JPS6224365B2 - - Google Patents

Description

Claim 1: A glass-crystalline material having a granite-like appearance and having the following component composition (% by mass) and mainly containing spherulite β-wollastonite crystals.

SiO ₂ 55.0-60.0 Al ₂ O ₃ 6.0-9.0 CaO 17.0-25.0 MgO 3.0-10.0 K ₂ O 5.0-7.0 Na ₂ O 1.0-2.0 F ^- 1.0-2.5 [However, SiO ₂ , Al ₂ O ₃ , CaO The total amount is less than 87% by weight. ] 2 0.05 to 4% by mass of at least one colorant
A glass-crystalline material according to claim 1, containing the glass-crystalline material of claim 1.

3. Glass-crystalline material according to claim 1, containing a colorant of oxide type.

4. The glass according to claim 1, 2, or 3, comprising components in the following proportions (mass%):
Crystalline substance.

SiO ₂ 55.0 ~ 57.0 Al ₂ O ₃ 6.0 ~ 9.0 CaO 17.0 ~ 23.0 MgO 3.0 ~ 10.0 Na ₂ O 1.0 ~ 2.0 K ₂ O 5.5 ~ 7.0 F ^- 1.5 ~ 1.8 Cr ₂ O ₃ 0.1 ~ 0.3 Co ₂ O ₃ 0.1 ~ 0.3 5. A glass-crystalline material according to claim 1 or claim 2, containing a colloidal type colorant.

6. The glass-crystalline material according to claim 1, 2, or 5, which contains components in the following proportions (mass%).

SiO ₂ 56.0-58.0 Al ₂ O ₃ 6.0-7.0 CaO 20.0-23.0 MgO 3.0-5.0 Na ₂ O 1.0-2.0 K ₂ O 6.0-7.0 F ^- 1.5-2.0 Sb ₂ S ₃ 2.0-2.5 7 Approximately 0.3-5 mm A glass-crystalline material according to any one of claims 1 to 6, having β-wollastonite of spherulite size.

8. By molding a glass from the melt, cooling it to a temperature 30 to 50 degrees Celsius lower than the glass transition temperature, and heat-treating it, a glass having the following component composition (mass%) and mainly spherulite β-wolast is formed. A method for producing a glass-crystalline material having a granite-like appearance containing night crystals.

SiO ₂ 55.0-60.0 Al ₂ O ₃ 6.0-9.0 CaO 17.0-25.0 MgO 3.0-10.0 K ₂ O 5.0-7.0 Na ₂ O 1.0-2.0 F ^- 1.0-2.5 However, the total of SiO ₂ , Al ₂ O ₃ , CaO The amount is less than 87% by weight. ] 9 Heat treatment of glass at 650-800°C in the first stage, followed by 930-950°C at a rate of 150-200°C/hour
9. The method of claim 8, wherein the glass is heated to a temperature of 100 mL and held for a sufficient time to convert the glass to the granite-like material.

10. The method according to claim 8 or 9, wherein the glass-crystalline material contains 0.05 to 4% by weight of at least one colorant.

11. A method according to any one of claims 8 to 10, wherein the glass-crystalline material contains a colorant of oxide type.

12 Glass - The following ratio of crystalline substances (mass%)
The method according to any one of claims 8 to 11, comprising the following components.

SiO ₂ 55.0 ~ 57.0 Al ₂ O ₃ 6.0 ~ 9.0 CaO 17.0 ~ 23.0 MgO 3.0 ~ 10.0 Na ₂ O 1.0 ~ 2.0 K ₂ O 5.5 ~ 7.0 F ^- 1.5 ~ 1.8 Cr ₂ O ₃ 0.1 ~ 0.3 Co ₂ O ₃ 0.1 ~ 0.3 13. A method according to any one of claims 8 to 10, wherein the glass-crystalline material contains a colloidal type colorant.

14 Glass - The following ratio of crystalline substances (mass%)
14. The method according to claim 8, 9, 10 or 13, comprising the following components.

SiO ₂ 56.0-58.0 Al ₂ O ₃ 6.0-7.0 CaO 20.0-23.0 MgO 3.0-5.0 Na ₂ O 1.0-2.0 K ₂ O 6.0-7.0 F ^- 1.5-2.0 Sb ₂ S ₃ 2.0-2.5 15 Spherulite β- Wolastonite is about 0.3 to 5
15. A method according to any one of claims 8 to 14, having dimensions in mm.

FIELD OF THE INVENTION The present invention relates to building materials, and more particularly to glass-crystalline materials and methods for their production.

Description of the Prior Art In the prior art, β-wollastonite, as a glassy decorative material similar to natural granite or marble, is grown in the form of needle-like crystals from the surface of the article perpendicularly inward through heat treatment. It takes advantage of its nature. Glass melts at a temperature of 1400-1550 ° C, depending on the glass composition.

The molded product is processed at temperatures between 1000 and 1200°C to form a plate of glass-crystalline material with a marble-like surface. The glass composition is within the range determined by the crystallization of β-wollastonite. Glass-crystalline materials having the following composition (% by weight) are known in the art:

SiO ₂ 46-75 Al ₂ O ₃ 3-35 CaO 15-40 The total amount of these components exceeds 90% by mass. This material is further combined with oxide-type colorants (Fe ₂ O ₃ ,
CoO, NiO) can be blended in an amount of 0.05 to 4.0% by mass.

A method of making articles from such materials consists of molding the article from molten glass and further heat treating the resulting glass article under the following conditions. That is, the temperature was raised to 700°C at a heating rate of 300°C/hour (first stage heat treatment), and then the temperature was raised at a heating rate of 120°C/hour.
Raise the temperature from 700°C to 1200°C at ~130°C/hour and hold at 1200°C for 1 hour (second stage heat treatment). To prevent the article from deforming during heat treatment, the surface of the article is precoated with a refractory agent that promotes crystal growth. These refractory agents include Al ₂ O ₃ and
It can consist of an aqueous suspension of ZrO ₂ (see GB 1342823).

Similarly, marble - glass with the appearance of granite -
Crystalline substances are known (U.S. Pat. No. 3,955,989)
), sintering of glass grains and their crystallization (temperature
1150℃). During heat treatment, β-
Needle-shaped crystals of wollastonite grow perpendicularly inward from the surface of the particle. Glass is SiO ₂ -
It is obtained by pouring a melt containing CaO—Al ₂ O ₃ and SiO ₂ —CaO—Al ₂ O ₃ —ZnO into water to form granules. After this procedure, the preformed granules are filled into a refractory mold and placed in a sintering and crystallization furnace. Instead of granules, glass rods with a diameter of 2-5 mm and a length of 100 cm may be sintered, uncolored glass granules may be mixed with colored glass granules, or salts (e.g. NiCl) may be used to obtain colored substances. It is also possible to spray the aqueous solution of ₂ ) onto the surface of the granules. A method for producing a material called "mottle pattern" is known (see U.S. Pat. No. 419,266, filed March 11, 1980 and U.S. Pat. No. 4,197,105, filed April 8, 1980).
It consists of applying various coloring pastes to glass-crystalline materials made from various compositions, followed by heat treatment to fix the colorants.

A method for producing a marble-like glass-crystalline material having the following composition (% by weight) is known:

SiO ₂ 40-68 Al ₂ O ₃ 4-35 CaO 15-40 In this method, glass is melted at a temperature of 1400-1550°C and formed into a plate-like object with a protruding end.
Heating at a temperature of 1000-1200°C, cooling, polishing to remove protrusions, and polishing.

During crystallization, needle-shaped β-wollastonite crystals appear and grow perpendicular to the glass surface.
When the protruding edges are polished away, a pattern appears on the surface (U.S. Patent No. 2, filed October 22, 1974).
(See No. 3843343).

In order to obtain a good decorative effect on the glass-crystalline materials mentioned above, mechanical methods are adopted (formation of protrusions, creation of articles with rough surfaces). Removal of these defects by polishing makes the method of manufacturing such glass-crystalline materials expensive.

The decorative patterns of these materials are for appearance and can be ground down when used as floor coverings. The structure of glass-crystalline materials by sintering of granules offers the possibility of obtaining various patterns on the surface. However, this method is batch-based, and a continuous method cannot be created based on it. Furthermore, it should be noted that the article shrinks considerably during sintering, so that it is not possible to obtain plates with uniform thickness. The resulting glass-crystalline material is porous and characterized by high water absorption;
Its application is limited.

The production of most of the above substances is characterized by high heat treatment conditions (1100-1200 °C).
This condition requires a high energy supply and requires the use of refractory molds in the crystallization furnace.

