JPS6365614B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing a crystallized glass article suitable for architectural, decorative, etc. uses.

[Conventional technology]

One of the methods known so far for making patterns appear on crystallized glass is
There are methods that mainly involve coloring, as exemplified by Japanese Patent Publication No. 46-43238 and Japanese Patent Publication No. 57-175751.
This method has the disadvantage that only a colored pattern is obtained on the surface, and the design effect on the appearance is poor.

Therefore, we aimed to obtain a very tasteful and beautiful pattern that can also have the appearance of natural stone, mainly due to the deep shading pattern caused by the crystal orientation and the mixture of crystals and matrix glass phase. The method was also published in Tokuko Sho 53-19607, Tokko Sho.
No. 55-29018.

However, in Japanese Patent Publication No. 53-19607, a flat patterned crystallized glass can only be obtained by completely removing the unevenness on the surface of a crystallized glass product obtained by heat treatment, and a mirror-like flat The disadvantage is that the grinding and polishing process to obtain this requires a great deal of effort and time.

In the so-called sintering method, as typified by Japanese Patent Publication No. 55-29018, crystalline glass bodies colored in various colors are accumulated and then heat treated to change the orientation of the crystals and the relationship between the crystals and the matrix glass phase. Although it is possible to obtain very beautiful crystallized glass that has a deep natural stone-like pattern due to the mixture of crystalline glass bodies and a colored design based on colored glass bodies, the voids between the accumulated crystalline glass bodies can be obtained. will necessarily remain as pores in the final crystallized glass product, which will impair the physical properties of the material.

Therefore, the present applicant has conducted various studies on methods for manufacturing crystallized glass articles that have the above-mentioned deep and aesthetically superior appearance, do not require complicated finishing processes, and are free from internal pores. In order to improve the above-mentioned design effect, it is necessary to form an interface in advance that becomes a starting point for crystal precipitation and growth inside the glass article during the heat treatment for crystallization, while at the same time not inviting defects such as pores. I focused on what I could do.

As one of such new manufacturing methods, the present applicant has developed a method of creating cracks in a crystalline glass article before heat treatment (hereinafter, the one before heat treatment is referred to as crystalline, and the one after heat treatment is referred to as crystallization). We have proposed a method of applying heat treatment after applying the crack (hereinafter referred to as the "crack-filling method").

[Purpose of the invention]

The present invention was made based on the above-mentioned points, and its purpose is to create a deep natural stone-like pattern due to crystal orientation and the mixture of crystals and matrix glass phase, as well as to create free coloring. Designs can be applied easily, without compromising the physical properties of the material, and the manufacturing process is simple.
The purpose of the present invention is to provide a method for making a pattern appear on crystallized glass.

[Means for solving problems]

The manufacturing method according to the present invention, which has been made to achieve the above object, is characterized by the step of preparing a melt of crystalline glass having a property that crystals precipitate and grow from the surface toward the inside by heat treatment; A step of molding the melt into a desired shape, a step of dispersing small glass pieces in the melt at the same time as this molding step or prior to the molding step, and a step of dispersing the glass molded product after molding for crystal precipitation and growth. It consists of a step of heat treatment.

The method of the present invention will be explained in detail below. First, a batch raw material that becomes crystalline glass, which has the property of precipitating and growing needle-like, dendritic, etc. crystals from the surface toward the inside when heat-treated, is melted and a melt is prepared. Separately, small pieces of amorphous glass or crystalline glass having the same properties as mentioned above are prepared, but the small pieces may have any shape such as granules, granules, spheres, rods, or plates. In addition, their size ranges widely from particles with a diameter of about 1 mm to quite large particles that can be mixed into the melt. Next, the amorphous glass pieces, the crystalline glass pieces, or a mixture thereof are dispersed in the above-mentioned crystalline glass melt, and the following method can be exemplified as the dispersion method.

(a) A method in which separately prepared glass pieces are introduced into the crystalline glass that is melted in a crucible, and the contents are then poured or scooped out onto a mold to form the glass. Press molding is also possible if the size of the glass pieces introduced is within the thickness of the desired molded product.

(b) A method of pouring molten crystalline glass onto a mold, scooping it out or dropping it as a gob, and then throwing separately prepared glass pieces onto the glass melt. By heating the upper surface of the glass melt and the inserted glass pieces with the flame of a burner, and by pressing the glass pieces by applying pressure from above using a method such as a press, the glass pieces can be embedded more completely. I can do it. Of course, press molding is also possible.

(c) A method in which a small piece of glass is placed on a mold in advance, and the molten crystalline glass is poured into the mold and dropped as a scoop or gob. By applying pressure from above using a method such as a press, the glass pieces can be more completely embedded.

