KR100579189B1 - Method for preparing the crystallized glass tile using cullet - Google Patents

Abstract

The present invention relates to a method for producing a crystalline glass tile having excellent strength by using a cullet, and a composition for producing a crystalline glass tile, 70 to 85 parts by weight of soda-lime-based cullet, 10 to 30 weight of slag Part, a first step of pulverizing the composition consisting of 1 to 10 parts by weight of zinc oxide, a second step of melting the pulverized composition at 1400 ~ 1500 ℃ for 2 to 4 hours, after molding the molten composition to form a mother glass by slow cooling It provides a method for producing a crystalline glass tile using a cullet comprising a third step, and a fourth step of heat-treating the mother glass at 800 ~ 1000 ℃ 2-4 hours. According to the present invention, raw materials for the production of glass tiles can be obtained from recycled cullet or steelmaking by-products, and recycled, and the strength is higher than that of amorphous glass tiles by melting at 1500 ° C. or lower and heat treatment at 1000 ° C. or lower. It is possible to produce crystalline glass tiles that are five times better.

Cullet, slag, zinc oxide, crystalline, glass tile

Description

Method for producing crystalline glass tile using cullet {METHOD FOR PREPARING THE CRYSTALLIZED GLASS TILE USING CULLET}             

1 is a photograph showing the results of X-ray diffraction analysis of the crystalline glass tile prepared according to an embodiment of the present invention.

Figure 2 is a graph showing the measured bending strength of the crystalline glass tile prepared according to the embodiment of the present invention according to the composition and the heat treatment temperature, respectively.

The present invention relates to a method for producing crystalline glass tiles using cullet, and to a composition for preparing crystalline glass tiles, in particular, a method for producing crystalline glass tiles having excellent strength and for producing such glass tiles. To a composition.

Conventionally, ceramic tiles made mainly of clay have been widely used as building tile products. However, in recent years, the use of glass tiles using glass materials is required in accordance with the trend of high-end building materials, and research has been continued to manufacture various kinds of glass tiles. The existing glass tile manufacturing methods developed in response to such demands can be classified into three types. Melting at high temperature by mixing glass raw materials such as silica sand, soda, lime, boric acid, etc. with colorant, milk white, clarifier, etc. Patent Publication No. 1995-8399) or melting and melting at a high temperature by mixing a glass raw material such as silicon oxide, lead oxide, aluminum oxide, iron oxide, sodium oxide, potassium oxide, and copper oxide and / or sulfur oxide (Korean Patent Publication) 2003-39944), a method of mixing a glass raw material and melting at a high temperature to form a mold; Molten powder is mixed with a pigment and the like to melt the pulverized pulverized glass, such as a method of pulverizing waste glass, mixing with a ceramic pigment and an organic binder, and forming a pressure, and then performing heat treatment at 750 to 950 ° C. (Korean Patent Publication No. 2003-88399). Baking at the above temperature (about 800 ° C); And a method in which the transparent cullet is cut in the forward direction, followed by screening or printing the pigment on the back surface, followed by heat treatment.

However, the glass tiles produced by these methods are amorphous glass tiles, which are aesthetically superior but have low strength and impact resistance, so they are fragile and can be very dangerous when broken. Follow. Therefore, while developing a crystalline glass tile having excellent strength and impact resistance as well as aesthetics, a core capable of producing a parent glass by melting the raw material for glass at a high temperature and crystallizing it therein A method of preparing a crystalline glass tile by mixing a forming material and heat treatment or by mixing a nucleating material in a glass raw material and melting at a high temperature to prepare a mother glass and then heat treatment. As part of such a method, Korean Patent Publication No. 1997-51751 discloses silica glass, magnesia, and steelmaking slag as a nucleation material, which are melted by heating and melting, followed by quenching to form a mother glass, which is then subjected to two-stage heat treatment to produce high-strength crystalline glass. The method is described. However, melting for producing crystalline glass of the prior art was necessary to be performed at 1500 ° C. or higher, and reheating or heat treatment after the production of the mother glass was also required at a high temperature, which was not preferable in view of cost versus effect.

It is an object of the present invention to provide a method for producing a high strength crystalline glass tile product by melting and heat treatment at a low temperature and a crystalline glass tile product produced according to such a method.

Still another object of the present invention is to provide a composition for preparing crystalline glass tiles, which is mixed at an appropriate ratio in order to prepare a high strength crystalline glass tile product.

In the present invention, as a result of intensive studies to achieve the above technical problem, melting and heat treatment of a composition in which cullet and steelmaking slag are the main raw materials, and a small amount of zinc oxide is added and mixed at an appropriate ratio. As a result, the inventors found that a crystalline glass tile having excellent strength can be produced, thus completing the present invention.

That is, the present invention, the first step of melting the mixture consisting of cullet, slag, and zinc oxide (ZnO), the second step of forming a molten mixture and then slowly cooling, and the third step of heat-treating the slow cooled resultant It provides a method for producing a crystalline glass tile using a cullet comprising a. In the mixture, the cullet, slag, and zinc oxide are preferably contained in a ratio of 70 to 85 parts by weight, 10 to 30 parts by weight, and 1 to 10 parts by weight, respectively, based on the total solids. In addition, the melting in the first step according to the present invention is preferably performed for 2 to 4 hours at 1400 ~ 1500 ℃ and the heat treatment in the third step is preferably performed for 2 to 4 hours at 800 ~ 1000 ℃.

In addition, the present invention provides a composition for producing crystalline glass tile consisting of 70 to 85 parts by weight of soda-lime-based cullet, 10 to 30 parts by weight of slag, and 1 to 10 parts by weight of zinc oxide.

In the present invention, the cullet is the most basic material for the production of crystalline glass tiles, in the present invention generally obtains a soda-lime-based cullet that can be easily obtained from plate glass, bottle glass, etc. Recycle it. In this way, the cullet is obtained from a glassy raw material that has been previously melted and manufactured, and thus can be satisfactorily melted even at a lower temperature than when mixing and melting necessary glass raw materials, and at a temperature lower than a conventional heat treatment temperature. It can be heat treated. In addition, since the cullet has good meltability with slag and zinc oxide, it also serves to improve the homogeneity of the glass tile product manufactured according to the present invention. The detailed chemical composition and color of the cullet may vary slightly depending on the type of glassy raw material, but the final glass tile product may be obtained by using cullet obtained from one glassy raw material or using cullet obtained from various glassy raw materials. The physical properties of do not have a big effect. Detailed chemical composition of a typical soda-lime cullet can be shown as Table 1 below.

ingredient SiO ₂ Al ₂ O ₃ Na ₂ O K ₂ O CaO MgO Fe ₂ O ₃ SO ₃ sum  (%)  70-75  0-3  10-15  5-10  5-15  0-5  0 ~ 1  0 ~ 1  100

It is preferable that the cullet of such a composition is contained in the ratio of about 70-85 weight part in the composition of this invention based on the total solid weight. If the cullet is present in less than 70 parts by weight, the content of slag and zinc oxide, which is a composition according to the present invention other than cullet, must be increased, so that the viscosity, softening point and melting temperature of the composition are increased so that the composition is at It is difficult to melt and difficult to obtain the desired crystals. On the other hand, when the cullet is present in excess of 85 parts by weight, it is not preferable because the crystallization is not made well and the strength improvement effect cannot be obtained.

Slag, which is one of the compositions according to the present invention, serves to convert amorphous mother glass formed by slow cooling after melting into crystalline glass, so that slag generated as a byproduct after steelmaking can be obtained and recycled. Since the slag itself is a kind of glassy material produced by melting and quenching at a high temperature, the melting and reaction temperatures are lower than those of natural mineral raw materials or chemical raw materials. It can be easily mixed with cullet to form a homogenized compound. The detailed chemical composition of the slag can be shown in Table 2 below.

ingredient SiO ₂ Al ₂ O ₃ Na ₂ O K ₂ O CaO MgO Fe ₂ O ₃ SO ₃ sum  (%)  30-35  10-15  0 ~ 2  0 ~ 2  40-45  0 ~ 2  0 ~ 1  1 ~ 2  100

As can be seen from Table 2, since the slag contains a large amount of Al ₂ O ₃ in particular, it contributes to the improvement of strength and water resistance of the glass tile product to be produced, while also increasing the melting temperature and softening point. In addition to the composition shown in Table 2, the slag contains a small amount of sulfides such as manganese or iron, and these act as nucleation materials for crystallization to convert amorphous mother glass into crystalline glass. Therefore, it is preferable that slag is contained in the composition according to this invention at an appropriate ratio, and it is preferable that it is contained in the ratio of about 10-30 weight part in the composition of this invention based on the total solid weight. If the slag is present in less than 10 parts by weight, the strength of the final glass tile product is reduced due to poor crystallization, and when present in excess of 30 parts by weight raise the melting temperature and softening point of the composition according to the present invention It is also not preferable because it can generate bubbles.