DISCLOSURE OF THE INVENTION The present invention provides a glass-crystalline material that has improved decorative and physical-mechanical properties and can be produced in a continuous process by selecting the quality and quantity of the ingredients under appropriate processing conditions, and a method for producing the same. directed towards doing.

The object is a glass-crystalline material containing SiO ₂ , Al ₂ O ₃ , CaO, which according to the invention has the following component ratios (mass percentages) and which contains mainly spherulite β-wollastonite crystals: This is achieved by providing a granite-like appearance, including:

SiO ₂ 55.0-60.0 Al ₂ O ₃ 6.0-9.0 CaO 17.0-25.0 MgO 3.0-10.0 K ₂ O 5.0-7.0 Na ₂ O 1.0-2.0 F ^- 1.0-2.5 The total amount of SiO ₂ , Al ₂ O ₃ and CaO is Less than 87% by mass.

The glass-crystalline material according to the invention has improved decorative properties due to its original nature and a long-life pattern made of β-wollastonite spherulites dispersed within the body of the material. Furthermore, it has higher physical and mechanical properties than natural granite.

In order to extend the color range and improve the decorative quality of the materials according to the invention, it is advantageous to include 0.05 to 4.0% by weight of at least one colorant.

It is likewise preferred to include oxide dyes in the glass-crystalline material according to the invention. Oxide dyes are milky white glass, β-
Adds various colors to wollastonite spherulites.

Preferred Embodiments of the Invention The glass-crystalline material according to the invention consists of components in the proportions (percent by weight) specified below.

SiO ₂ 55.0 ~ 57.0 Al ₂ O ₃ 6.0 ~ 9.0 CaO 17.0 ~ 23.0 MgO 3.0 ~ 10.0 Na ₂ O 1.0 ~ 2.0 K ₂ O 5.5 ~ 7.0 F ^- 1.5 ~ 1.8 Cr ₂ O ₃ 0.1 ~ 0.3 Co ₂ O ₃ 0.1 ~ 0.3 This material contains a mixture of oxide type dyes Cr ₂ O ₃ and Co ₂ O ₃ giving a greenish blue color.

It is also desirable to include colloidal type pigments in the glass-crystalline materials according to the invention to impart a certain color, eg, brown color, to the final material and to ensure spherulites of predetermined size.

According to the invention, the glass-crystalline material containing the colloidal type colorant comprises the following components in the following proportions (percent by weight):

SiO ₂ 56.0~58.0 Al ₂ O ₃ 6.0~7.0 CaO 20.0~23.0 MgO 3.0~5.0 Na ₂ O 1.0~2.0 K ₂ O 6.0~7.0 F ^- 1.5~2.0 Sb ₂ S ₃ 2.0~2.5 High mechanical strength properties In order to produce a glass-crystalline material with a spherule size of about 0.3 to 5 mm, it is desirable that the size of the β-wollastonite spherulites be in the range of about 0.3 to 5 mm.

The method for producing a glass-crystalline material according to the present invention is
It consists of molding a glass from a melt containing SiO ₂ , Al ₂ O ₃ , CaO and heat-treating it until it changes into a glass-crystalline material; according to the invention, it further comprises MgO, It is molded from glass containing Na ₂ O, K ₂ O, F ^- , cooled to a temperature lower than the glass temperature (vitrific-ation temperature) of 30 to 50 °C, and heat treated to form a spherulite of β-wollastonite. This process is continued until it changes to a granite-like substance consisting mainly of crystals.

By using a continuous mechanized process, the method according to the present invention achieves a
It makes it possible to produce decorative building materials with ~3 times lower production costs.

After heat treatment of the glass is carried out at a temperature of 650-800°C, the temperature is increased to a temperature of 930-950°C at a rate of about 150-200°C/hour and maintained at that temperature for a sufficient period of time to transform it into a granite-like material. Preferably, it is transformed into a glass-crystalline material.

These heat treatment conditions form an original pattern throughout the material according to the invention and improve its physical-mechanical properties compared to natural granite.
Contains all the factors necessary for the crystallization of wollastonite. Furthermore, these conditions make it possible to eliminate deformation of the glass during heat treatment and to reduce the input energy for the treatment.

The glass-crystalline material according to the invention has a granite-like appearance and consists essentially of spherulite β-wollastonite crystals having the following composition (in weight percent):

SiO ₂ 55.0-60.0 Al ₂ O ₃ 6.0-9.0 CaO 17.0-25.0 MgO 3.0-10.0 K ₂ O 5.0-7.0 Na ₂ O 1.0-2.0 F ^- 1.0-2.5 The inherent nature of the pattern formed in this material is , is ensured by the formation of spherulite aggregates during volume crystallization against a background of small-sized crystallized glasses of different colors or opacified glass.

