JPH0345531A - Colored crystallized glass composite material and production thereof - Google Patents

Abstract

PURPOSE:To improve reduction in productivity resulting from change of material in production of colored crystallized glass composite material by piling plural sheets of crystallized glass material of volume crystallization type showing different color tones after crystallization treatment and heating the material. CONSTITUTION:A raw material containing a nucleating agent and a colorant is continuously heated, melted and clarified to give molten glass. Then the glass is annealed and cut into a given dimension to produce a raw plate of transparent colored crystallized glass. Then the raw plate of colored crystallized glass is piled on a raw plate of crystallized glass not containing a colorant produced separately, heated and maintained at a given temperature for a given time to fuse both the raw plate glass and to subject to crystallization treatment. By the treatment, crystals of diopside, aluminum-containing diopside and enstatite are grown in TiO2, etc., as a crystal nucleating agent and precipitated to fuse both the glass plates.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a composite of colored crystallized glass.

[Prior art] Among crystallized glasses in which a crystalline phase is precipitated in an amorphous phase,
Larger sizes are mainly used as artificial marble for wall materials. Current wall materials on the market include Asahi Glass's Criston (trade name) and Nippon Electric Glass's Neopalier (same name). The biggest difference between the two is that the former performs volume crystallization type crystal growth in which crystals are mainly grown around a nucleation material, whereas the latter performs surface crystallization type crystal growth. Once these crystallized glasses were 14
Glass is melted at a high temperature of 00°C to 1500°C and then cooled to produce a completely amorphous base glass (hereinafter referred to as base plate), which is then reheated to 600°C.
The crystal nuclei are grown between ℃ and 1000℃, and then further grown at 900℃.
Crystals are grown between ~1200°C. This process of crystallization through heat treatment is called ceramic. The raw plate before ceraming has absorption in the visible range when it contains a coloring material, but is essentially transparent, and when crystals grow in the ceramic, reflection occurs in the crystal lattice and it becomes opaque.

There are two types of crystallized glass: volume crystallization type, in which when crystals develop, nuclei are generated uniformly from inside the base plate, and crystals grow around the nucleus, and the other is the volume crystallization type, where the crystals grow around the nucleus. There is a surface crystallization type in which crystals grow from the inside toward the inside. In the latter case, in order to grow crystals to the inside, the blank is first crushed, then heat treated, and the dense blank pieces are fused together (this is called the integration method). In the former case, a plate-shaped base plate is prepared in advance using known sheet glass manufacturing technology, and then ceramic is applied as is, which simplifies handling as a manufacturing method for crystallized glass for wall materials. .

The present invention is directed to a volume crystallization type colored crystallized glass composite in which crystals are mainly grown around this nucleation material.

[Problems to be Solved by the Invention] When producing colored crystallized glass, the coloring component must be mixed into the raw material from the stage of melting the base plate.

For this reason, all of the molten glass in the glass kiln has a component concentration that should give the target color tone, and if a different color tone is to be obtained, the molten glass in the entire kiln must be replaced. Typically, this replacement work involves adding raw materials of a new composition onto the old molten glass. (This work is called resurfacing.) As a result, the intermediate tone glass until resurfacing is completed cannot be used as a product and is lost.

The purpose of the present invention is to reduce this loss, and to produce a colored crystallized glass composite having a structure that has not been previously known as a crystallized glass mainly used as a wall material for buildings. The purpose is to provide new information.

[Means for Solving the Problems] The present invention is a composite body formed by bonding two or more volumetric crystallized glass plates, in which at least one crystallized glass plate located on the outside has a colorant added thereto. The object of the present invention is to provide a crystallized glass composite characterized in that it is colored by:

The crystallized glass in the present invention mainly contains precipitated crystals that grow mainly from a nucleating agent by heat treatment. The nucleating agent and crystals are not particularly limited, and examples include diopside, aluminum-containing diopside, and enstatite precipitated by nucleating agents such as TiO□, ZrO, and F.

Further, the crystallization rate is not particularly limited, and a commonly used crystallization rate of about 4 to 50% is used.

The coloring agent is not particularly limited, and may include Mn0a and CoO.

Fears, Cr1es, NiO, Se, Van
Known materials such as s, CaO, etc. are widely used.

There is no particular limit to the thickness of the crystallized glass, but if it is used as a wall material, it needs to be strong, so a composite material with a thickness of about 12 to 20 mm is recommended.
JS is preferred.