In addition, zinc oxide, which is one of the compositions according to the present invention, promotes texture purification by the slag, lowers the melting temperature, softening point and coefficient of thermal expansion of the composition, and serves to improve weather resistance of the final glass tile product. When the sulfur (S) component contained in the composition according to the present invention is fixed in the form of zinc sulfide (ZnS), it is also a substance that whitens the color of the crystallization. Such zinc oxide is preferably contained in the composition according to the present invention in a ratio of about 1 to 10 parts by weight based on the total weight of solids. When present in less than 1 part by weight, the softening point and thermal expansion of the composition by zinc oxide The effect of reducing the coefficient is not obtained, and the effect of improving the weather resistance of the final glass tile product is not obtained. On the other hand, when zinc oxide is present in excess of 10 parts by weight, the coefficient of thermal expansion is reduced, but rather undesirable because excessively promoted crystallization.

As mentioned above, the composition for preparing crystalline glass tiles of the present invention, which is composed of the composition of cullet, slag, and zinc oxide, is subjected to the steps of melting and heat treatment according to a general method for preparing crystalline glass. However, according to the properties of the composition according to the present invention, in the present invention, by forming the conditions for the melting by melting for 2 to 4 hours at a relatively low temperature of 1400 ~ 1500 ℃, it is possible to produce an amorphous mother glass, and also heat treatment The conditions for the crystalline glass tile product can be produced by forming a heat treatment at a relatively low temperature of 800 ~ 1000 ℃ 2 to 4 hours. At this time, when melting at less than 1400 ℃ or less than 2 hours, the reaction of the composition is incomplete to obtain a uniform melting product, it is not preferable because a bubble may occur, melting at a temperature exceeding 1500 ℃ Or melting for more than 4 hours is not preferred because it is non-economical. The melting temperature and the melting time can be appropriately adjusted to each other to compensate as necessary. On the other hand, in the case of heat treatment, heat treatment below 800 ° C. is not preferable because crystallization does not occur, and heat treatment at a temperature above 1000 ° C. is not preferable because it results in remelting. In addition, if the heat treatment for crystallization is performed for less than 2 hours, there is a fear that the crystals are insufficiently formed and the strength is lowered. If the heat treatment is performed for more than 4 hours, the size of the crystals may be so large that the strength may be lowered. not.

Hereinafter, with reference to Examples and drawings showing a preferred embodiment of the present invention, the composition for producing a crystalline glass tile and the method for producing a crystalline glass tile using cullet according to the present invention will be described in more detail. However, the following description and drawings are not intended to limit the invention, the invention may be appropriately modified and modified based on the matter described in the claims.

Example

A composition having a content as shown in Table 3 below was prepared.

Soda-lime cullet                                              Slag Zinc oxide A-1 A-2 73 83 25 15 2 2 B-1 B-2 B-3 79 78 77 20 20 20 1 2 3

                                                       (Unit: weight%)

These A-1, A-2, B-1, B-2, and B-3 compositions were put into a ball mill, respectively, and mixed and ground to prepare a particulate mixture. Each of the obtained mixtures was charged in a platinum crucible and placed in a box-type electric furnace, and melted at 1500 ° C. for 2 hours. The molten mixture was poured into a metal mold in this state and molded into a plate to prepare square specimens (parent glass) for each composition, and then put into a heat treatment furnace and slowly cooled at a cooling rate of 2 ° C. per minute from 600 ° C. to room temperature. . The mother glass obtained by melting and slow cooling after melting according to the method of the present invention was all transparent, and as a result of observation by X-ray diffractometer, it was confirmed that the mother glass is in an amorphous state, and the bending strength showed a distribution of 4 to 10 kgf / mm 2 ( See Table 5 below).

The transparent mother glass was put back into an electric furnace and heat-treated under the conditions as shown in Table 4, and then slowly cooled to room temperature at a cooling rate of 2 ° C. to obtain crystalline glass tiles in an opaque state.