The presence of SiO ₂ and CaO in concentrations within a certain range ensures the formation of spherulites during heat treatment of the glass. Spherulites are composed of crystals of β-wollastonite and have high physico-mechanical properties, which determine the high physico-mechanical properties of the final glass-crystalline material.

The presence of Al ₂ O ₃ , MgO, Na ₂ O specified above ensures certain viscosity properties of the glass melt. This ensures that the molten glass can be pressed, continuously rolled and free cast. _K2O needs to be present in the composition to avoid deformation of the article during crystallization. This increases the viscosity of the glass during heat treatment and promotes the liquefaction process in the glass, thus contributing to crystallization.

The conditions for the formation of β-wollastonite spherulites, which guarantee the inherent nature of the pattern formed in the glass-crystallized material according to the invention, can be determined by the factors specified below. Found out.

The phase that develops should belong to chain silicates.

The glass should have a liquiation structure and a well-developed surface at the interface. The dimensions of the elution domain are
It should be 0.1-0.2 μm. Similarly, chemical differentiation of the glass structure
The factor of is important so that one of the glass phases has a composition close to that which would be crystalline.

The formation of spherulites requires a highly viscous system. It impedes the growth of the crystals, resulting in their separation into individual crystals and a spherulite structure.

Wollastonite is a chain silicate and should form a spherulite aggregate under appropriate conditions. In order to form the elution structure of the glass and initiate the production of β-CaSiO ₃ spherulites, fluorine is present in the glass composition from 1 to 1.
Must be present in a strictly specified amount of 2.5% by mass. Fluorine contributes to the elution of the glass, resulting in the formation of microphases enriched in CaO and F ^- , causing chemical deviations in their structure and forming interfaces. Separation of crystallization centers (nuclei) and growth of spherulites occur in the fluorine-rich glass phase. The amount of fluorine is 1% by mass to ensure elution and form a certain number of crystallization fragments.
Must not be less. At the same time, it is about 2.5
It should not be more than % by weight. Otherwise, the number of crystallization centers would be too large and finely dispersed crystallization would occur, producing pyroceram (devitrified glass).

Due to its special crystalline chemical structure, the glass-crystalline material according to the invention has high physico-mechanical properties that meet the requirements imposed on surface building materials.
The table below summarizes the physical-mechanical properties of the materials according to the invention in comparison with natural granite and marble.

Table: From the properties shown in the table above, it can be seen that the material according to the invention is superior in its flexural strength, compressive strength and abrasion resistance compared to granite and marble. These properties as well as fire resistance, weather resistance and increased chemical stability provide the material according to the invention with a long service life in addition to its excellent decorative properties. Furthermore, the material according to the invention has no water absorption properties;
This makes the material according to the invention an indispensable material for protecting the foundations of houses from the strong influence of atmospheric sediments and also for the interior decoration of metro stations.

The glass-crystalline material according to the invention is between 0.05 and 4.0.
Any shade is possible depending on the colorants or colorant mixtures incorporated in the proportions by weight. Colorants of the oxidic or colloidal type can be used in the preparation of the materials according to the invention. Oxide-type dyes consist of oxides of elements with variable valence. During heat treatment, these colorants are distributed non-uniformly in the glass phase and in the spherulites, depending on their crystal chemistry. Wollastonite, which develops upon crystallization, is unlikely to undergo extensive isomorphic substitutions that result in different colorations of opalescent glass regions and spherulites. Furthermore, elements with variable valences upon heat treatment and crystallization tend to change their bonding (coordination) state and provide different colors. Oxide type colorants include Cr ₂ O ₃ , Co ₂ O ₃ , Fe ₂ O ₃ , NiO, Mn ₂ O ₃ ,
Select from the group of TiO ₂ and V ₂ O ₅ . Cr ³⁺ gives the spherulite a green color, Co ²⁺ gives it a blue color, Ni ²⁺ gives it a gray color, and Ti ^3-1 gives it a purple color. The colorants may be used alone as well as in mixtures, so that the color of the opalescent glass and spherulites has different shades depending on the selective penetration of the colorants therein.

In the production of glass crystalline materials according to the invention, it is desirable to use colloidal type colorants (copper, antimony sulfide, cadmium sulfide). These colorants provide a range of colors not available with the use of oxide type colorants. Thus, copper colloids offer the possibility of producing red materials, antimony sulfide provides the possibility of light brown colors, and cadmium sulfide provides the possibility of yellow colors. These colorants not only impart the desired color to the material, but are also present in the glass in the form of particles of colloidal size, forming interfaces that facilitate the process of formation of β-wollastonite spherulites. Facilitate.

The inventors have also developed a method for producing glass-crystalline materials according to the invention. The process consists of melting a charge containing raw materials containing silica sand, iron furnace slag, chalk, dolomite, alumina, caustic potash and fluorine in a glass melting tank furnace at a temperature of 1450-1520°C. At this stage it is possible to incorporate pigments of the oxide or colloid type into the filling. The quantitative proportions of the filler components are determined by the chemical composition of the glass-crystalline material. Then,
Forming glass from the resulting melt using conventional methods (pressing method, free casting method, continuous roll processing method)
Let's do it. Then the glass has a glass transition temperature Tg
Cool to the following temperature of 30-50°C and perform heat treatment. The conditions for heat treatment depend on the glass composition.
In the stage, the temperature is further increased to 930℃ at a heating rate of approximately 150 to 200℃/hour.
Temperature before heating up to ~950℃ (650~800
Determined by ℃). In the second step, the glass is held at the above temperature (930-950°C) for a sufficient period of time to transform the glass into a granite-like glass-crystalline substance consisting mainly of spherulite β-wollastonite with a particle size of approximately 0.3-5 mm. let During heat treatment, the number of crystallization nuclei formed to initiate further growth of β-wollastonite spherulites is strictly specified, the grain size of the system is specified to prevent glass deformation, and the growth of spherulites is provide the necessary conditions for The number and size of spherulites can be varied by adjusting the heat treatment conditions and the amount of initiator (fluorine).

At the temperature of the first stage of heat treatment, the following processes occur in the glass. namely, relaxation processes that achieve equilibrium in the glass, metastable elution, fluctuation processes in the local physical or chemical order of the structure, dissolution of elution or fluctuation domains already present in the initial glass, and β-wolast. Formation or partial annihilation of nuclei of critical dimension contributing to further growth of night spherulites.

The temperature of the first stage is selected depending on the amount of fluorine in the glass and the degree of completeness of the relaxation process that occurs upon cooling the glass to a temperature of 30-50° C. below Tg. If the fluorine content in the glass is such that it does not ensure that a sufficient amount of fluorine, which acts as the crystallization center (nucleus) of β-wollastonite spherulites, is released during cooling, Temperature of 1st stage Tg
The temperature should be selected close to , that is, within the range of 650 to 700°C. If the amount of fluorine exceeds the optimum amount for the given composition and some of the crystallization centers must be melted to avoid fine dispersion crystallization in the body, the temperature of the first stage should be increased to 750-800°C. Select within the range of ℃. The very important parameters in the heat treatment stage are
The heating rate is 150-200°C/hour. This affects the deformation of the glass-crystalline material according to the invention,
and give rise to processes of elution and isolation of metastable phase crystals that contribute to the "reinforcing" of the glass.

The method according to the invention produces a granite-like glass-crystalline material consisting essentially of β-wollastonite spherulites which have no water absorption and high physico-mechanical properties compared to natural materials, especially granite. make it possible. This method ensures a high degree of mechanization of the manufacturing process and its continuous nature. By appropriate selection of the composition of the glass and the temperature-time parameters of the heat treatment, it is possible to avoid deformation of the glass during heat treatment without artificial techniques, such as refractory coatings. Furthermore, a decorative effect is provided due to the tendency of the glass to crystallize spherulites, which avoids troubles in the molding step and eliminates the need for the formation of protrusions and rough surfaces.

Some specific examples illustrating compositions and methods of manufacture of glass-crystalline materials are discussed below to better understand the present invention.

Example 1: 61.0 parts by weight of silica sand, 26.0 parts of chalk, dolomite
A charge consisting of 18.1 parts of alumina, 5.03 parts of alumina, 10.0 parts of caustic potash and 4.3 parts of cryolite is melted in a bath-type glass melting furnace at 1500° C. in a mildly oxidizing atmosphere.

