KR102200844B1 - Glaze composition for forming glaze layer having high contact angle and manufacturing method of ceramic tile using the composition - Google Patents

Abstract

The present invention is a glaze composition for forming the glaze layer in a ceramic tile comprising a base layer, an engobe layer provided on the base layer, and a glaze layer provided on the upper part of the base layer, comprising 90 to 98 weight of glass frit powder % And 2 to 10% by weight of kaolin powder, and 1 to 20 parts by weight of Ni powder coated with Cu nano-powder based on 100 parts by weight of the glaze raw material, and the same It relates to a method of manufacturing a ceramic tile used. According to the present invention, self-cleaning is possible due to high contact angle characteristics, excellent durability, and a glaze layer can be formed without the need for a process such as UV irradiation (Ultraviolet ray irradiation).

Description

Glaze composition for forming glaze layer having high contact angle and manufacturing method of ceramic tile using the composition

The present invention relates to a glaze composition and a method of manufacturing a ceramic tile using the same, and more particularly, a glaze composition capable of forming a glaze layer capable of self-cleaning by high contact angle characteristics, and self-cleaning using the same It relates to a possible ceramic tile manufacturing method.

Ceramic tiles are widely used as interior and exterior materials for buildings due to their excellent durability and aesthetics through surface control.

Glazed ceramic tiles with a glazed layer on the surface can manufacture various functional ceramic tiles by controlling the composition and microstructure of the glaze.

Since ceramic tiles are used as interior and exterior materials of buildings, cleanliness becomes a very important index, and therefore, the development of self-cleaning functional tiles is constantly required.

In the self-cleaning of ceramic tiles, many studies have been conducted to remove foreign substances from the surface by securing a hydrophilic surface through TiO ₂ coating. However, in the case of TiO _2, the hydrophilic coating has the disadvantage that requires the product to be produced TiO ₂ coating layer hydrophilic through a further process after firing, UV irradiation (Ultraviolet ray irradiation). In particular, it is a big problem that the durability of the TiO ₂ hydrophilic coating layer is weak.

Korean Patent Application Publication No. 10-2015-0030733

The problem to be solved by the present invention is a glaze composition capable of self-cleaning by high contact angle characteristics, excellent durability, and forming a glaze layer without the need for processes such as UV irradiation (Ultraviolet ray irradiation), and It is to provide a method of manufacturing a ceramic tile capable of self-cleaning using this.

The present invention is a glaze composition for forming the glaze layer in a ceramic tile comprising a base layer, an engobe layer provided on the base layer, and a glaze layer provided on the upper part of the base layer, comprising 90 to 98 weight of glass frit powder % And 2 to 10% by weight of kaolin powder, and 1 to 20 parts by weight of Ni powder coated with Cu nano-powder based on 100 parts by weight of the glaze raw material. do.

It is preferable that the Cu nanopowder has an average particle diameter of 10 to 300 nm.

It is preferable that the Ni powder has an average particle diameter of 1 to 10 μm.

The Cu nanopowder is preferably 0.1 to 25 parts by weight based on 100 parts by weight of the Ni powder.

The glaze composition may further include 0.1 to 10 parts by weight of zircon powder based on 100 parts by weight of the glaze raw material.

In addition, the present invention comprises the steps of forming an engobe layer on top of the molded and first fired base layer, forming a glaze layer by applying and drying a glaze composition on the upper part of the engobe layer, and the result of forming the glaze layer. Including the step of secondary firing, wherein the glaze composition comprises a glaze raw material comprising 90 to 98% by weight of glass frit powder and 2 to 10% by weight of kaolin powder, and Cu nanopowder based on 100 parts by weight of the glaze raw material It provides a method of manufacturing a ceramic tile, characterized in that it further comprises 1 to 20 parts by weight of the coated Ni powder.

It is preferable that the Cu nanopowder has an average particle diameter of 10 to 300 nm.

It is preferable that the Ni powder has an average particle diameter of 1 to 10 μm.

The Cu nanopowder is preferably 0.1 to 25 parts by weight based on 100 parts by weight of the Ni powder.

The glaze composition may further include 0.1 to 10 parts by weight of zircon powder based on 100 parts by weight of the glaze raw material.

The glaze layer is preferably formed to a thickness of 100 to 200㎛.

According to the glaze composition of the present invention, it has high contact angle characteristics, excellent durability, and can form a glaze layer without the need for UV irradiation (Ultraviolet ray irradiation), and the glaze layer is self-cleaning due to high contact angle properties. -cleaning) may be possible.

According to the method of manufacturing a ceramic tile of the present invention, since a glaze layer having a high contact angle characteristic is formed on the surface, self-cleaning is possible.

1 is a diagram showing the structure of a ceramic tile.
2 is a scanning electron microscope (SEM) photograph showing a state in which Cu nanopowder is coated on the surface of Ni powder after high energy milling.
3 is a photograph showing a state in which Cu nanopowder is coated on the surface of Ni powder after high energy milling and an elemental mapping analysis result.
4 is a photograph showing a ceramic tile prepared by mixing 10 parts by weight of Ni powder coated with Cu nanopowder according to Experimental Example 3 and making the thickness of the glaze layer 150 mm.
5 is a photograph showing a contact angle with respect to the glaze layer of a ceramic tile prepared by mixing 10 parts by weight of Ni powder coated with Cu nano-powder according to Experimental Example 3 and setting the thickness of the glaze layer to 150 mm.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the following embodiments are provided so that the present invention may be sufficiently understood by those of ordinary skill in the art, and may be modified in various other forms, and the scope of the present invention is limited to the embodiments described below. It does not become.

