KR940005534B1 - Process for producing glass ceramics - Google Patents

Abstract

The natural stone patterned crystallized glass is produced by (a) mixing crystalline glass particles, 1-5 wt.% Zn-Fe-Cr based inorganic pigment and 1-10 wt.% an organic binder, (b) molding the mixture to sphere type body having particle size of 1-10 mm, (c) mixing this molded body and two species of crystalline glass particles added to coloring agents which are black type agent(mixture of ferric oxide, titania and cobalt oxide) and deep grey type agent (mixture of ferric oxide, nickel oxide and cobalt oxide), respectively (d) heating at 1,060 deg.C for 2 hrs.

Description

Natural Stone Pattern and Inorganic Crystalline Glass Using Inorganic Pigment and Its Manufacturing Method

1 is a view schematically showing the surface state of the architectural crystallized glass according to the present invention.

2 is a cross-sectional view showing a state in which spherical particles in which crystalline glass powder, an inorganic pigment and an organic binder are mixed are filled in a fireproof box coated with the siblings.

* Explanation of symbols for main parts of the drawings

1: crystallized glass for building

2: spherical particles having fine β-willastonite crystals deposited uniformly and inorganic pigments dispersed well between these crystals to give a homogeneous color

3: β-willastonite crystal 4: inorganic pigment

5: spherical particle interface 6: release agent layer

7: fireproof

8: Spherical particles mixed with crystalline glass powder, pigmentless and organic binder

The present invention relates to a crystallized glass for construction of natural stone pattern using inorganic pigments and a manufacturing method.

Crystallized glass, which is obtained by countlessly generating fine crystals inside glass by reheating it, has excellent mechanical strength, abrasion resistance, chemical durability, etc., and thus is used in various fields. Is increasing.

The crystallized glass shown in Korean Patent No. 38854 and Patent Application No. 89-5196, which is the invention of the applicant, is a representative example.

In recent years, the diversification and quality of building materials is required, and architectural crystallized glass should be able to exhibit various colors and patterns. As in the case of producing colored glass, it is common to make the glass itself colored by adding a colored component to the glass raw material and melting the same as in the production of colored glass. However, this method is bonded to mass production, such as melting in a tank furnace, but it is uneconomical for producing small quantities of various products, and there are limited types of colors that can be produced, and there is a problem that the color is not stable depending on the composition of glass or the melting atmosphere. . Therefore, there is a need for a new method for variously colored architectural crystallized glass. By mixing inorganic pigments with crystallized glass particles and heat-treating them, various colors can be exhibited. The method is introduced in Patent Application No. 88-16463, which can use various colors of inorganic pigments as it is. It is a coloring method. However, this method only mixes the inorganic pigments around the glass particles so as to disperse the inner color of the glass after the heat treatment, and the boundary surface with the particles shows the color of the pigment. In addition to giving a feeling, especially when various kinds of inorganic pigments are combined to make a variety of colors mixed, heterogeneous colors appear at the interface where glass particles with different colors of inorganic pigments come into contact with each other. This is undesirable because of the problem that unwanted mixed colors appear.

The present invention is intended to suggest a method that can improve the above-mentioned shortcomings and the color and pattern closer to the natural stone pattern and give a very natural feeling. By controlling the size of the crystalline glass particles to be close to the powder state, the crystalline glass powder and the inorganic pigment are uniformly mixed, and after adding the organic binder therein to obtain spherical particles using a granulator. Separately, by adding a colorant to the glass raw material composition to obtain crystallized glass particles, by mixing and heat-treating them, a unique color by spherical particles and simply colored crystallized glass are combined with each other to obtain architectural crystallized glass showing a more natural color and pattern. Can lose. In particular, this method has the advantage that various colors can be harmonized using inorganic pigments of various colors. When spherical particles are made of crystalline glass powder mixed with pigments of different colors, and mixed and heat-treated, surface patterns in which different colors are mixed appear to produce various products in which various colors are harmonized. In addition, the production of crystallized glass for construction in various color tones and patterns can be made freely by mixing the crystalline glass powder and the crystalline glass particles with the inorganic pigment and the crystalline glass particles having the color of the glass itself.

Referring to the production method according to the invention in detail as follows.

The crystalline glass particles obtained by melting and then quenching the combined glass raw materials for use as architectural crystallized glass are dried, and then passed through a vibrating body to take fine powder of 0.5 mm or less. Glass particles larger than 0.5mm are not only difficult to make spherical particles using a granulator, but also unevenly mixed with inorganic pigments. An inorganic pigment and an organic binder of a desired color are added to the crystalline glass powder. Approximately an inorganic pigment is added to the crystalline glass powder in a weight ratio of 1 to 5%, and an organic binder is added to 1 to 10%, and mixed in a mixer. If the amount of the inorganic pigment is less than 1%, the color is too light, so it is not preferable. If the color is more than 5%, the color becomes too dark, the color of the inorganic pigment is not uniform after the heat treatment, and the surface of the crystallized glass is smooth. A problem that does not soften easily occurs. In addition, when the addition amount of the glass binder is less than 1%, the bonding force is weak, making it difficult to form spherical particles in the granulator, and when it is 10% or more, it is not preferable because a large amount of pores remain in the crystallized glass after heat treatment.

The raw material mixed with crystalline glass powder, inorganic pigment and organic binder is put into plate or cylinder type granulator and sprayed with water to make spherical particles of 1 ~ 10mm size and dried by hot air to harden them. When the size of the spherical particles is larger than 10mm, the filling density is low when filling the saggar pack, so that the surface is not smooth after heat treatment.