The resulting glass is molded into a plate using an automatic press machine at a temperature of 600°C, i.e. 50°C below the glass transition temperature.
Cool to low temperature. Put the plate into the crystallization furnace,
Heat treatment is performed at a temperature of 750°C, and the temperature is further increased to 930°C at a rate of 150°C/hour. The plate is held at 930°C for approximately 1 hour. After heat treatment, the plate is cooled to room temperature and transferred to a conveyor for machining to expose the texture of the material and give it a commercial appearance.

The resulting platelets are white and 0.5-2 mm
It has spherulites with dimensions of and the following components (composition is in mass %)
has.

SiO ₂ 60.0 Al ₂ O 6.0 CaO 20.0 MgO 3.6 Na ₂ O 1.6 K ₂ O 6.3 F ^- 2.5 This material has a density of 2700 Kg/m ³ , a bending strength of 30 MPa,
Compressive strength 350MPa, abrasion resistance 0.11g/m ² , chemical resistance NaOH - 86.5%, acid - 98.8%.

Example 2 A charge with the same starting materials as described in Example 1 is melted at a temperature of 1480° C. in an oxidizing medium. The molding of the plate and its cooling are carried out as in Example 1. The plate-like material is placed in a crystallization furnace and heat-treated at a temperature of 650℃,
The temperature is further increased to 950°C at a rate of 200°C/hour and held at that temperature for 45 minutes. The resulting plate consists of a glass-ceramic material having the following composition (% by weight): SiO ₂ 55.0, Al ₂ O ₃ 9.0, CaO 17.0,
MgO9.2, _Na2O1.3 , _K2O7.0 , F ^- 1.5. This material consists of light blue colored spherulites 3-5 mm in size. This material has the following properties: Density 2650Kg/
m ³ , bending strength 25 MPa, wear resistance 0.15 g/m ² , water absorption 0%, compressive strength 320 MPa.

Example 3 A charge containing the starting materials described in Example 1 and the colorant Cr ₂ O ₃ is melted at 1520°C. The resulting glass is molded into plates as described in Example 1, cooled and heat treated. However, cooling is performed at a temperature of 620°C, that is, 30°C lower than the glass transition temperature.
The first stage heat treatment is 800°C. The plate-like material thus produced consists of a glass-crystalline material having the following composition (% by mass). _SiO2 57.3, _{Al2O3 6.32} ,
CaO22.3, MgO4.8, Na ₂ O0.13, K ₂ O6.1,
F ^- 1.78, _{Cr2O3 0.1} . This material consists of opalescent green glass and grey-green spherulites, approximately 5 mm in size.
The distribution of spherulites is uneven, which gives the material a special decorative effect, which is especially evident after sanding and polishing this material.

Example 4 Cr ₂ O ₃ as colorant in the starting material described in Example 1
The charge containing Co ₂ O ₃ and Co 2 O 3 is melted at 1520 °C.
The resulting glass is molded into plates as described in Example 1, cooled and heat treated. However, the first stage heat treatment is at 800°C, and the residence time in the second stage heat treatment of the plate-like material is 2 hours. The plate-like material thus produced consists of a glass-crystalline material having the following composition (% by mass). _SiO2 55.0, _{Al2O3 6.0} ,
CaO25.0, MgO5.0, NaO2.0, _K2O7.0 , F ^- 1.6,
_{Cr2O3 0.3} , _{Co2O3 0.1} . The resulting material is spherulites of large size 4-5 mm with non-uniform color;
The color is the darkest in the center, and the color fades toward the periphery. It is generally blue-green in color and has properties similar to those described in the examples.

Example 5 The starting material described in Example 1 was combined with the colorant Cu ₂ O and
The charge containing Ni ₂ O ₃ is melted and the resulting glass is shaped into plates as described in Example 1, cooled and heat treated. The plate-like material thus produced consists of a glass-crystalline material having the following composition (% by mass). SiO ₂ 55.3, Al ₂ O ₃ 6.6, CaO 17.9, MgO 10.0,
Na ₂ O1.5, K ₂ O6.2, F ^- 1.8, Cu ₂ O0.3,
_{Ni2O30.4 .} The material is red in color with gray spherulites against a background of finely crystallized glass.