In the detailed description of the invention or in the claims, when any one component "includes" another component, it is not construed as being limited to consisting of only the component unless otherwise stated, and other components are further included. It should be understood that it may contain.

Hereinafter, the term “nano” is used to mean a size of 1 to 1000 nm as the size of a nanometer unit, and the term “nano powder” is used to mean a powder having a size of 1 to 1000 nm.

The glaze composition according to a preferred embodiment of the present invention is a glaze composition for forming the glaze layer in a ceramic tile including a base layer, an engobe layer provided on the base layer, and a glaze layer provided on the upper part of the engobe layer. , Including a glaze raw material comprising 90 to 98% by weight of glass frit powder and 2 to 10% by weight of kaolin powder, and further comprises 1 to 20 parts by weight of Ni powder coated with Cu nanopowder based on 100 parts by weight of the glaze raw material .

It is preferable that the Cu nanopowder has an average particle diameter of 10 to 300 nm.

It is preferable that the Ni powder has an average particle diameter of 1 to 10 μm.

The Cu nanopowder is preferably 0.1 to 25 parts by weight based on 100 parts by weight of the Ni powder.

The glaze composition may further include 0.1 to 10 parts by weight of zircon powder based on 100 parts by weight of the glaze raw material.

The method of manufacturing a ceramic tile according to a preferred embodiment of the present invention includes forming an engobe layer on an upper portion of the base layer that is molded and first calcined, and forming a glaze layer by applying a glaze composition on the upper part of the engobe layer and drying it. The glaze composition comprises a glaze raw material comprising 90 to 98% by weight of glass frit powder and 2 to 10% by weight of kaolin powder, the glaze It further includes 1 to 20 parts by weight of Ni powder coated with Cu nano-powder based on 100 parts by weight of the raw material.

It is preferable that the Cu nanopowder has an average particle diameter of 10 to 300 nm.

It is preferable that the Ni powder has an average particle diameter of 1 to 10 μm.

The Cu nanopowder is preferably 0.1 to 25 parts by weight based on 100 parts by weight of the Ni powder.

The glaze composition may further include 0.1 to 10 parts by weight of zircon powder based on 100 parts by weight of the glaze raw material.

The glaze layer is preferably formed to a thickness of 100 to 200㎛.

Hereinafter, a glaze composition according to a preferred embodiment of the present invention will be described in more detail.

Ceramic tiles are generally used for building interiors, and are divided into wall tiles and floor tiles.

Ceramic tile is an eco-friendly building material made of soil, and has excellent strength and durability by firing at a high temperature of 1000℃ or higher.

Among ceramic tiles, the glaze layer is formed on the surface of the ceramic tile by the application of the glaze composition, so that it not only maintains cleanliness through contamination prevention, but also can add aesthetics and various functions. Accordingly, wall tiles are widely used as interior materials in residential environments such as kitchens and floors as well as toilets.

1 is a diagram showing the structure of a ceramic tile.

Referring to FIG. 1, a ceramic tile has a structure in which a base layer 110, an engobe layer 120, and a glaze layer 130 are sequentially stacked. The glaze composition according to a preferred embodiment of the present invention is a glaze composition for forming the glaze layer 130 in ceramic tiles.

The ceramic tile is glazed by applying the engobe composition on the primary sintered base layer 110 by mixing and molding a base material such as clay to form the engobe layer 120, and applying the glaze composition on the upper part of the engobe layer 120 After forming the layer 130, it is manufactured through secondary firing. In the case of manufacturing a floor tile among ceramic tiles, the first firing process is not performed.

The Engobe layer 120 functions as an intermediate layer capable of concealing the color of the base layer 110 and controlling the thermal expansion of the base layer 110 and the glaze layer 130. It is preferable that the Enkobe layer 120 has a thickness of about 50 to 300 μm.

The glaze layer 130 plays a role of reinforcing (protecting) the surface of the ceramic tile and performing a decoration. It is preferable that the glaze layer 130 has a thickness of about 100 to 200 μm. Self-cleaning may be possible by making the glaze layer 130 have high contact angle characteristics. In forming the glaze layer 130 of ceramic tiles, it is possible to form the glaze layer 130 having high contact angle characteristics through composition control.

The glaze composition according to a preferred embodiment of the present invention comprises a glaze raw material comprising 90 to 98 wt% of glass frit powder and 2 to 10 wt% of kaolin powder, and Cu nanopowder is coated with respect to 100 parts by weight of the glaze raw material. It further contains 1 to 20 parts by weight of Ni powder.

It is preferable that the Cu nanopowder has an average particle diameter of 10 to 300 nm. It is preferable that the Ni powder has an average particle diameter of 1 to 10 μm. The Cu nanopowder is preferably 0.1 to 25 parts by weight based on 100 parts by weight of the Ni powder.

Since ceramic tiles are used as interior and exterior materials of buildings, cleanliness becomes a very important index, and therefore, the development of self-cleaning functional tiles is constantly required.

In the self-cleaning of ceramic tiles, many studies have been conducted to remove foreign substances from the surface by securing a hydrophilic surface through TiO ₂ coating. However, there is a drawback that requires plastic products (secondary firing) be a hydrophilic coating TiO ₂ prepared by further processing and then, irradiated UV (Ultraviolet ray irradiation) In the case of TiO _2, a hydrophilic coating. In particular, it is a big problem that the durability of the TiO ₂ hydrophilic coating layer is weak.

In recent years, research on implementing a hydrophobic coating layer of lotus leaves and securing self-cleaning characteristics through this has been underway. In general, products that implement hydrophobicity by coating a polymer material on the glaze surface of ceramic tiles have been announced, but such products have a problem in durability.

Therefore, it is very important to maximize the hydrophobicity without an additional process by controlling the microstructure of the ceramic tile surface glaze, and in particular to implement the formation of such a hydrophobic glaze layer by applying the ceramic tile mass production process (rapid firing process) as it is.

According to the experiment, it was confirmed that a high contact angle property was exhibited when the glaze layer 130 was formed by using a glaze composition in which the glaze material including glass frit powder and kaolin powder was mixed with Ni powder coated with Cu nanopowder. .

The glaze composition may further include 0.1 to 10 parts by weight of zircon powder based on 100 parts by weight of the glaze raw material. The zircon powder may serve to increase whiteness and increase surface hardness.

According to the glaze composition of the present invention, it has high contact angle characteristics, excellent durability, and can form the glaze layer 130 without the need for a process such as UV irradiation (Ultraviolet ray irradiation), and the glaze layer 130 has high contact angle properties. By this, self-cleaning may be possible.

Hereinafter, a method of manufacturing a ceramic tile according to a preferred embodiment of the present invention will be described in more detail.

The ceramic tile has a structure in which the base layer 110, the solid solid layer 120 and the glaze layer 130 are sequentially stacked. The ceramic tile is glazed by applying the engobe composition on the primary sintered base layer 110 by mixing and molding a base material such as clay to form the engobe layer 120, and applying the glaze composition on the upper part of the engobe layer 120 After forming the layer 130, it is manufactured through secondary firing. In the case of manufacturing a floor tile among ceramic tiles, the first firing process is not required.

In order to manufacture a ceramic tile having the above structure, first, a base material is mixed to form a base composition. The base material forms the basic framework of the ceramic tile. For example, the base material may include 8 to 15% by weight of limestone, 20 to 25% by weight of clay, 40 to 45% by weight of pottery, 10 to 15% by weight of pyrophyllite, and 5 to 15% by weight of kaolin. The mixing may be performed by various methods such as a ball mill, a planetary mill, and an attraction mill.

Hereinafter, the mixing process by the ball mill method will be described in detail. The base material is charged into a ball milling machine and mixed. The base material is uniformly mixed by rotating at a constant speed using a ball mill. Balls used in the ball mill may be balls made of ceramics such as alumina and zirconia, and all of the balls may be of the same size, or balls having two or more sizes may be used together. By adjusting the size of the ball, milling time, and rotational speed per minute of the ball mill, pulverize and mix to the target particle size. For example, considering the size of the particles, the size of the ball may be set in the range of 1 mm to 50 mm, and the rotation speed of the ball mill may be set in the range of about 100 to 500 rpm. It is preferable to perform the ball mill for 1 to 48 hours in consideration of the target particle size and the like.

The base composition may be in the form of a slurry, and in the base composition, the base material is dispersed in a solvent to form a solid content. In this case, the solvent is preferably contained in the base composition in an amount of 30 to 80 parts by weight based on 100 parts by weight of the solid content.

The body composition may be prepared from granular powder for body containing 8 to 15% by weight of limestone, 20 to 25% by weight of clay, 40 to 45% by weight of pottery stone, 10 to 15% by weight of pyrophyllite, and 5 to 15% by weight of kaolin. have.

The body composition obtained by the above-described method is molded into a desired shape. For the molding, various methods such as commonly known pressure molding and injection molding may be used. In addition, prior to the molding, a process of de-ironing the base composition, a process of classifying and filtering, and the like may be additionally performed.

The molded product is first fired. The molded result is charged into a furnace such as an electric furnace, and the first firing process is performed. It is desirable to keep the pressure inside the furnace constant during the primary firing. The primary firing is preferably performed at a temperature of about 1000 to 1250°C. If the primary firing temperature is less than 1000°C, thermal or mechanical properties of the ceramic tile may be poor due to incomplete firing, and if it exceeds 1250°C, energy consumption is high, which is uneconomical. The primary firing is preferably carried out in an oxidizing atmosphere (eg, oxygen (O ₂ ) or air atmosphere). In the case of manufacturing a floor tile among ceramic tiles, the first firing process is not performed.

The Engobe composition is applied on the top of the base layer 110 formed by primary firing and dried to form the Engobe layer 120. An Engobe composition is prepared to form the Engobe layer 120 on the surface of the base layer 110, and the Engobe composition is applied to the surface of the base layer 110 that is molded and first fired, and then dried. The Engobe composition is in a slurry state containing a solid content such as clay and a solvent, and the solvent is preferably contained in an amount of 30 to 80 parts by weight based on 100 parts by weight of the solid content in the Engobe composition. For example, the solid content includes 45 to 75% by weight of glass frit, 2 to 15% by weight of feldspar powder, 10 to 30% by weight of silicate powder, 10 to 25% by weight of kaolin powder, and 0.1 to 10% by weight of zircon powder can do. The Engobe composition preferably has a specific gravity of about 1.4 to 1.8, more preferably about 1.5 to 1.7. It is preferable that the Enkobe layer 120 is formed to have a thickness of about 50 to 300 μm. The Engobe layer 120 functions as an intermediate layer capable of concealing the color of the base layer 110 and controlling the thermal expansion of the base layer 110 and the glaze layer 130.

The glaze composition is applied on the upper portion of the engobe layer 120 and dried to form the glaze layer 130. A glaze composition is prepared to form the glaze layer 130 on the engobe layer 120, and the glaze composition is applied to the surface of the engobe layer 120 and dried. The glaze composition is in the form of a slurry containing a solid content and a solvent, and the solvent is preferably made to contain 30 to 80 parts by weight based on 100 parts by weight of the solid content in the glaze composition. For example, the glaze composition comprises a glaze raw material containing 90 to 98 wt% of glass frit powder and 2 to 10 wt% of kaolin powder, and Cu nanopowder is coated with respect to 100 parts by weight of the glaze raw material. It further contains 1 to 20 parts by weight of Ni powder. It is preferable that the Cu nanopowder has an average particle diameter of 10 to 300 nm. It is preferable that the Ni powder has an average particle diameter of 1 to 10 μm. The Cu nanopowder is preferably 0.1 to 25 parts by weight based on 100 parts by weight of the Ni powder.

By using Ni powder coated with Cu nanopowder to form the glaze layer 130 of the ceramic tile, the glaze layer 130 may have a hydrophobic property having a high contact angle with water after the secondary firing. By using Ni powder coated with Cu nanopowder, hydrophobicity is maximized, and in particular, it is possible to apply the ceramic tile mass production process (rapid firing process) as it is for the formation of such a hydrophobic glaze layer. According to the experiment, it was confirmed that a high contact angle property was exhibited when the glaze layer 130 was formed by using a glaze composition in which the glaze material including glass frit powder and kaolin powder was mixed with Ni powder coated with Cu nanopowder. .

The glaze composition may further include 0.1 to 10 parts by weight of zircon powder based on 100 parts by weight of the glaze raw material. The zircon powder may serve to increase whiteness and increase surface hardness.

The glaze layer 130 forms a glassy film on the surface of the ceramic tile where micropores are present, thereby inducing strength enhancement and reduction in absorption rate, and expressing a unique color and texture. The method of application may be performed in various ways, for example, immersing the resulting engobe layer 120 in the glaze composition, applying the glaze composition with a tool such as a brush, or spraying the glaze composition with a spray device. I can.

It is preferable that the glaze layer 130 is formed to have a thickness of about 100 to 200 μm, more preferably about 120 to 150 μm. The thickness of the glaze layer 130 may be controlled by controlling the application time and the number of applications of the glaze composition. According to the experimental example, a change in the contact angle characteristic was also observed according to the thickness of the glaze layer 130, and particularly, when the glaze layer 130 has a thickness of about 120 to 150 μm, the contact angle characteristic was very excellent.

Secondary firing of the resultant glaze layer 130 formed thereon to provide a base layer 110, an engobe layer 120 provided on the base layer 110, and a glaze layer 130 provided on the engobe layer 120 A ceramic tile containing is obtained. The resultant glaze layer 130 is formed is charged into a furnace such as an electric furnace, and a secondary firing process is performed. During the secondary firing, it is desirable to keep the pressure inside the furnace constant. The secondary firing is preferably performed at a temperature of about 1000 to 1200°C. If the secondary firing temperature is less than 1000°C, thermal or mechanical properties of the ceramic tile may be poor due to incomplete firing, and if it exceeds 1200°C, energy consumption is high, which is uneconomical. The secondary firing is preferably carried out in an oxidizing atmosphere (eg, oxygen (O ₂ ) or air atmosphere).

Hereinafter, a method of forming Ni powder coated with Cu nanopowder will be described in detail.

Ni powder coated with Cu nanopowder can be formed using high-energy milling.

An example of a high-energy milling machine may be a planetary milling machine or a planetary mixer. Insert Cu nanopowder and Ni powder into a high-energy milling machine, and mill by adjusting the size of the ball, milling time, and rotational speed per minute of high-energy milling. Balls used in Goreness milling may be made of ceramic or metal such as alumina and zirconia, and all of the balls may be of the same size, or balls of two or more sizes may be used together. For example, in consideration of the size of a target particle, the size of the ball may be set in the range of 1 mm to 50 mm, and the rotational speed of high energy milling may be set in the range of 1500 to 4500 rpm. For example, high-energy milling may be performed by repeating the operation of milling for 5 to 30 minutes at a speed of about 1500 to 4500 rpm and stopping for 2 to 20 minutes. High-energy milling is preferably carried out for 30 minutes to 12 hours in consideration of the target particle size and the degree of solid phase reaction. It is preferable that the ball and the total raw material powder (Cu powder, Ni powder) to be put into the high-energy milling are about 5-30:1 by weight. If the content of the balls for the raw powder is too small, sufficient milling may not be performed, so there may be limitations to agglomeration of the particles or miniaturizing the size of the particles, and it is not efficient if the content of the balls to the raw powder is too large. By high-energy milling, the size of the raw material powder is reduced in a short time, and the direct contact area of the reactive particles increases, and the temperature increases due to collision between the ball and the raw material powder, and the ball and the ball, resulting in a solid-solid reaction. . In the high-energy milling machine, mechanical polishing by balls and chemical action by solid-solid-phase reaction occur at the same time, resulting in mechanical and chemical treatment. The Cu powder and Ni powder, which do not undergo chemical reactions well, undergo a solid-solution reaction by high-energy milling to form a new phase.

In the following, experimental examples according to the present invention are specifically presented, and the present invention is not limited to the experimental examples presented below.

<Experimental Example 1>

In order to prepare the base layer of the ceramic floor tile, 12% by weight of limestone, 23% by weight of clay, 42% by weight of pottery stone, 13% by weight of pyrophyllite, and 10% by weight of kaolin were blended as base materials, and loaded into a metal mold, and then 250kgf/ A disk-shaped molded specimen was prepared by uniaxial pressing at a pressure of cm2. The molded specimen was manufactured with a diameter of 30 mm. The molded specimen was first fired. The first firing was carried out in a rapid firing process in which the furnace was passed through the feed car method. The maximum temperature for the primary firing was 1150°C, and the time for feeding tea was 50 minutes. The primary firing was carried out in an air atmosphere.

In order to form an Engobe layer, frit 60% by weight, feldspar 5% by weight, silica stone 17% by weight, kaolin 15% by weight, and zircon 3% by weight were prepared as raw materials. Put a 10mm alumina ball into a ball mill container, and add raw materials for forming the Engobe layer and deionized water, and then ball milling at 300 rpm for 24 hours for wet mixing. After that, in order to remove air bubbles, it was aged (left to stand) at room temperature for 3 hours to form an Engobe composition. The Engobe composition was formed by blending with the distilled water to achieve 60% solid content. The Engobe composition was tested on the first fired specimen using Belsi oil and dried for 6 hours.

In order to form a glaze layer on the upper part of the engobe layer, a glaze composition was prepared by mixing 95% by weight of frit and 5% by weight of kaolin as a glaze raw material. Put 10mm alumina balls in a ball mill container, and charge the glaze raw material and deionized water so that solid content (frit, kaolin) is 60% by weight, and then ball at 300rpm for 24 hours. After wet mixing by ball milling, the glaze composition was formed by aging (left) at room temperature for 3 hours to remove air bubbles.

The glaze composition was spray-applied on the surface to which the Engobe composition was applied, and dried for 6 hours. The thickness of the glaze layer was controlled by controlling the time and frequency of spray application of the glaze composition.

A ceramic tile was obtained by performing secondary firing on the resultant glaze composition tested. A ceramic tile was obtained by performing a rapid sintering process in which the glaze composition was applied and the resultant passed through a furnace in a feed tea manner. The maximum temperature of the secondary firing was 1050°C, and the feeding time was 40 minutes. The secondary firing was carried out in an air atmosphere.

<Experimental Example 2>

Ni powder was prepared. The Ni powder was used having an average particle diameter of 5 μm.

Cu nanopowder was prepared. The Cu nanopowder was used with an average particle diameter of 200 nm.

The Cu nanopowder and the Ni powder were mixed at a weight ratio of 1:9 and subjected to high-energy milling to coat the surface of the Ni powder with the Cu nanopowder. The high-energy milling was performed using a planetary mill, and a 1 mm-sized ZrO ₂ ball, the Cu nanopowder and the Ni powder were charged into the planetary mill, and milled at a speed of 3000 rpm for 10 minutes. And stopping for 5 minutes was repeated three times to perform high-energy milling. 1000 parts by weight of the ZrO ₂ balls were charged with respect to 100 parts by weight of the total content of the Cu nano powder and the Ni powder.

2 is a scanning electron microscope (SEM) photograph showing a state in which Cu nanopowder is coated on the surface of Ni powder after high energy milling, and FIG. 3 is a photo of Cu nanopowder coated on the surface of Ni powder after high energy milling. This is a picture showing the appearance and the result of element mapping analysis.

2 and 3, as a result of observing the Ni powder coated with the Cu nanopowder obtained after high energy milling, it was observed that the Cu nanopowder was uniformly coated on the surface of the Ni powder, and as a result of element mapping analysis, Cu It was observed that was uniformly coated.

In order to prepare the base layer of the ceramic floor tile, 12% by weight of limestone, 23% by weight of clay, 42% by weight of pottery stone, 13% by weight of pyrophyllite, and 10% by weight of kaolin were blended as base materials, and loaded into a metal mold, and then 250kgf/ A disk-shaped molded specimen was prepared by uniaxial pressing at a pressure of cm2. The molded specimen was manufactured with a diameter of 30 mm. The molded specimen was first fired. The first firing was carried out in a rapid firing process in which the furnace was passed through the feed car method. The maximum temperature for the primary firing was 1150°C, and the time for feeding tea was 50 minutes. The primary firing was carried out in an air atmosphere.

In order to form an Engobe layer, frit 60% by weight, feldspar 5% by weight, silica stone 17% by weight, kaolin 15% by weight, and zircon 3% by weight were prepared as raw materials. Put a 10mm alumina ball into a ball mill container, and add raw materials for forming the Engobe layer and deionized water, and then ball milling at 300 rpm for 24 hours for wet mixing. After that, in order to remove air bubbles, it was aged (left to stand) at room temperature for 3 hours to form an Engobe composition. The Engobe composition was formed by blending with the distilled water to achieve 60% solid content. The Engobe composition was tested on the first fired specimen using Belsi oil and dried for 6 hours.

In order to form a glaze layer on the upper part of the engobe layer, a glaze composition was prepared by mixing 95% by weight of frit, 5% by weight of kaolin, and Ni powder coated with the Cu nanopowder as a glaze raw material. The Ni powder coated with the Cu nanopowder was mixed with 5 parts by weight based on 100 parts by weight of the total content of the frit and kaolin. Put 10 mm alumina balls in a ball mill container, and mix the glaze raw material and deionized water so that the solid content (frit, kaolin, and Ni powder coated with Cu nanopowder) constitutes 60% by weight. After charging, ball milling at 300 rpm for 24 hours and wet mixing, and then aged for 3 hours at room temperature to remove air bubbles (left to stand) to form the glaze composition.

The glaze composition was spray-applied on the surface to which the Engobe composition was applied, and dried for 6 hours. The thickness of the glaze layer was controlled by controlling the time and frequency of spray application of the glaze composition.

A ceramic tile was obtained by performing secondary firing on the resultant glaze composition tested. A ceramic tile was obtained by performing a rapid sintering process in which the glaze composition was applied and the resultant passed through a furnace in a feed tea manner. The maximum temperature of the secondary firing was 1050°C, and the feeding time was 40 minutes. The secondary firing was carried out in an air atmosphere.

<Experimental Example 3>

Ni powder was prepared. The Ni powder was used having an average particle diameter of 5 μm.

Cu nanopowder was prepared. The Cu nanopowder was used with an average particle diameter of 200 nm.

The Cu nanopowder and the Ni powder were mixed at a weight ratio of 1:9 and subjected to high-energy milling to coat the surface of the Ni powder with the Cu nanopowder. The high-energy milling was performed using a planetary mill, and a 1 mm-sized ZrO ₂ ball, the Cu nanopowder and the Ni powder were charged into the planetary mill, and milled at a speed of 3000 rpm for 10 minutes. And stopping for 5 minutes was repeated three times to perform high-energy milling. 1000 parts by weight of the ZrO ₂ balls were charged with respect to 100 parts by weight of the total content of the Cu nano powder and the Ni powder. As a result of observing the Ni powder coated with the Cu nanopowder obtained after high-energy milling, it could be observed that the Cu nanopowder was uniformly coated on the surface of the Ni powder.

In order to prepare the base layer of the ceramic floor tile, 12% by weight of limestone, 23% by weight of clay, 42% by weight of pottery stone, 13% by weight of pyrophyllite, and 10% by weight of kaolin were blended as base materials, and loaded into a metal mold, and then 250kgf/ A disk-shaped molded specimen was prepared by uniaxial pressing at a pressure of cm2. The molded specimen was manufactured with a diameter of 30 mm. The molded specimen was first fired. The first firing was carried out in a rapid firing process in which the furnace was passed through the feed car method. The maximum temperature for the primary firing was 1150°C, and the time for feeding tea was 50 minutes. The primary firing was carried out in an air atmosphere.

In order to form an Engobe layer, frit 60% by weight, feldspar 5% by weight, silica stone 17% by weight, kaolin 15% by weight, and zircon 3% by weight were prepared as raw materials. Put a 10mm alumina ball into a ball mill container, and add raw materials for forming the Engobe layer and deionized water, and then ball milling at 300 rpm for 24 hours for wet mixing. After that, in order to remove air bubbles, it was aged (left to stand) at room temperature for 3 hours to form an Engobe composition. The Engobe composition was formed by blending with the distilled water to achieve 60% solid content. The Engobe composition was tested on the first fired specimen using Belsi oil and dried for 6 hours.

In order to form a glaze layer on the upper part of the engobe layer, a glaze composition was prepared by mixing 95% by weight of frit, 5% by weight of kaolin, and Ni powder coated with the Cu nanopowder as a glaze raw material. The Ni powder coated with the Cu nanopowder was mixed with 10 parts by weight based on 100 parts by weight of the total content of the frit and kaolin. Put 10 mm alumina balls in a ball mill container, and mix the glaze raw material and deionized water so that the solid content (frit, kaolin, and Ni powder coated with Cu nanopowder) constitutes 60% by weight. After charging, ball milling at 300 rpm for 24 hours and wet mixing, and then aged for 3 hours at room temperature to remove air bubbles (left to stand) to form the glaze composition.

The glaze composition was spray-applied on the surface to which the Engobe composition was applied, and dried for 6 hours. The thickness of the glaze layer was controlled by controlling the time and frequency of spray application of the glaze composition.

A ceramic tile was obtained by performing secondary firing on the resultant glaze composition tested. A ceramic tile was obtained by performing a rapid sintering process in which the glaze composition was applied and the resultant passed through a furnace in a feed tea manner. The maximum temperature of the secondary firing was 1050°C, and the feeding time was 40 minutes. The secondary firing was carried out in an air atmosphere.

<Experimental Example 4>

Ni powder was prepared. The Ni powder was used having an average particle diameter of 5 μm.

Cu nanopowder was prepared. The Cu nanopowder was used with an average particle diameter of 200 nm.

The Cu nanopowder and the Ni powder were mixed at a weight ratio of 1:9 and subjected to high-energy milling to coat the surface of the Ni powder with the Cu nanopowder. The high-energy milling was performed using a planetary mill, and a 1 mm-sized ZrO ₂ ball, the Cu nanopowder and the Ni powder were charged into the planetary mill, and milled at a speed of 3000 rpm for 10 minutes. And stopping for 5 minutes was repeated three times to perform high-energy milling. 1000 parts by weight of the ZrO ₂ balls were charged with respect to 100 parts by weight of the total content of the Cu nano powder and the Ni powder. As a result of observing the Ni powder coated with the Cu nanopowder obtained after high-energy milling, it could be observed that the Cu nanopowder was uniformly coated on the surface of the Ni powder.

In order to prepare the base layer of the ceramic floor tile, 12% by weight of limestone, 23% by weight of clay, 42% by weight of pottery stone, 13% by weight of pyrophyllite, and 10% by weight of kaolin were blended as base materials, and loaded into a metal mold, and then 250kgf/ A disk-shaped molded specimen was prepared by uniaxial pressing at a pressure of cm2. The molded specimen was manufactured with a diameter of 30 mm. The molded specimen was first fired. The first firing was carried out in a rapid firing process in which the furnace was passed in the way of feeding. The maximum temperature for the primary firing was 1150°C, and the time for sending tea was 50 minutes. The primary firing was carried out in an air atmosphere.

In order to form an Engobe layer, frit 60% by weight, feldspar 5% by weight, silica stone 17% by weight, kaolin 15% by weight, and zircon 3% by weight were prepared as raw materials. Put a 10mm alumina ball into a ball mill container, and add raw materials for forming the Engobe layer and deionized water, and then ball milling at 300 rpm for 24 hours for wet mixing. After that, in order to remove air bubbles, it was aged (left to stand) at room temperature for 3 hours to form an Engobe composition. The Engobe composition was formed by blending with the distilled water to achieve 60% solid content. The Engobe composition was tested on the first fired specimen using Belsi oil and dried for 6 hours.

In order to form a glaze layer on the upper part of the engobe layer, a glaze composition was prepared by mixing 95% by weight of frit, 5% by weight of kaolin, and Ni powder coated with the Cu nanopowder as a glaze raw material. The Ni powder coated with the Cu nanopowder was mixed with 15 parts by weight based on 100 parts by weight of the total content of the frit and kaolin. Put 10 mm alumina balls in a ball mill container, and mix the glaze raw material and deionized water so that the solid content (frit, kaolin, and Ni powder coated with Cu nanopowder) constitutes 60% by weight. After charging, ball milling at 300 rpm for 24 hours and wet mixing, and then aged for 3 hours at room temperature to remove air bubbles (left to stand) to form the glaze composition.

The glaze composition was spray-applied on the surface to which the Engobe composition was applied, and dried for 6 hours. The thickness of the glaze layer was controlled by controlling the time and frequency of spray application of the glaze composition.

A ceramic tile was obtained by performing secondary firing on the resultant glaze composition tested. A ceramic tile was obtained by performing a rapid sintering process in which the glaze composition was applied and the resultant passed through a furnace in a feed tea manner. The maximum temperature of the secondary firing was 1050°C, and the feeding time was 40 minutes. The secondary firing was carried out in an air atmosphere.

<Experimental Example 5>

Ni powder was prepared. The Ni powder was used having an average particle diameter of 5 μm.

Cu nanopowder was prepared. The Cu nanopowder was used with an average particle diameter of 200 nm.

The Cu nanopowder and the Ni powder were mixed at a weight ratio of 1:9 and subjected to high-energy milling to coat the surface of the Ni powder with the Cu nanopowder. The high-energy milling was performed using a planetary mill, and a 1 mm-sized ZrO ₂ ball, the Cu nanopowder and the Ni powder were charged into the planetary mill, and milled at a speed of 3000 rpm for 10 minutes. And stopping for 5 minutes was repeated three times to perform high-energy milling. 1000 parts by weight of the ZrO ₂ balls were charged with respect to 100 parts by weight of the total content of the Cu nano powder and the Ni powder. As a result of observing the Ni powder coated with the Cu nanopowder obtained after high-energy milling, it could be observed that the Cu nanopowder was uniformly coated on the surface of the Ni powder.

In order to prepare the base layer of the ceramic floor tile, 12% by weight of limestone, 23% by weight of clay, 42% by weight of pottery stone, 13% by weight of pyrophyllite, and 10% by weight of kaolin were blended as base materials, and loaded into a metal mold, and then 250kgf/ A disk-shaped molded specimen was prepared by uniaxial pressing at a pressure of cm2. The molded specimen was manufactured to have a diameter of 30 mm. The molded specimen was first fired. The first firing was carried out in a rapid firing process in which the furnace was passed in the way of feeding. The maximum temperature for the primary firing was 1150°C, and the time for sending tea was 50 minutes. The primary firing was carried out in an air atmosphere.

In order to form an Engobe layer, frit 60% by weight, feldspar 5% by weight, silica stone 17% by weight, kaolin 15% by weight, and zircon 3% by weight were prepared as raw materials. Put a 10mm alumina ball into a ball mill container, and add raw materials for forming the Engobe layer and deionized water, and then ball milling at 300 rpm for 24 hours for wet mixing. After that, in order to remove air bubbles, it was aged (left to stand) at room temperature for 3 hours to form an Engobe composition. The Engobe composition was formed by blending with the distilled water to achieve 60% solid content. The Engobe composition was tested on the first fired specimen using Belsi oil and dried for 6 hours.

In order to form a glaze layer on the upper part of the engobe layer, a glaze composition was prepared by mixing 95% by weight of frit, 5% by weight of kaolin, and Ni powder coated with the Cu nanopowder as a glaze raw material. The Ni powder coated with the Cu nanopowder was mixed with 20 parts by weight based on 100 parts by weight of the total content of the frit and kaolin. Put 10 mm alumina balls in a ball mill container, and mix the glaze raw material and deionized water so that the solid content (frit, kaolin, and Ni powder coated with Cu nanopowder) constitutes 60% by weight. After charging, ball milling at 300 rpm for 24 hours and wet mixing, and then aged for 3 hours at room temperature to remove air bubbles (left to stand) to form the glaze composition.

The glaze composition was spray-applied on the surface to which the Engobe composition was applied, and dried for 6 hours. The thickness of the glaze layer was controlled by controlling the time and frequency of spray application of the glaze composition.

A ceramic tile was obtained by performing secondary firing on the resultant glaze composition tested. A ceramic tile was obtained by performing a rapid sintering process in which the glaze composition was applied and the resultant passed through a furnace in a feed tea manner. The maximum temperature of the secondary firing was 1050°C, and the feeding time was 40 minutes. The secondary firing was carried out in an air atmosphere.

The contact angles of the glaze layers of ceramic tiles manufactured according to Experimental Examples 1 to 5 were measured and shown in Table 1 below. This is the case when the thickness of the glaze layer is about 200 μm after the secondary firing by controlling the time and number of application of the glaze composition.

Experimental Example 1 Experimental Example 2 Experimental Example 3 Experimental Example 4 Experimental Example 5 Contact angle ( ^o ) 23.5 98.4 112.1 84.6 58.0

Referring to Table 1, a change in the contact angle of the glaze surface was observed according to the content of Ni powder coated with Cu nanopowder. According to Experimental Example 2, when the glaze layer was formed by using the glaze composition to which the Cu nanopowder coated Ni powder was not added, the contact angle was 23.5°, indicating a very low value. In the case of Experimental Example 3 (when 10 parts by weight of Ni powder coated with Cu nanopowder was mixed), the contact angle was found to be the highest.

The contact angle according to the thickness of the glaze layer with respect to the ceramic tile manufactured according to Experimental Example 3 was measured and shown in Table 2 below.

Glaze layer thickness 50 mm 80 mm 120 mm 150 mm 200 mm Contact angle ( ^o ) 33.8 60.9 108.5 112.1 81.7

Referring to Table 2, a contact angle (hydrophobicity) of 100 ^o or more was observed in the range of 120 to 150 mm in thickness of the glaze layer. When the thickness of the glaze layer was 120mm, the contact angle was the highest.

4 is a photograph showing a ceramic tile prepared by mixing 10 parts by weight of Ni powder coated with Cu nanopowder according to Experimental Example 3 and making the thickness of the glaze layer 150mm, and FIG. This is a photograph showing the contact angle of the ceramic tile prepared by mixing 10 parts by weight of the coated Ni powder and making the thickness of the glaze layer 150 mm.

In the above, a preferred embodiment of the present invention has been described in detail, but the present invention is not limited to the above embodiment, and various modifications are possible by those of ordinary skill in the art.

110: substratum
120: Enkobe layer
130: glaze layer

Claims (11)

As a glaze composition for forming the glaze layer in a ceramic tile including a base layer, an engobe layer provided on the base layer, and a glaze layer provided on the upper part of the base layer,
A glaze raw material comprising 90 to 98% by weight of glass frit powder and 2 to 10% by weight of kaolin powder,
Further comprising 1 to 20 parts by weight of Ni powder coated with Cu nanopowder based on 100 parts by weight of the glaze raw material,
The Cu nanopowder has an average particle diameter of 10 to 300 nm,
The glaze composition, characterized in that the Ni powder has an average particle diameter of 1 to 10㎛.
delete delete The glaze composition according to claim 1, wherein the Cu nanopowder comprises 0.1 to 25 parts by weight based on 100 parts by weight of the Ni powder.
The glaze composition according to claim 1, wherein the glaze composition further comprises 0.1 to 10 parts by weight of zircon powder based on 100 parts by weight of the glaze raw material.
Forming an engobe layer on the top of the base layer that is molded and first fired;
Forming a glaze layer by applying a glaze composition on top of the engobe layer and drying it; And
It includes the step of secondary firing the resultant glaze layer is formed,
The glaze composition,
Including a glaze raw material containing 90 to 98% by weight of glass frit powder and 2 to 10% by weight of kaolin powder,
Further comprising 1 to 20 parts by weight of Ni powder coated with Cu nanopowder based on 100 parts by weight of the glaze raw material,
The Cu nanopowder has an average particle diameter of 10 to 300 nm,
The method of manufacturing a ceramic tile, wherein the Ni powder has an average particle diameter of 1 to 10 μm.
delete delete The method of claim 6, wherein the Cu nanopowder comprises 0.1 to 25 parts by weight based on 100 parts by weight of the Ni powder.
The method of claim 6, wherein the glaze composition further comprises 0.1 to 10 parts by weight of zircon powder based on 100 parts by weight of the glaze raw material.
The method of claim 6, wherein the glaze layer is formed to a thickness of 100 to 200 μm.

Images