When embedding small glass pieces, if the temperature is low, the glass melt will cool down at the contact surface with the crystalline glass melt and increase its viscosity, making it difficult to completely embed the glass pieces. Small glass pieces can be used in any of the above methods (a), (b), and (c).
It is desirable that it be preheated to about 300 to 900°C. If the glass piece is crystalline glass and has been preheated to a high temperature of about 900°C, crystals have already begun to precipitate on its surface, which has the effect of promoting crystal growth from the interface with the matrix glass after embedding. There is also.

Although any number of glass pieces may be embedded, it is naturally preferable to use a plurality of glass pieces in order to make the pattern that appears wider and lively. In addition, it is also possible to pre-color the crystalline glass that forms the matrix and the glass pieces that are embedded in various ways using a coloring agent. A crystallized glass article that also has a design pattern will ultimately be obtained.

a step of dispersing glass pieces into a glass melt;
In the forming process that is carried out simultaneously with or following this process, in order to prevent the internal interface, which is the starting point of crystal precipitation in the crystallization heat treatment process, from disappearing.
After dispersing the glass pieces, it is desirable to complete the molding process as soon as possible and proceed to the crystallization heat treatment process.

When a crystallized glass object formed by the pouring method, pressing method, etc. and having glass particles present in a crystalline glass matrix is heat-treated as described above, needle-like or dendritic crystals form the crystalline glass. Precipitation and growth begins to occur from the surface of the object, from the interface between the surface of the glass piece and the crystalline glass, or from the surface of the glass piece itself if the glass piece is crystalline glass, and if heat treatment is continued, the whole becomes coarse. It becomes an aggregate of crystals. When the upper surface of the obtained crystallized glass article is polished, a very beautiful and deep natural stone-like pattern appears due to the orientation of the crystals and the coexistence of the crystals and the matrix glass phase.

It is also possible to use a cracking method in combination by cracking the crystalline glass object by thermal shock or mechanical shock before proceeding to the heat treatment step. In this case, in addition to the surface of the crystalline glass object and the interface between the surface of the embedded glass piece and the crystalline glass, crystals precipitate and grow from the given cracks, resulting in a more interesting pattern. become.

The crystalline glass used in the present invention may be of the known composition described in the above publication or may be of other types, and the method of the present invention is not limited by the glass composition. . Also,
The composition of the glass pieces embedded in the crystalline glass that becomes the matrix can be the same as that of the matrix glass, or as mentioned above, various colored glasses can be used by using a coloring agent. By combining glasses, it is also possible to freely design the proportion and distribution of vitreous and crystalline materials in the final crystallized glass article by varying their crystallization rates.

[Embodiments of the invention]

Examples of the present invention will be described below. FIG. 1 shows a cross section of a crystalline glass object 3 in which embedded crystalline glass pieces 2 are scattered in a crystalline glass matrix 1, and 4 indicates the interface between the two. There is. FIG. 2 shows a cross-sectional view of a crystallized glass article 5 obtained by heat-treating the crystalline glass object 3, and 6 indicates the surface of the crystalline glass object, the surface of the embedded crystalline glass pieces, and This shows crystals that have precipitated and grown from the interface between the two. Drawing 3 shows a pattern that appeared by polishing the upper surface of the crystallized glass article 5, and 7 shows what the embedded crystalline glass pieces 2 have crystallized. ing. FIG. 4 shows a cross section of a crystalline glass article 8 in which amorphous glass pieces 10 are embedded in a crystalline glass object, and 9 shows the surface of the crystalline glass object and the amorphous glass pieces and the crystalline glass object. This shows crystals precipitated from the interface.

Example 1 Using silica powder, aluminum hydroxide, calcium carbonate, calcium borate, potassium nitrate, zinc white, and arsenous acid as raw materials, a glass batch was prepared to satisfy the following glass composition, and this was placed in a crucible and heated at 1450°C in an electric furnace. Melt at temperature for about 6 hours. _SiO2
35.4wt%, _{Al2O3 26.6wt} %, CaO 26.6wt%,
_{B2O3 1.0wt} %, _K2O 1.0wt%, ZnO 8.9wt%,
_{As2O3 0.5wt} %. Separately, a plurality of glass particles having a diameter of about 3 to 5 mm were prepared in advance by crushing a glass having the same composition.

After preheating the glass particles to approximately 400°C on a heater, they were placed into a crucible in which glass of the same composition was being melted, and the contents were immediately poured into a preheated iron mold frame with internal dimensions of 300 x 300 x 30 mm. poured out. The upper surface of the poured melt is heated with a burner flame to make it smooth, and then cooled at a temperature lowering rate that does not cause cracks.
A plate-shaped crystalline glass object 3 of approximately 300 x 300 x 20 mm as shown in the figure was obtained.