Composition Heat treatment temperature (℃), 2 hours heat treatment                                              A-1 A-2 800 800 900 900 1000 1000 B-1 B-2 B-3 800 800 800 900 900 900 1000 1000 1000

X-ray diffraction analysis results of the glass tiles completed with the B-1 composition in the resultant glass tiles are shown in FIG. 1, and the results of measuring the bending strength of the glass tiles completed with the A-1 to B-3 compositions are shown in Table 5 and FIG. 2 is shown.

First, as shown in Figure 1, the glass tile prepared with the B-1 composition did not show a clear crystal phase peak when the heat treatment at 800 ℃, but when the heat treatment at 900 ℃ and 1000 ℃ showed a clear peak of the crystal phase. In particular, when the heat treatment at 1000 ℃ showed a large crystal phase peak. This tendency was confirmed to be the same in the case of glass tiles made with other compositions.

Next, Table 5 below.

Flexural Strength of Mother Glass and Final Glass Tiles by Heat Treatment Temperature Mother glass                                              800 ℃ heat treatment 900 ℃ heat treatment 1000 ℃ heat treatment A-1 A-2 6.72 7.33 17.92 13.76 10.62 5.12 8.67 5.24 B-1 B-2 B-3 9.55 4.72 4.34 11.3 9.81 8.48 13.06 20.12 19.22 8.62 8.89 15.42

                                                    (Unit: kgf / mm2)

 As can be seen in Figure 2, when comparing the bending strength of the glass tiles (glass tiles made with A-1 and A-2 composition) prepared by changing the content of the slag without changing the content of zinc oxide, slag The greater the content of (glass tile made from the composition A-1), the more the curvature was improved by heat treatment, especially when the heat treatment at 800 ℃ improved the bending strength up to about 3 times compared to the mother glass before heat treatment. In addition, when comparing the bending strength of the glass tiles (glass tiles made with B-1, B-2, and B-3 composition) prepared by changing the zinc oxide content without changing the slag content, the content of zinc oxide When 2 parts by weight of the total composition and the heat treatment at 900 ℃ exhibited the highest degree of improvement in strength, which is about 5 times the strength of the glass before the heat treatment.

As can be seen from these results, according to the present invention, by changing the content of the slag or zinc oxide in the composition or by controlling the heat treatment temperature, it is possible to prepare a product suitable for the properties of the desired crystalline glass tile, such as strength and degree of crystallization. have.

According to the present invention, raw materials for the production of glass tiles can be obtained from recycled cullet or steelmaking by-products, and recycled, and the strength is higher than that of amorphous glass tiles by melting at 1500 ° C. or lower and heat treatment at 1000 ° C. or lower. It is possible to produce crystalline glass tiles that are five times better. As described above, the present invention is an economical and environmentally friendly method, and the product manufactured according to the method of the present invention is excellent in strength as well as aesthetics and can be used in various fields such as building materials.

Claims (7)

A first step of grinding and melting the mixture comprising soda-lime-based cullet, slag, and zinc oxide; A second step of slowly cooling after molding the molten mixture; And A third step of heat-treating the slow cooled product; Method for producing a crystalline glass tile using a cullet comprising a. The method of claim 1, In the mixture, the cullet, slag, and zinc oxide are characterized in that contained in the ratio of 70 to 85 parts by weight, 10 to 30 parts by weight, and 1 to 10 parts by weight based on the total solids, respectively. Method for producing crystalline glass tile using cullet. The method of claim 1, The melting is performed for 2 to 4 hours at 1400 ~ 1500 ℃ Method for producing crystalline glass tile using cullet. The method of claim 1, The heat treatment is performed for 2 to 4 hours at 800 ~ 1000 ℃  Method for producing crystalline glass tile using cullet. A first step of pulverizing the mixture consisting of 70 to 85 parts by weight of soda-lime-based cullet, 10 to 30 parts by weight of slag, and 1 to 10 parts by weight of zinc oxide; A second step of melting the ground mixture at 1400-1500 ° C. for 2-4 hours; A third step of forming a molten mixture by molding the molten mixture followed by slow cooling; And A fourth step of thermally cooling the mother glass at 800 to 1000 ° C. for 2 to 4 hours; Method for producing a crystalline glass tile using a cullet comprising a. 70 to 85 parts by weight of soda-lime-based cullet, 10 to 30 parts by weight of slag, and 1 to 10 parts by weight of zinc oxide. Composition for preparing crystalline glass tiles. delete

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