The crystallized glass plate can be bonded to the picture tone plate through an adhesive, or it can be directly bonded by heat fusing without using an adhesive. In the former case, they may be bonded in a ceraming process using an adhesive such as solder glass, or they may be bonded using an adhesive after each piece of glass is ceramed. Furthermore, in the latter case, it is preferable to bond in a ceraming process in terms of improving productivity.

When bonding is performed by heating, it is preferable to minimize the difference in thermal expansion coefficients between the two glass sheets in order to reduce distortion such as warping and thereby maintain adhesive strength. Specifically, the difference in expansion coefficients is preferably within IOX 10-'/'C.

The colored crystallized glass composite in the present invention can be produced as follows.

A raw material containing a nucleating agent and a coloring agent is continuously heated and melted and clarified to obtain molten glass, which is formed into a ribbon-shaped glass of a predetermined thickness by a roll-out method or the like. Next, this is slowly cooled and cut into a predetermined size to produce a material plate of colored crystallized glass that has absorption in the visible range but is substantially transparent. Next, this colored crystallized glass base plate and a separately manufactured crystallized glass base plate that does not contain a colorant are stacked together, and heated and held at a predetermined temperature for a predetermined time to fuse the pixel glass plates and ceramicize them. Perform processing. The temperature and time of this ceraming treatment vary depending on the composition of the base plate. For example, 5iOi
50-70 wt%, Ahas 2-17 it%,
ao O~10 wt%, Mg06~15 wt%
In the case of a base plate composition of 0.2 to 6 wt% TiOi, by holding it at a temperature of 950°C to 1150°C for about 4 hours, the crystals of diopside, aluminum-containing diopside, and enstadite form crystal nuclei of TiO□, etc. It grows and precipitates as an agent, and the image tone plate is fused.

Further, it is also possible to interpose solder glass between the pixel plates during the ceraming process and to bond them with the solder glass during the ceraming process.

[Example] Example 1 High purity silica sand as 5iOi source, A1.0. Alumina hydroxide as a source, limestone as a CaO source, magnesium hydroxide as an MgO source, soda ash as a Na*0 source,
To! Potassium carbonate is used as a 0 source, lithium carbonate is used as a LixO source, titanium oxide powder is used as a TiOx source, zinc white is used as a ZnO source, borax is used as a Btus source, calcium phosphate is used as a has source, and the target composition is 5iOa.
61.0%, A1.0.7%, Ca04.0%,
MgO12.0%, Nano 4.5%, K, OO
,5%, Li2O0,2%, Bib, 1.5%,
Pieces 0.5%, Zn 07.0%.

TiO□1.5%, FO, 3% (weight percent)
Mix the raw materials so that 1450
It was melted and clarified at ℃ for 5 hours. This glass was poured into a refractory mold and cooled in a small electric furnace to form a 11 cm x 1
A transparent blank plate of 1 cm x 12 am thick was obtained.

Meanwhile, a base glass having the above composition in which 0.5 g of iron oxide powder Fears was added per 100 g was prepared in the same manner and melted under the same conditions to obtain a base glass of 11 cm x 11 cm x 6 mm thick. This blank plate contained the colorant F620m, so although it was colored deep brown, it was essentially transparent.

After cutting these two blank plates into 10cm x 10cm pieces, the surfaces were polished using calcium carbonate slurry using a small polishing machine until they became flat, and after washing and drying, the polished surfaces were placed against each other on a refractory base plate. I placed them one on top of the other. Next, it was placed in a heat treatment furnace, heated at 50° C./hr, and subjected to crystallization treatment at 1000° C. for 4 hours.