Next, the crystalline glass object was transferred to a refractory mold whose inner surface was coated with mold release agent powder, placed in a crystallization furnace, and heated at a rate of 200°C/hr. to a temperature of 1050°C. Heat treatment was carried out by holding at ℃ for 3 hours.
When the temperature exceeds 900℃ due to heat treatment, dendritic crystals begin to precipitate and grow from the surface of the crystalline glass object, the surface of the embedded granulated glass particles, and the interface between the two toward the inside of each object. Further heat treatment resulted in a dense aggregate of coarse dendrites without pores. Of course, the crystallization rate can be changed within a certain range by changing the heat treatment conditions.

When the upper surface of the obtained crystallized glass plate was polished, a beautiful and deep natural stone-like pattern as shown in FIG. 3 appeared. The patterns that appeared varied greatly depending on the shape, size, and number of embedded glass pieces.

Example 2 A glass having the same composition as in Example 1 is melted in the same manner as in Example 1 using silica powder, aluminum hydroxide, calcium carbonate, calcium borate, potassium nitrate, zinc white, and arsenous acid as raw materials. Separately, a plurality of glass particles having a diameter of about 3 to 5 mm obtained by crushing glass of the same composition were prepared in advance and preheated to about 400°C on a heater. After pouring the molten glass into a preheated iron formwork with inner dimensions of 300 x 300 x 30 mm, a plurality of preheated glass particles are immediately poured onto the upper surface of the molten glass in the formwork, and the molten glass is further poured into the formwork. The upper surface of the glass and the glass particles introduced are heated with the flame of a burner,
The glass particles were completely embedded in the molten glass. At this time, it was very effective to apply pressure from above using a method such as a press to force the glass particles into the molten glass.

After that, when the upper surface is polished by heat treatment using the same schedule as in Example 1, it has a beautiful and deep natural stone-like pattern as shown in Figure 3.
A crystallized glass plate of ×20 mm was obtained.

This embedding method is highly practical in that it is possible to select the embedding position of the glass piece intentionally to a certain extent, and it is possible to make a pattern appear according to the desired design if it is a simple letter or picture.

Example 3 A glass having the same composition as in Example 1 is melted in the same manner.
Separately, prepare several glass particles with a diameter of about 3 to 5 mm obtained by crushing glass of the same composition in advance, and scatter them in an iron formwork with internal dimensions of 300 x 300 x 30 mm. After placing it in the heater, approx.
Preheated to 600°C. The previously prepared molten glass was poured into it, and pressure was applied from above using a press to obtain a crystalline glass plate with the shape shown in FIG. 1 upside down.

When this was heat-treated on the same schedule as in Example 1 and the surface where the crystalline glass pieces were embedded was polished, it had a beautiful and deep natural stone-like pattern of about 300 x 300 x 20 mm as shown in Figure 3. A crystallized glass plate was obtained.

In the case of this embedding method as well, as in the case of the method of Example 2, a design pattern could be made to appear in accordance with simple letters and pictures.

Example 4 Effective amounts of cobalt oxide, chromium oxide, and iron oxide, which are known colorants, were added to a glass batch raw material prepared to satisfy the glass composition shown in Example 1, and melted. Prepare blue, green, and black crushed glass particles with a diameter of about 3 to 5 mm. By embedding a plurality of these three types of colored granulated glass grains in molten glass having the glass composition shown in Example 1 in the same manner as in Example 1, heat-treating them, and polishing the upper surface, a beautiful and deep A very clean crystallized glass article was obtained which, in addition to a certain natural stone-like pattern, also had blue, green and black polka dot patterns. In addition, by preparing pre-colored molten glass, embedding a large number of glass pieces colored in various colors into it and heat-treating it, it is possible to obtain a crystallized glass article having a very vibrant and deep colored pattern. Ta.

Example 5 A crystalline glass object 3 as shown in FIG. 1 is produced in the same manner as in Example 1. Next, the crystalline glass object is transferred into a fireproof mold whose inner surface is coated with mold release agent powder, held at about 300°C for about 20 minutes, and then water is applied to give a thermal shock. cracked the object. Thereafter, the cracked crystalline glass object was transferred to a crystallization furnace together with the refractory mold, and heat-treated according to the same schedule as in Example 1. In addition to the interface, crystals precipitate and grow from cracks, and when the top surface of the resulting crystallized glass product is polished, a very tasteful and beautiful pattern with a variety of crystal orientation and density appears. did.