Example 6 A charge comprising the starting material as described in Example 1 with the colorant Cu ₂ O is melted under reduced pressure at a temperature of 1520° C., a plate is molded from the resulting melt, a temperature of 620° C., i.e.
It is cooled to a temperature 30°C lower than the glass transition temperature, and then heat treated at a temperature of 700°C in the first stage and further to 950°C at a heating rate of 170°C/hour. The platelets consist of a glass-crystalline material with the following composition (% by weight): SiO ₂ 57.0, Al ₂ O ₃ 6.2, CaO2 3.1, MgO3.2,
_Na2O2.00 , _K2O7.0 , F ^- 1.0, _Cu2O0.5 . This material has a black surface layer. When this thin layer is removed by polishing, an opalescent glass phase is revealed, with a greenish tint of blue and a non-uniform distribution of orange spherulites.
This material has high decorative properties and the following physico-mechanical properties: Density 2620Kg/m ³ , bending strength
25MPa, compressive strength 300MPa, wear resistance 0.22g/cm ² .

Example 7 The starting material described in Example 1 is introduced with the reducing agent SnO into a charge containing Cu ₂ O, melted, shaped into plates as described in Example 1, cooled and Heat treatment. The platelets consist of a glass-crystalline material with a composition similar to that described in Example 6, red in color and with spherulites of size 0.3 to 4 mm. This material has the following properties: Density 2700Kg/ ^m3 , bending strength 27MPa, compressive strength 400MPa, wear resistance 0.15g/m3
^cm2 .

Example 8 A charge containing the starting material described in Example 1 and the colorant Sb ₂ S ₃ is melted at a temperature of 1470° C. in a mildly reducing medium. Plates were molded from the resulting melt and in the first stage of heat treatment at a temperature of 750 °C, then Example 1
Process in the same way as . The plate is held in the second stage for 30 minutes. The obtained plate-like material had the following composition (mass%)
glass - consisting of a crystalline substance.
SiO ₂ 56.3, Al ₂ O ₃ 6.32, CaO22.3, MgO3.4,
_Na2O1.3 , _K2O6.1 , F ^- 1.78, _{Sb2S3 2.5} . This material is brown-orange in color with dark brown spherulites 1-5 mm in size. The properties of the glass-crystalline material obtained are similar to those described in Example 7.

Example 9 A charge containing the starting material described in Example 1 and the colorant Co ₂ O ₃ is melted at a temperature of 1500° C. in a mildly oxidizing atmosphere. Forming a plate from the resulting melt,
It is cooled and heat treated to a temperature of 620°C, ie 30°C below the glass transition temperature, the first stage being 800°C and then increasing to 950°C at a rate of 150°C/hour. The plate consists of a glass-crystalline material with the following composition (% by mass): _SiO2 57.0, _{Al2O3 6.7} ,
CaO22.25, MgO3.0, _K2O7.0 , _Na2O2.0 ,
F ^- 2.0, _{Co2O3 0.05} . It is blue-white in color and the properties are similar to those described in Example 2.

Example 10 A charge containing the starting material as described in Example 1 and the colorant NiO is melted, and plates are cast from the glass melt as described in Example 1, cooled and heat treated. The plate consists of a glass-crystalline material with the following composition (% by mass): SiO ₂ 55.0, Al ₂ O ₃ 6.0, CaO 18.0,
MgO7.0, _K2O7.0 , _Na2O2.0 , F ^- 1.0, NiO4.0.
This material is gray in color and has similar properties to the material described in Example 7.

Example 11 A charge consisting of 50 parts by weight of blast furnace slag, 40 parts of silica sand, 10 parts of caustic alkali, 3.4 parts of cryolite, and 2.5 parts of Sb ₂ O ₃ was melted in a bath-type glass melting furnace in a gentle annealing atmosphere at 1,450 parts by weight. Melts at temperatures of ~1470°C. A plate-like product is molded from the resulting melt using an automatic press machine, and 625
℃, that is, 30℃ lower than Tg. The plate is then heat treated first at 800°C and then at 930°C for 30 minutes and cooled. The resulting platelet has small dimensions (2 mm
Consists of a glass-crystalline material with brown spherulites (below). Its composition is as follows (% by mass).
SiO ₂ 56.3, Al ₂ O ₃ 7.0, CaO2 1.0, MgO3.8,
_Na2O1.25 , _K2O6.2 , F ^- 1.3, ^S2-0.6 , _{Sb2O3 2.4} ,
FeO0.1, MnO0.05.

Industrial Applicability The glass according to the present invention is similar in appearance to the naturally occurring crystalline material granite and has higher physical and mechanical properties, so it can be used on the outdoor side of various buildings, houses, subway stations, etc. Useful as a decorative material on both sides of the interior.