Separately, crystalline glass particles are granulated by adding, melting, and cooling a colorant to a conventional glass composition.

The size of the glass particles is preferably about 1-3mm. The crystalline glass particles and the spherical particles thus obtained are mixed well and then filled into a saggar and heat treated. Particles filled in the saggar pack are softened during heat treatment, are fused and integrated with each other, and when the crystallized glass plate has a smooth surface, the organic binder is burned and blown off during this heat treatment. Polishing the surface with these automatic polishers results in architectural crystallized glass with beautiful surface patterns and colors.

The crystallized glass which can be used in the present invention is preferably the composition shown in the above-mentioned Korean Patent No. 38854 and Patent Application No. 89-5196, but has a characteristic of softening the surface and smoothing of the crystals upon precipitation. If it is a composition, it can be used.

In addition, any inorganic pigment that can be used in the present invention can be used as an oxide capable of exhibiting a desired color, which is excellent in heat resistance and can be maintained as an oxide without discoloration even when heat-treated with crystallized glass.

Further details of the invention are illustrated by the following examples.

Example 1

[Production of Spherical Particles]

60% SiO ₂ , 8% Al ₂ O ₃ , CaO 19%, ZnO 1.5%, BaO 4%, Na ₂ O 3%, K ₂ O 1.4%, LiO 1.5%, B ₂ O ₃ 1.6% by weight The glass raw materials combined to form the composition are melted at 1500 ° C., quenched in water to dry the granulated crystalline glass, and passed through a vibrating body to take a fine powder of 0.5 mm or less. Zn-Fe-CrrP brown inorganic pigment is added to this crystalline glass powder in a weight ratio of 2.0%, and then 3% of an organic binder (methyl cellulose powder) is added, followed by sufficient mixing for 10 minutes in a mixer. The mixture was introduced into a granulator to spray spherical water into spherical particles 1-10 mm in size.

Example 2

[Preparation of spherical particles of various colors]

1%, 2%, and 1 of inorganic pigments of Al-Co-Cr-based, Zn-Fe-Cr-based, and Al-Zn-Co-Cr-based crystalline glass powders of 0.5 mm or less in the same composition as in Example 1, respectively % Is added, and 5% of the organic binder is added thereto, mixed, and used in a granulator to make the blue, brown, and green spherical particles 1 to 5 mm, 3 to 5 mm, and 1 to 5 mm in size.

Example 3

Fe ₂ O ₃ , TiO ₂ , CoO were added to the glass composition by melting and cooling to prepare black crystalline glass particles (1 to 3 mm). Further, NiO, CoO, Fe ₂ O ₃ was added as a colorant to melt and cool to prepare dark gray crystalline glass particles (1 to 3 mm). The spherical particles prepared in Example 1 (3 to 8 mm), the black glass particles and the dark gray glass particles were mixed well by weight ratio of 30%, 30% and 40%, respectively, and placed in a fireproof sachet to 1060 ° C per minute. By heating at a rate of 2 ° C., holding at this temperature for 2 hours, and slowly cooling, black, dark gray, and brown were well harmonized to obtain architectural crystallized glass exhibiting a natural surface pattern such as natural stone.

1 is a schematic view of the surface state (1) of the architectural crystallized glass produced by the present invention, (2) is a spherical particle formed by mixing a crystalline glass powder, an inorganic pigment and an organic binder, showing a homogeneous color. (3) is fine β-wollastonite crystals that are uniformly precipitated after heat treatment, (4) are inorganic pigment particles dispersed well between the crystals, and (5) is formed by spherical particles. The surface pattern is represented by the interface.

FIG. 2 shows a state in which a spherical particle 8 formed by mixing crystalline glass powder, an inorganic pigment and an organic binder is filled in a fireproof sacks 7 coated with a releasing agent 6, and the spherical particles are heat-treated in this state. The crystallized glass for building which these were integrated is obtained.

Claims (6)

A crystallized glass for construction of natural stone pattern obtained by mixing spherical particles obtained by mixing and molding a crystalline glass powder, an inorganic pigment, and an organic binder with crystalline glass particles obtained by adding a colorant to a glass raw material composition, and heat treating the same. According to claim 1, wherein the inorganic pigment is 1 to 5% by weight based on the weight of the crystalline glass powder, and the organic binder is added in an amount of 1 to 10% by weight based on the weight of the crystalline glass powder. Crystallized glass for building of the natural stone pattern. The crystallized glass for building a natural stone pattern according to claim 1 or 2, wherein the inorganic pigment is a Zn-Fe-Cr-based inorganic pigment. The method of claim 1, as a coloring agent a crystallized glass obtained by adding a coloring agent to the glass material composition of,, Fe ₂ O _3, TiO ₂ and Fe ₂ O as a mixture of crystallized glass particles, the colorant of the black with the CoO _3, NiO And a mixture of dark gray crystalline glass particles using a mixture of CoO. 5. The crystallized glass for building natural stone according to claim 4, wherein the spherical particles, the black glass particles, and the dark gray glass particles are mixed at a weight ratio of 30 to 50:20 to 40:20 to 40, respectively. Melting and quenching the glass composition capable of forming the crystallized glass to obtain a crystalline glass powder, by adding 1 to 5% by weight of inorganic pigment and 1 to 10% by weight of organic binder based on the weight of the crystalline glass powder. After mixing, the mixture is formed into spherical particles having a particle size of 1 to 10 mm using a granulator, and separately, a colorant is added to the glass raw material composition, melted, and then quenched in water to form crystalline glass particles. Obtaining a mixture of these particles and spherical particles, filling them in a saggar, heat treating them, and integrating them so that these two particles are dispersed evenly.