Example 6 Using silica powder, aluminum hydroxide, calcium carbonate, calcium borate, potassium nitrate, zinc white, and arsenous acid as raw materials, a glass batch was prepared and melted to satisfy the following glass composition, and this was poured into water. A plurality of crushed glass particles each having a diameter of about 3 to 5 mm were prepared. _SiO2 35.4wt%,
_{Al2O3 26.6wt} %, CaO 26.6wt%, _{B2O3 1.0wt}
%, _K2O 2.0wt%, ZnO 7.9wt%, _{As2O3 0.5wt}
%. Next, by introducing the glass particles into a glass melt having the glass composition shown in Example 1 in the same manner as in Example 1, a crystalline glass object 3 as shown in FIG. Obtained.

When this was heat-treated on the same schedule as in Example 1 and the upper surface was polished, a beautiful polka dot light and dark pattern caused by the difference in crystallization rate appeared. That is,
Because the crystal growth rate of the embedded glass grains is slower than the crystal growth rate of the glass matrix, parts with a large amount of glass phase are scattered like polka dots in the deep white matrix.
The above pattern was obtained.

Example 7 Glass with the same composition as Example 1 was melted to a thickness of about 10 mm.
After press-forming into a plate shape, heat treatment was performed using the same schedule as in Example 1 to obtain a natural stone-like crystallized glass plate, and this crystallized glass plate was crushed with a hammer to obtain small pieces of crystallized glass with a diameter of about 3 to 5 mm. Prepare multiple pieces. After embedding a plurality of prepared crystallized glass pieces into molten glass having the same composition as in Example 1 in the same manner as in Example 1, and further heat-treating on the same schedule, the crystalline glass matrix surface and crystals Dendritic crystals precipitated and grew toward the interior of the crystalline glass matrix from the interface between the crystallized glass matrix and the embedded crystallized glass pieces, and a crystallized glass article was obtained. When the upper surface of this crystallized glass article was polished, a beautiful and deep natural stone-like pattern with rich variations in crystal orientation and density was revealed.

The small pieces of crystallized glass to be embedded may be those obtained by crystallizing small glass pieces, or may be ones obtained by crushing previously crystallized glass pieces as described above.
In the latter case, an interesting pattern with more variation in crystal orientation was obtained. Furthermore, when small crystalline glass pieces having the same composition as the crystalline glass matrix are embedded, it is difficult to obtain a pattern due to a difference in crystallization rate, that is, a change in crystal density. When small pieces of crystallized glass are embedded,
A polka dot-like shading pattern due to changes in crystal density can be easily obtained depending on the heat treatment conditions. Furthermore, since the crystallized glass pieces have better heat resistance than the crystalline glass pieces, they also have the advantage of being difficult to dissolve into the crystallized glass melt when embedding. In addition, the glass pieces to be embedded may be amorphous glass or a mixture of various glass pieces.

〔Effect of the invention〕

According to the method of the present invention, an extremely beautiful and deep natural stone-like pattern can be created in crystallized glass through a simple manufacturing process that does not require much labor or time without impairing the physical properties of the material. can. The shape and size of the embedded glass pieces,
Depending on the number, color, and even crystal growth rate in the case of crystalline glass, there is a wide variety of patterns that appear, and it is also possible to create any design depending on the position in which the glass grains are embedded. It also has the very excellent advantage that the artificial pattern can be easily combined with a natural stone-like pattern. As described above, the method of the present invention is a decoration method with a very high degree of freedom, and its usefulness is extremely large.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of a crystalline glass object in which small pieces of crystalline glass are embedded in a crystalline glass matrix, and FIG. FIG. 3 is a diagram showing a cross-sectional appearance of a crystallized glass article, and FIG. 4 is a diagram showing a pattern that appears by polishing the upper surface of the crystallized glass article. FIG. It is a figure which shows the appearance of the cross section of a crystallized glass article when a small piece is embedded.

Claims (1)

[Scope of Claims] 1. A step of preparing a melt of crystalline glass having a property that crystals precipitate and grow from the surface toward the inside by heat treatment, a step of shaping the melt into a desired shape, and a step of forming the melt into a desired shape. A crystallization method comprising the steps of dispersing small glass pieces in the melt simultaneously with the molding process or prior to the molding process, and heat-treating the glass molded product after molding for crystal precipitation and growth. Method for manufacturing a chemically converted glass article. 2. The method for producing a crystallized glass article according to claim 1, wherein the glass pieces are crystalline glass before heat treatment or heat-treated crystallized glass. 3. The method for manufacturing a crystallized glass article as set forth in claim 1, wherein the glass pieces are amorphous glass.