When taken out from the electric furnace after slow cooling, this composite consisting of crystallized glass was firmly fused. Both surfaces were covered with a thin crust rich in diopside, and when this layer was polished off with a diamond grindstone, spots with an average diameter of about 1 mm had appeared. The thickness of the part that does not contain coloring agent is approximately 11 m.
m, the thickness of the colored layer was reduced to 4 mm by polishing away the epidermis, yielding a composite with a total thickness of about 15 mm. When this sample was sliced in the thickness direction with a diamond blade and the cross section was observed with the naked eye, a uniform boundary layer with a thickness of about 0.1 mm was formed on both sides of the fused surface, and no air bubbles were observed. There wasn't. The term "mottle" here refers to the fact that crystals initially develop into concentric spherical shapes around the crystal nuclei generated in the plate during the heating process of the ceramic, and after the grain boundaries come into contact with each other, the remaining matrix is formed. Crystals grow in the filling direction, resulting in crystal grain boundaries consisting of polyhedrons, so when the surface layer is cut and removed, artificial marble-like spots appear over the entire surface. When observing the area near this boundary layer using a scanning electron microscope, it is found that the crystals in this area are densely developed, generally perpendicular to the boundary surface, and the crystal grain size is smaller than the bulk parts on both sides, making it extremely strong. It was found that the two layers were fused at this boundary layer. Moreover, when the same part was observed with an X-ray microanalyzer, the peak ratio of "Fe" was found to be
0 (arbitrary unit) and white layer 1, whereas in the boundary layer it gradually decreases from 1O to 1, indicating that during the fusion process during ceraming, the glass structures of the layers on both sides diffused into each other and fused together. confirmed that.

From this sample, width 10mm, thickness 15cm, length 10cm
A rod-shaped sample was cut out and subjected to a three-point loading type destructive test to determine the bending strength, which was approximately 500 kg 7 cm, and compared to the strength of crystallized glass of the same composition without lamination of the same thickness, there was no significant difference. I didn't admit it.

Example 2 Using the same composition as in Example 1 and under completely similar melting and cooling conditions, a transparent blank plate and a colored transparent blank plate were obtained. The surfaces of these two blank plates were each 11 cm x 11 cm square, and as a characteristic of the molding method, the central part of the plane was raised higher than the peripheral part. These two sheets were stacked on a refractory table without going through any cutting or polishing steps. Next, Example 1
A heat treatment was performed under the same conditions as in Example 1, and the surface was polished to obtain a composite sample similar to that in Example 1. When this sample is sliced in the thickness direction and the cross section is observed, there is a thickness of O, ln at the boundary.
m produced a boundary layer similar to any of Example 1. However, this boundary layer exhibits undulations corresponding to poor flatness of the blank plate, and does not have a straight cross section like in Example 1, and there is a thickness of 0.2 + nm and a length of 0. .5mm
There were some scattered micropores (cut air bubbles). This sample has a width of 10mm, a thickness of 15mm+, and a length of lOc+n.
It was cut into a rod shape and its bending strength was measured at approximately 500.
kg/c-, and no significant difference was observed in the strength of crystallized glass of the same thickness and the same composition without lamination.

Example 3 Two blank plates obtained through the same process as Example 2 were cut,
They were placed one on top of the other on a refractory table with soda lime glass having the same thickness of 0.5 mm interposed therebetween, without going through a polishing process. Next, a composite sample was obtained in the same manner as in Example 2. When this sample was sliced in the thickness direction and the cross section was observed, two sheets of crystallized glass were firmly adhered to each other through the transparent soda lime glass. Soda lime glass becomes completely fluid in the highest temperature range during ceramicing, so the thickness of the glass after cooling was reduced to about 0.3 mm, and the excess flowed down from the edge of the plate. Therefore, since it is difficult to control the overall thickness, it is preferable not to use an adhesive in the case of actual part production.

[Effects of the Invention] According to the present invention, it is possible to extremely reduce the decrease in productivity caused by changing the base plate in manufacturing a base plate of colored crystallized glass.

That is, compared to the conventional method, since the proportion of colored crystallized glass in the entire composite is extremely small, the production amount of colored crystallized glass blanks can be reduced. Therefore, products of different colors can be produced in a planned manner, and the frequency of substrate changes can be significantly reduced. In particular, if colored crystallized glass blanks are produced in a small kiln, the drop in productivity due to substrate changes can be further reduced.

1 - fortune telling

Claims (4)

[Claims] (1) A composite formed by bonding two or more volume crystallized glass plates, characterized in that at least one crystallized glass plate located on the outside is colored by the addition of a coloring agent. A crystallized glass composite. (2) A composite body according to claim 1, in which a plurality of volume crystallized crystallized glass materials that exhibit different color tones after ceraming are stacked, and the base plates are heated to ceramize and adhere together. Production method. (3) The method for producing a composite according to claim 2, wherein the composite is fused without using an adhesive. (4) The composite according to claim 2, wherein the composite is bonded using an inorganic amorphous compound having a coefficient of linear expansion substantially equal to the coefficient of linear expansion of the crystallized glass after ceraming. How the body is manufactured.