterized in that the interface between the crystallized glass and the ceramic substrate is fused and integrated.

Possible ceramic substrates include ceramics such as tiles (which may be molded objects before firing or after firing), cement materials, and the like. The compositions of glasses that are currently commercially available as crystallized glass include SiO ₂ -Al ₂ O ₃ -Li ₂ O, SiO ₂ -Al ₂ O ₃ -MgO, SiO ₂ -Al ₂ O ₃ -CaO, There are _SiO2 - _{Al2O3 - CaF2} series, _SiO2 - _{Al2O3 - TiO2} series, _SiO2 - _{Al2O3 -} ZnO series, etc. Since the glass having such a composition was designed to precipitate specific crystals for a specific use, the composition had to be limited to a certain range.

However, since glass generally has a tendency to crystallize to a greater or lesser extent, the composition of the crystallized glass used in the present invention may be one that has the above-mentioned composition as long as the crystallized glass has a natural stone-like texture. You can choose freely without any restrictions.

〔Example〕

An embodiment of the method for manufacturing a crystallized glass composite of the present invention will be described as follows. That is, a glass raw material having a composition that melts and vitrifies at a temperature lower than the melting temperature of the substrate is placed on a ceramic substrate, and the glass raw material is heated at a temperature at which the ceramic substrate does not melt and the glass raw material melts and becomes a uniform glass. After firing, the temperature is lowered to an appropriate temperature higher than the glass strain point of the glass, maintained at that temperature, and cooled to fuse the interface between the crystallized glass and the ceramic substrate, resulting in an integrated crystallization process. Manufacture of glass composites. In this case, if the difference in thermal expansion coefficient between the crystallized glass and the ceramic substrate is 5×10 ^-7 /deg or more, the product may break due to stress, so it is better to match the thermal expansion coefficients as much as possible. good. The glass raw material may be a natural raw material or a so-called frit that has been vitrified and pulverized.

A more specific example will be described.

_SiO2 is 59.1%, _{Al2O3 is} 6.8%, CaO is 17.9%,
Silica, alumina, lithium carbonate, zinc white, barium carbonate, and lime were mixed at a ratio of 7.2% ZnO, 4.0% BaO, and 5.0% Li ₂ O, and placed on a mullite ceramic substrate. 1400 in electric furnace
°C, heat for 1 hour to melt. Then, in the same electric furnace, the temperature is raised to 1000℃, which is above the strain point of glass.
Cool at a rate of 100°C/hr and hold at that temperature for 2 hours to allow crystallization. Thereafter, it is cooled to room temperature at a rate of 100°C/hr. As a result, a crystallized glass composite in which β-wollastonite (CaO.SiO ₂ ) was precipitated and integrated with the ceramic substrate was obtained. The composition is expressed in weight %, and the same applies hereinafter.

A second example will be explained.

_SiO2 is 59.3%, _{Al2O3 is} 7.0%, CaO is 17.7%,
7.1% ZnO, 4.2% BaO, 1.8% _Na2O , _K2O
Silica, feldspar, zinc white, barium carbonate, and lime are mixed at a ratio of 2.9% and heated in an electric furnace at 1450°C for 1 hour to melt and vitrify. After crushing the glass, it is placed on a mullite ceramic substrate and heated in an electric furnace at 1300°C for 1 hour to melt it. Subsequently, in the same electric furnace, it is cooled at a rate of 100°C/hr to 1100°C, which is above the strain point of glass, and held at that temperature for 2 hours to crystallize. Thereafter, it is cooled to room temperature at a rate of 100°C/hr. By this, β-wollastonite (CaO・SiO ₂ )
was precipitated, and a crystallized glass composite integrated with a ceramic substrate with a natural stone pattern was obtained.

In all of the above embodiments, a crystallized glass composite integrated with a ceramic substrate having the texture of natural stone is obtained, and the appearance can be further improved by polishing. In this case, since the glass has been melted once, the surface is smooth and polishing is extremely easy.

〔effect〕

As described above, according to the present invention, since crystallized glass is created on a ceramic substrate, complete integration of the crystallized glass and the ceramic substrate can be obtained, so when used as a building material, etc., peeling, falling, etc. There is no danger of There is no need for a frit or the like to increase the adhesion between the substrate and the crystallized glass. In addition, since the glass is crystallized, the unique opacity of crystallized glass creates a natural stone-like texture, and it is stronger than ordinary glass, being more resistant to impact and less likely to break.
In addition, regarding the color of the glass composite, it is possible to place any glass raw material in any ratio on each ceramic substrate, and also to mix ceramic particles into the glass raw material, so crystallization can be controlled. The pattern can be freely controlled. Therefore, it is possible to produce a wide variety of products in small quantities, and to meet the diverse needs of consumers.

Therefore, it can be said that the crystallized glass composite according to the present invention has excellent functionality as a building material and also has high decorative properties.

Claims (1)

[Claims] 1. A glass raw material having a composition that melts and vitrifies at a lower temperature than that of the substrate is placed on a ceramic substrate formed into an arbitrary shape, and the ceramic substrate does not melt and the glass raw material melts to form a uniform glass. The interface between the crystallized glass and the ceramic substrate is fused and integrated by firing at a temperature of A method for producing a crystallized glass composite, characterized in that: