KR101384968B1 - Composite for porous ceramic ware and manufacturing method of porous ceramic ware using the composite - Google Patents

Abstract

The present invention provides 20 to 50% by weight of quartzite having particles smaller than 100 μm, 15 to 40% by weight of feldspar, 25 to 55% by weight of clay, 0.1 to 15% by weight of silica sand having coarse particles of 200 μm to 2 mm and porous A breathable porcelain composition comprising 0.1 to 10% by weight of zeolite as a crystal, wherein the clay is made of swellable clay that expands when 2 to 50% by weight of water is absorbed relative to the total content of clay, and the swellable clay is It consists of a layered clay containing water molecules between the layers, the porcelain relates to a breathable porcelain holding composition which is a white porcelain, celadon or powder blue dust and a method for producing a breathable porcelain using the same. According to the present invention, a plurality of pores can be formed to impart breathability, can be used as a breathing container to improve the taste of food, it is possible to manufacture a breathable porcelain excellent in heat resistance and excellent strength.

Description

Composite material for breathable porcelain and method for manufacturing breathable porcelain using same {Composite for porous ceramic ware and manufacturing method of porous ceramic ware using the composite}

The present invention relates to a magnetic holding composition and a method of manufacturing porcelain using the same, and more particularly, to a magnetic holding composition and a method of manufacturing a breathable porcelain using a plurality of pores are formed to exhibit breathability.

Recently, with the explosive interest in eco-friendly materials, the interest in Korean traditional materials, which have been handed down from ancient times, has increased greatly.

Pottery is a term that includes pottery and porcelain. Ceramics are mainly made of materials such as clay, feldspar, silica, pyrophyllite, and stonite. Ceramics are products obtained by mixing and molding these materials at a certain ratio, followed by firing and curing. Pottery has a high absorption rate, so it produces a dull sound when tapped and has a relatively low durability. It has a low absorption rate and gives a clear sound when touched and has excellent durability.

In recent years, research is being actively conducted on physically and chemically refining raw materials used for improving properties and characterizing ceramic products or replacing them with other raw materials.

In recent years, the field of the lifestyle device is required to have a product with light, thin and large new physical properties.

In particular, Onggi, which has developed our own food culture, has been used for a long time as a storage container as a living tableware. There is an active discussion about the excellence of the taste of foods cooked using such an Onggi. Onggi is known as a pottery breathing due to its unique pore structure.

However, white porcelain, celadon or bonsai fructose and porcelain are more commonly used as a tableware, and if they are made of breathing containers, the ripple effect of the tableware is expected to be great.

The problem to be solved by the present invention is that it can be used as a breathing container to improve the taste of food can be given a plurality of pores are formed breathability, excellent heat resistance, excellent strength of the porcelain holding composition and breathable porcelain using the same To provide a method of manufacturing.

The present invention provides 20 to 50% by weight of quartzite having particles smaller than 100 μm, 15 to 40% by weight of feldspar, 25 to 55% by weight of clay, 0.1 to 15% by weight of silica sand having coarse particles of 200 μm to 2 mm and porous A breathable porcelain composition comprising 0.1 to 10% by weight of zeolite as a crystal, wherein the clay comprises 2 to 50% by weight of swellable clay with respect to the total content of clay, and the swellable clay contains water molecules between layers. Consisting of layered clay, the porcelain provides a porcelain composition for breathable porcelain, which is white porcelain, celadon or powder dust.

The swellable clay may be composed of layered clay containing exchangeable cations together with water molecules between layers.

In addition, the swellable clay may be made of a layered clay in which water molecules in the layers are partially exchanged with an organic material to form a clay-organic complex.

In addition, the swellable clay may be made of one or more layered clays selected from bentonite, montmorillonite, saponite, hectorite, Weidelite, halosite, vermiculite, soconite and nontronite.

The zeolite may contain an exchangeable cation in a crystal structure and a part of the cation is substituted with an anion to exhibit antimicrobial activity.

The breathable magnetic material composition may further comprise 0.1 to 5% by weight of feldspar.

In addition, the breathable magnetic base material composition may further comprise 0.1 to 5% by weight of cordierite having heat resistance.

In addition, the breathable magnetic material composition may further comprise 0.1 to 5% by weight of magnesium aluminate (MgAl ₂ O ₄ ).

In addition, the breathable porcelain holding composition may further comprise 0.1 to 5% by weight of mullite (mullite).

In addition, the breathable magnetic material composition may further comprise 0.1 to 5% by weight of zirconia (ZrO ₂ ).

In addition, the breathable magnetic holding composition may further comprise 0.1 to 5% by weight of petalite.

The present invention also pulverizes a starting material comprising 20-50% by weight of silica with particles smaller than 100 μm, 15-40% by weight of feldspar, 25-55% by weight of clay and 0.1-10% by weight of zeolite as a porous crystal. And mixing 0.1 to 15% by weight of the silica sand having coarse particles of 200 μm to 2 mm to the pulverized starting material, shaping and drying the starting material mixed with the silica sand to a desired shape and forming Calcining the starting material at a temperature of 900 to 1200 ° C. to form a breathable porcelain, wherein the clay is composed of 2 to 50 wt% of swellable clay with respect to the total content of clay, and the swellable clay is interlayered. Comprising a layered clay containing water molecules, the porcelain is a white porcelain, celadon or powder blue dust provides a method for producing a breathable porcelain characterized in that.

The swellable clay may be composed of layered clay containing exchangeable cations together with water molecules between layers.

In addition, the swellable clay may be made of a layered clay in which water molecules in the layers are partially exchanged with an organic material to form a clay-organic complex.

In addition, the swellable clay may be made of one or more layered clays selected from bentonite, montmorillonite, saponite, hectorite, Weidelite, halosite, vermiculite, soconite and nontronite.

The zeolite may contain an exchangeable cation in a crystal structure and a part of the cation is substituted with an anion to exhibit antimicrobial activity.

The starting material may further comprise 0.1 to 5% by weight of feldspar.

In addition, the starting material may further comprise 0.1 to 5% by weight of cordierite having heat resistance.

In addition, the breathable magnetic material composition may further comprise 0.1 to 5% by weight of magnesium aluminate (MgAl ₂ O ₄ ).

In addition, the breathable porcelain holding composition may further comprise 0.1 to 5% by weight of mullite (mullite).

In addition, the starting material may further comprise 0.1 to 5% by weight of zirconia (ZrO ₂ ).

In addition, the starting material may further comprise 0.1 to 5% by weight of petalite.

According to the breathable porcelain holding composition of the present invention, a number of pores are formed on the porcelain to exhibit breathability, and thus, as a living table, the breathable porcelain can be used as a breathing container, and the effect of improving food taste can be expected.

In addition, according to the present invention, it is possible to manufacture a breathable porcelain having excellent heat resistance by containing cordierite or petalite having excellent heat resistance and heat shock resistance in the breathable porcelain holding composition.

In addition, according to the present invention, a breathable porcelain having excellent strength can be manufactured by containing magnesium aluminate (MgAl ₂ O ₄ ), mullite, or zirconia (ZrO ₂ ) having excellent strength in the breathable porcelain composition.

1 is an example of a transmittance measurement graph.
2 is a schematic diagram of an apparatus for measuring transmittance.
Figure 3 is a photograph showing the actual appearance of the device for measuring the transmittance.
4 is a photograph according to the firing temperature of the celadon specimen.
5 is a photograph according to the firing temperature of the powder sprayer specimens.
6 is a photograph according to the firing temperature of the white porcelain specimen.
7A is a scanning electron microscope (SEM) photograph showing pores of a celadon specimen prepared by firing at 1200 ° C., and FIG. 7B is a scanning electron microscope showing a pore of celadon specimen prepared by firing at 1300 ° C. FIG. (SEM) This is a picture.
Figure 8a is a scanning electron microscope (SEM) photograph showing the pore state of the powder sprayer specimen prepared by firing at 1200 ℃, Figure 8b is a scanning electron microscope (SEM) showing the pore state of the powder sprayer specimen prepared by firing at 1300 ℃ ) Photo.
9A is a scanning electron microscope (SEM) photograph showing the pores of the white porcelain specimen prepared by firing at 1200 ℃, Figure 9b is a scanning electron microscope (SEM) photograph showing the pores of the white porcelain specimen prepared by firing at 1300 ℃ to be.
10 is a graph showing the transmittance according to the firing temperature of the celadon specimen prepared by firing at 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃.
11 is a graph showing the transmittance according to the firing temperature of the powder sprayer specimens prepared by firing at 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃.
12 is a graph showing the transmittance according to the firing temperature of the white porcelain specimen prepared by firing at 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃.
FIG. 13 is a scanning electron micrograph of a white porcelain specimen prepared by firing at 1200 ° C. according to Example 2. FIG.
14 is a graph showing the transmittance according to the firing temperature of the white porcelain specimen prepared by firing at 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃ according to Experimental Example 2.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, it should be understood that the following embodiments are provided so that those skilled in the art will be able to fully understand the present invention, and that various modifications may be made without departing from the scope of the present invention. It is not. Wherein like reference numerals refer to like elements throughout.

Hereinafter, the term "self" means used to include white porcelain, celadon and buncheongsa, which are mainly used in daily life.

Breathable porcelain holding composition according to a preferred embodiment of the present invention, 20 to 50% by weight of silica, 15 to 40% by weight feldspar, 25 to 55% by weight of clay having particles smaller than 100㎛ A breathable porcelain composition comprising 0.1 to 15% by weight of silica sand with particles and 0.1 to 10% by weight of zeolite, which is a porous crystal, wherein the clay comprises 2 to 50% by weight of swellable clay with respect to the total content of clay, The swellable clay may be made of layered clay containing water molecules between layers.

The swellable clay may be composed of layered clay containing exchangeable cations together with water molecules between layers.

In addition, the swellable clay may be made of a layered clay in which water molecules in the layers are partially exchanged with an organic material to form a clay-organic complex.

In addition, the swellable clay may be made of one or more layered clays selected from bentonite, montmorillonite, saponite, hectorite, Weidelite, halosite, vermiculite, soconite and nontronite.

The zeolite may contain an exchangeable cation in a crystal structure and a part of the cation is substituted with an anion to exhibit antimicrobial activity.

The breathable magnetic material composition may further comprise 0.1 to 5% by weight of feldspar.

In addition, the breathable magnetic base material composition may further comprise 0.1 to 5% by weight of cordierite having heat resistance.

In addition, the breathable magnetic material composition may further comprise 0.1 to 5% by weight of magnesium aluminate (MgAl ₂ O ₄ ).

In addition, the breathable porcelain holding composition may further comprise 0.1 to 5% by weight of mullite (mullite).

In addition, the breathable magnetic material composition may further comprise 0.1 to 5% by weight of zirconia (ZrO ₂ ).

In addition, the breathable porcelain holding composition may further comprise 0.1 to 5% by weight of Petalite having heat resistance.

In the method of manufacturing a breathable porcelain according to a preferred embodiment of the present invention, 20 to 50% by weight of silica, 15 to 40% by weight of feldspar, 25 to 55% by weight of clay and particles of zeolite 0.1 to 10 having particles smaller than 100 μm Pulverizing a starting material comprising a weight%, mixing 0.1 to 15% by weight of silica sand having coarse particles of 200 μm to 2 mm to the ground starting material; Shaping and drying in the form and calcining the starting material at a temperature of 900 ~ 1200 ℃ to form a breathable porcelain, the clay is 2 to 50% by weight relative to the total content of the clay as swellable clay The swellable clay is made of a layered clay containing water molecules between layers, and the porcelain is a white porcelain, blue porcelain, or powdered blue yarn.

The swellable clay may be composed of layered clay containing exchangeable cations together with water molecules between layers.

In addition, the swellable clay may be made of a layered clay in which water molecules in the layers are partially exchanged with an organic material to form a clay-organic complex.

In addition, the swellable clay may be made of one or more layered clays selected from bentonite, montmorillonite, saponite, hectorite, Weidelite, halosite, vermiculite, soconite and nontronite.

The zeolite may contain an exchangeable cation in a crystal structure and a part of the cation is substituted with an anion to exhibit antimicrobial activity.

The starting material may further comprise 0.1 to 5% by weight of feldspar.

In addition, the starting material may further comprise 0.1 to 5% by weight of cordierite having heat resistance.

In addition, the breathable magnetic material composition may further comprise 0.1 to 5% by weight of magnesium aluminate (MgAl ₂ O ₄ ).

In addition, the breathable porcelain holding composition may further comprise 0.1 to 5% by weight of mullite (mullite).

In addition, the starting material may further comprise 0.1 to 5% by weight of zirconia (ZrO ₂ ).

In addition, the starting material may further comprise 0.1 to 5% by weight of petalite.

Hereinafter, the breathable magnetic holding composition of the present invention will be described in more detail.

As a starting material of the breathable porcelain composition according to a preferred embodiment of the present invention, 20 to 50% by weight of silica, 15 to 40% by weight of feldspar, 25 to 55% by weight of clay, and 200 μm to 2 having particles smaller than 100 μm. 0.1 to 15% by weight of silica sand with mm thick particles and 0.1 to 10% by weight of zeolite as a porous crystal. The clay is made of swellable clay that expands when 2 to 50% by weight of water is absorbed based on the total content of clay, and the swellable clay may be made of layered clay containing water molecules between layers.

Quartzite increases the whiteness of the porcelain body and maintains its own skeleton. The silica is preferably contained in the breathable porcelain base material 20 to 50% by weight. When the content of silica is less than 15% by weight, the whiteness of the breathable porcelain may be lowered. When the content of the silica is more than 50% by weight, it may be difficult to obtain desired breathability due to a decrease in porosity.

Feldspar starts to melt at a relatively low temperature and acts as a flux to melt raw materials such as silica. Feldspar contains a lot of K ₂ O and Na ₂ O as an alkaline component, and increasing the content of feldspar promotes melting and lowers the melting point so that it can be fired at a lower temperature. However, when the content of feldspar is increased, the viscosity of the raw material at the time of baking decreases, so that the amount of plastic deformation due to stress such as self weight at the time of baking increases. That is, when it contains many feldspar components, plastic deformation by softening of a base material increases as baking of a breathable magnetic base material advances. In view of this point, feldspar is preferably contained in the breathable magnetic holding composition 15 to 40% by weight.

Clay provides plasticity to the body during the molding process and maintains sufficient molding strength to withstand the process of moving and decorating the molded body. In addition, after firing, the mullite phase and the glass phase are formed in the substrate, thereby contributing to making the substrate white light-transmitting while maintaining sufficient strength in the use environment.

By adding swellable clay, plasticity is improved, and it is possible to manufacture lightweight breathable porcelain. Swellable clay is a layered clay having a particulate form (shape) in which the clay platelets are held by weak van der Waals forces. Such swellable clays are generally able to absorb moisture well and provide a factor that can shrink when moisture absorbed evaporates upon firing to form pores. It is preferable that 2-50 weight% consists of swellable clay with respect to the total content of clay.

These swellable clays that absorb and expand water include not only layered clays containing water molecules between layers, but also water exchangeable cations (usually alkali ions Na ⁺ , Li ^+, etc.) with water molecules between layers. Layered clays and layered clays in which water molecules between layers are partially exchanged with organics to form clay-organic complexes can be used.

In the swellable clay in which water molecules enter together with exchangeable cations, water molecules are basically coordinated with exchangeable cations, and hydrogen bonds are formed between water molecules and oxygen at the bottom. On the other hand, the amount of such interlayers, that is, the number of water molecules, is changed step by step depending on the ambient humidity and the types of exchangeable cations entered between the layers, thereby changing the interlayer spacing. These swellable clays, which contain exchangeable cations, have a surface-substituted reaction with colloidal particles having different cationic surface charges or inorganic cluster cations due to their intrinsic cation exchange properties, forming so-called crosslinked clays. There is a characteristic to. Since the crosslinked clay exists as an inorganic oxide crosslinks between layers, stable pores may be formed.

 The layered clay in which water molecules in the layers are partially exchanged with organics to form a clay-organic complex is intercalated by ion exchange reaction between exchangeable cations and organic cations present in the layers, or by adsorption of polar organic molecules. Organic matter is incorporated. For example, a heavy component such as ethylene glycol glycerol or an organic cation such as alkyl ammonium may be added.

Such swellable clays are bentonite, montmorillonite, saponite, hectorite, beidelite, halloysite, vermiculite, vermiculite, soconite and It may be composed of one or more layered clays selected from nontronite.

Bentonite is strong in viscous force and has high swelling and cation exchangeability.

Montmorillonite exhibits unique swelling characteristics by hydration of interlayer ions in aqueous solution. Montmorillonite has a high cation exchange capacity, so that lattice peeling is easily caused by swelling in an aqueous solution. In the case of montmorillonite having Na ⁺ or Li ⁺ as an exchangeable cation, the interlaminar distance is measured in water up to about 40 ~ 140Å, which causes the clay to adsorb water between layers in water and expand (swelling). to be.

Haloysite (halloysite) is a water molecule in the interlaminar water in the wet state, but does not contain exchangeable cations. The interlayer number of these halosites is easily dehydrated when dried, and the interlayer spacing is reduced to about 7.4 to 7.5 kPa from about 10 kPa.

Zeolite is a porous crystal made of silicon (Si) and aluminum (Al) and has a property of selectively and strongly adsorbing unsaturated hydrocarbons or polar substances by the action of cations in its crystal structure. Since zeolites have a fixed pore size, they have a characteristic of selectively passing small molecules and adsorbing them, and because they contain exchangeable cations in the crystal structure, they are easily exchanged freely with other cations. . Substituting anions for some of the cations constituting the zeolite is expected to be able to be utilized as a breathable porcelain having antimicrobial properties. The zeolite is preferably contained in an amount of 0.1 to 10% by weight in the breathable porcelain base material composition.

Pyrophyllite is a swellable material that serves to form pores on its surface. Pyrite is a mineral having a layered structure, and the chemical formula is (MgFe, Al) ₃ (Al, Si) ₄ O ₁₀ (OH) ₂ · 4H ₂ O, and has a size of 200 μm to 2 mm by layer separation due to water vapor during firing. It acts as a factor in forming pores. The feldspar is preferably contained in an amount of 0.1 to 5% by weight based on the air permeable composition. If the content of the feldspar is less than 0.1% by weight, it is difficult to obtain the desired porosity by the pores, and if the content of the feldspar exceeds 5% by weight, the pore size and porosity may be too large.

Cordierite has a chemical formula of 2MgO-2Al ₂ O ₃ -5SiO ₂ , and is a material having excellent heat resistance. Cordierite is a material with a low coefficient of thermal expansion, excellent thermal shock resistance and excellent corrosion resistance. Such cordierite is preferably contained in an amount of 0.1 to 5% by weight in the breathable porcelain holding composition.

Cordierite, a material having excellent heat resistance, has a low coefficient of thermal expansion, and thus has excellent thermal shock resistance, but poor mechanical properties. This problem can be solved by addition according to the firing temperature and the type and amount of hard material in order to obtain a high strength material. As the hard material, magnesium aluminate (MgAl ₂ O ₄ ), mullite (mullite) or zirconia (ZrO ₂ ) may be used, and fine MgAl ₂ O ₅ , mullite, ZrO _2, etc. around cordierite may be used. Since it is uniformly distributed, it is possible to increase the strength by reducing the particle growth of cordierite and reducing microcracks.

In the case of porcelain, due to the difference in the thermal expansion coefficient of the matrix of the glass phase and the crystal phases distributed therein, a strong compressive force is applied to the glass phase, leading to an increase in the strength of the base. Magnetic strength is influenced by the matrix of the glass phase formed after firing and the type and characteristics (size, shape, etc.) of the crystal phases present in the glass matrix. High-strength breathable porcelain can be produced by adding hard materials from the breathable porcelain. The hard material increases the viscosity of the molten body in the firing process, promotes crystallization of the liquid phase, lowers the heat deformation and enhances the strength of the fired body (fired breathable magnetic). As the addition amount of the hard material is increased, high strength is obtained and the plastic deformation amount is small, but the firing temperature is somewhat higher. Therefore, in consideration of this point, it is preferable that the hard material is contained in the breathable porcelain holding composition within the range of 0.1 to 5% by weight. For example, 0.1-5% by weight of magnesium aluminate (MgAl ₂ O ₄ ), 0.1-5% by weight of mullite, or 0.1-5% by weight of zirconia (ZrO ₂ ) is added as a hard material.

Petalite is a material with excellent heat resistance. When used at high temperature and room temperature, a temperature gradient occurs in the material, and the thermal stress generated at such a temperature change may destroy the material, but there is an advantage of suppressing this phenomenon by the addition of petalite. It is preferable that such a petalite contains 0.1 to 5 weight% in a breathable porcelain holding composition.

Hereinafter, a method of manufacturing porcelain using the above-mentioned breathable porcelain holding composition will be described.

The starting materials of the breathable porcelain base material composition of the present invention are blended and mixed at a desired ratio. A solvent and a dispersant may be further added during the mixing, and distilled water, ethanol, methanol, or the like may be used as the solvent. The dispersant is added to suppress aggregation of raw material particles and to increase dispersibility. The dispersant is preferably added 0.1 to 5 parts by weight relative to the starting material solids of the breathable porcelain holding composition.

The starting material is ground in order to micronize. In general, feldspar, silica, etc., used as a raw material for breathable porcelain, is made of coarse rock material having a size of up to several mm. In general, when these rocky raw materials are used as they are, there is a limit in lowering the firing temperature. Therefore, raw materials such as feldspar and silica are micronized to 100 micrometers (µm) or less (for example, 1 to 100 µm) in order to produce breathable porcelain with less thermal deformation using these materials. When the raw material powder is micronized (micronized) in order to reduce the plastic deformation amount, the deformation during firing is small. By micronizing these raw materials, not only thermal deformation but also the firing temperature can be lowered, which is advantageous for energy saving. When the starting material of the porcelain porcelain is pulverized, finely divided and fractionally charged, the density increases in the molded body stage, the firing density can be increased, the absorption rate is decreased, and the firing temperature is lowered. As a method for micronizing feldspar, silica and the like used as starting materials for breathable porcelain, various grinding methods such as dry or wet ball milling and milling media can be used.

Hereinafter, the grinding process by the ball milling method will be described in detail. The starting materials are charged into a ball milling machine and wet mixed with the solvent. The solvent may be water, alcohol, or the like. Rotate at a constant speed using a ball mill to mechanically grind and uniformly mix the starting materials. The ball used for ball milling may be a ball made of ceramics such as alumina or zirconia, and the balls may be all the same size or may be used together with balls having two or more sizes. The size of the balls, the milling time, and the rotation speed per minute of the ball miller are adjusted so as to be crushed to the target particle size. For example, in consideration of the size of the particles, the size of the ball can be set in the range of about 0.1 mm to 50 mm, and the rotational speed of the ball mill can be set in the range of about 10 to 500 rpm. Ball milling is performed for 1 to 72 hours in consideration of the target particle size and the like. The ball mill causes the starting material to be ground into particles of fine size, to have a uniform particle size distribution, and to be mixed uniformly.

A dehydration process is performed on the starting materials in the slurry state. After dehydration using an extrusion filter, the mixture is mixed with a refiner. In order to remove iron (Fe) components, etc. contained in the starting material before the dehydration process may be carried out a step of de-ironing with a degasser. A known method can be used for the de-ironing process, and a description thereof will be omitted here. It is preferable to add 0.1-15 weight% of the silica sand which has 200 micrometers-2 mm thick particle at the time of mixing with a refiner.

The breathable porcelain holding composition that has undergone the above-described process may form breathable porcelain through a molding, drying, and baking process described later. The molding may use various methods such as injection molding and extrusion molding.

In more detail, the pulverized product is molded into a desired shape, and a drying process is performed. The drying process may be dried for 2 to 24 hours in an 80 to 150 ℃ oven, spray spray method may be used. Spray drying may be carried out at a temperature of 80 to 150 ℃ by spraying hot air through the nozzle to dry. Most of the solvent components are removed by the drying process.

The dried specimen is fired to produce a breathable porcelain. The firing is carried out for 1 to 48 hours at a temperature of 900 ~ 1200 ℃. The firing step is performed by heating up to a firing temperature (900-1200 ° C.) at a constant heating rate (for example, 2-50 ° C./min), maintaining the baking for a predetermined time (1 to 48 hours), and cooling to room temperature. can do. The firing is preferably performed in an oxidizing atmosphere (for example, oxygen (O ₂ ) or air atmosphere).

The firing process may be performed as follows. The conglomerate is heated to a second temperature (700 to 900 ° C) at a first temperature (for example, room temperature) to carry out firing, and to maintain a predetermined time (1 to 48 hours) at a third temperature (for example, 900 to 1200 ° C). After firing, the process may be performed to cool to room temperature. After performing the above-mentioned firing, the chaebol firing may be performed by cooling to room temperature and raising the temperature to a third temperature (eg, 900 to 1200 ° C).

When the dispersant is added during the process, the dispersant is composed of the organic component and thus burns away when it reaches a temperature of 300 to 400 ° C. The firing temperature is higher than the burning temperature of the organic component. The components are all removed, and the space in which the dispersant is located forms pores. In addition, the water molecules contained between the layers of the swellable clay are evaporated in the firing process, so that the space in which the water molecules are located becomes a pore as the plastic shrinkage occurs, and the pores of the calcining process have porosity and are breathable. In addition, when the swellable clay consists of layered clay in which water molecules in the interlayer are partially exchanged with organics to form a clay-organic complex, the organics are burned away during the firing process and the space where the organics are located forms pores. In addition, porcelain, which has undergone a calcination process, has the advantage of being porous and breathable.

Hereinafter, a device for measuring the permeability of a breathable porcelain manufactured using the composition for breathable porcelain and a method for measuring the permeability using the same will be described.

Permeability Measurement Principle

It uses the principle that the gas flows from the high pressure to the low pressure. It is a principle to measure the change in the time that the high-pressure gas passes through the pores of the breathable porcelain to the low pressure.

Permeability Measurement Method

In the following experimental examples, the transmittance was measured in the following manner.

The measurement of permeability begins after loading the specimen into a 1000torr gas under vacuum, one measurement time is 90 minutes, and the gas passes through the pores of the specimen (see Fig. 1 (b)) again. As the gas is filled (see (a) of FIG. 1), the point where (a) and (b) meet in the graph of FIG. 1 is a process until the gas is completely transmitted.

Permeability Measuring Device

Figure 2 is a schematic diagram of a device for measuring the transmittance, Figure 3 is a photograph showing the actual appearance of the device for measuring the transmittance.

2 and 3, the transmittance measuring device includes a high pressure providing device 200, a vacuum providing device 300, a high pressure chamber 50, a vacuum chamber 70, and a fixing device 400.

The high pressure providing device 200 includes a gas container 10, valves 12 to 18, a buffer chamber 20, a baratrone gauge 22, a digital gauge 24, and a pipe connecting them. .

The vacuum providing apparatus 300 includes a vacuum pump 30, valves 32 to 36, a buffer chamber 40, a baratrone gauge 42, a digital gauge 44, and a pipe connecting them. .

In the above-described configuration, all of the valves 12, 16, and 18 should be kept open to supply gas to the high pressure chamber 50, and the valve 18 may be used for sensing in a state where the high pressure chamber 50 is set to high pressure. Should open and valve 16 should remain closed.

And, in order to pump the gas in the vacuum chamber 70, all the valves 32, 34, and 25 should be kept open, and the valve 36 is opened for sensing in the state where the vacuum chamber 70 is set to vacuum. The valve 34 must remain closed.

Permeability Measurement Method

A cap is formed of an epoxy resin on the edge of the ceramic specimen 100. The capped magnetic specimen is disposed between the high pressure chamber 50 and the vacuum chamber 70 in which the open faces face each other.

After the magnetic specimen 100 is disposed, the high pressure chamber 50 is driven to move in a linear direction, and the magnetic specimen 100 is driven between the high pressure chamber 50 and the vacuum chamber 70 by driving the high pressure chamber 50. Is squeezed. At this time, the open surfaces of the high pressure chamber 50 and the vacuum chamber 70 are compressed on both sides of the cap 102 without directly contacting the magnetic specimen 100 in order to increase the airtightness, thereby opening the high pressure chamber 50. The opened surface and the open surface of the vacuum chamber 70 are kept airtight by the magnetic specimen 100.

Thereafter, gas is supplied into the high pressure chamber 50 so that a predetermined level of high pressure is formed on one surface of the magnetic specimen 100, that is, the surface on which the high pressure chamber 50 is in close contact. At the same time, the gas inside the vacuum chamber 70 is pumped so that a predetermined level of vacuum is formed on the other surface of the magnetic specimen 100, that is, the surface on which the vacuum chamber 70 is in close contact.

When the high pressure chamber 50 and the vacuum chamber 70 reach a predetermined level of high pressure and vacuum, the supply and pumping of the gas is stopped, and the gas in the high pressure chamber 50 penetrates the magnetic specimen 100 so that the vacuum chamber ( The pressure change in the high pressure chamber 50 and the vacuum chamber 70 as it moves to 70 is sensed for a predetermined time.

The gas supplied to provide the high pressure may be selected from at least one of air, nitrogen gas, argon gas, and hydrogen gas, and the pressure forming the high pressure may be formed at 1000 Torr.

And, the vacuum may be formed at a pressure in the range of 0.1 Torr to 0.05 Torr.

The high pressures and vacuums described above can be measured using baratron gauges 22 and 42 which are typically used to measure pressure.

Hereinafter, the experimental examples according to the present invention will be more specifically shown, and the present invention is not limited to the following experimental examples.

<Experimental Example 1>

Celadon, powder duster and white porcelain were prepared at various temperatures and the permeability (breathability) was measured.

The blending ratio of starting materials for producing porcelain is shown in Table 1 below. In Table 1 below, the kaolin-based clay produced in Gangjin, Jeollanam-do, was used for the manufacture of the celadon and buncheongsa, and the kaolin-based clay produced in New Zealand was used.

Celadon Buncheong fraud White porcelain Feldspar (wt%) 29.70 29.67 20.94 Clay (% by weight) 44.70 45.83 38.19 Quartz (% by weight) 25.60 24.50 40.87 Total (% by weight) 100 100 100

To add 100 parts by weight of the starting material shown in Table 1, 5 parts by weight of silica sand consisting of coarse particles having an average particle diameter of 200 μm was added to prepare celadon, powdered blue dust, and white porcelain.

Looking specifically at the manufacturing process, the starting material corresponding to each batch composition shown in Table 1 was ground by ball milling. Looking specifically at the ball milling process, the starting materials were charged into a ball milling machine and wet-mixed with water, and the starting materials were mechanically ground and uniformly mixed by rotating at a speed of 200 rpm using a ball milling machine. . The ball used for ball milling used a 10 mm size ball made of alumina (Al ₂ O ₃ ), and ball milling was performed for 2 hours.

After the starting material was pulverized, the resultant was dehydrated with an extruder and mixed with a refiner. 5 parts by weight of silica sand consisting of coarse particles having an average particle diameter of 200 µm was additionally added when mixing with a refining machine.

The base material composition containing the silica sand which consists of coarse particle whose average particle diameter is 200 micrometers was press-molded in order to make the disk shaped specimen. The molding was performed for 30 seconds while applying a load of 4 tons to the metal mold.

The specimen thus formed was dried again for 10 minutes in a drying oven at 110 ° C., and then fired at 900˜1300 ° C. for 2 hours.

The components of each porcelain thus prepared are shown in Table 2 below.

Celadon Buncheong fraud White porcelain SiO ₂ (% by weight) 61.90 61.20 72.20 Al ₂ O ₃ (% by weight) 22.40 22.70 18.90 Fe ₂ O ₃ (% by weight) 2.50 2.90 0.30 TiO ₂ (% by weight) 0.50 0.50 <0.10 MnO (% by weight) <0.10 <0.10 <0.10 CaO (% by weight) 1.30 1.30 0.10 MgO (wt%) 0.80 0.80 0.10 Na ₂ O (% by weight) 0.70 0.70 0.70 K ₂ O (% by weight) 2.40 2.40 2.40 P ₂ O ₅ (wt%) 0.10 <0.10 <0.10 Cr ₂ O ₃ (% by weight) <0.10 <0.10 <0.10 ZrO ₂ (% by weight) <0.10 <0.10 <0.10 Weight loss 7.40 7.50 5.30

4 is a photograph according to the firing temperature of the celadon specimen, FIG. 5 is a photograph according to the firing temperature of the powder sprayer specimen, and FIG. 6 is a photograph according to the firing temperature of the white porcelain specimen. 4 to 6, (a) is the case of firing at 900 ° C, (b) is the case of firing at 1000 ° C, (c) is the case of firing at 1100 ° C, and (d) is firing at 1200 ° C. (E) is the case where it baked at 1300 degreeC.

7A is a scanning electron microscope (SEM) photograph showing pores of a celadon specimen prepared by firing at 1200 ° C., and FIG. 7B is a scanning electron microscope showing a pore of celadon specimen prepared by firing at 1300 ° C. FIG. (SEM) is a photograph, Figure 8a is a scanning electron microscope (SEM) photograph showing the pore state of the powdered spinneret specimen prepared by firing at 1200 ℃, Figure 8b is a pore of the powdered spinneret specimen prepared by firing at 1300 ℃. 9 shows a scanning electron microscope (SEM) picture, Figure 9a is a scanning electron microscope (SEM) picture showing the pores of the white porcelain specimen prepared by firing at 1200 ℃, Figure 9b is a pore of the white porcelain specimen prepared by firing at 1300 ℃ A scanning electron microscope (SEM) image showing the appearance.

7A to 9B, it can be seen that the pore formation is clearly observed when the scanning electron microscope is observed. It can be seen that pores are formed when fired at a temperature of 1200 ° C. in all of the celadon, blue dust, and white porcelain, and when pores are fired at 1300 ° C., pores having various sizes of 20 to 150 μm appear.

10 is a graph showing the transmittance according to the firing temperature of the celadon specimen prepared by firing at 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, Figure 11 is 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, It is a graph showing the permeability according to the firing temperature of the powder sprayer specimen prepared by firing at 1300 ℃, Figure 12 according to the firing temperature of the white porcelain specimen prepared by firing at 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃ It is a graph showing the transmittance.

Referring to FIGS. 10 to 12, as the firing temperature is increased, the time for the gas to penetrate the pores of the specimen is faster, which is consistent with the observation of the microstructure of the surface after firing.

<Experimental Example 2>

Swellable clays generally can absorb moisture well and provide a factor that allows water absorbed upon firing to evaporate and shrink to form pores. Therefore, the possibility of breathable self-manufacturing was examined by adding swellable clay. In order to confirm this effect, the raw material of white porcelain shown in Table 1 and bentonite, which is swellable clay, were mixed and fired. Bentonite was mixed by adding 5 parts by weight based on 100 parts by weight of the starting material of white porcelain shown in Table 1. Production of white porcelain according to Experimental Example 2 was performed in the same manner as in Experimental Example 1, except that silica sand consisting of coarse particles having an average particle diameter of 200 µm was not added.

13 is a scanning electron micrograph of a white porcelain specimen prepared by firing at 1200 ℃ according to Example 2, Figure 14 is prepared by firing at 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃ according to Experimental Example 2 A graph showing the permeability according to the firing temperature of the white porcelain specimen.

Referring to FIGS. 13 and 14, when the sinterable clay bentonite is added at a firing temperature of 900 ° C., 1000 ° C., 1100 ° C., and 1200 ° C., gas permeates, but as the firing temperature increases, the permeation time gradually increases. It could be seen that, when fired at 1300 ℃ gas permeation did not occur. Therefore, it can be seen that the low-temperature firing at 1200 ° C. or lower shows breathability when bentonite as swellable clay is added.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, This is possible.

10: gas container
12, 14, 16, 18, 32, 34, 36: valve
20: buffer chamber
22, 42 baratron gauge
24, 44: digital gauge
30: vacuum chamber
40: buffer chamber
50: high pressure chamber
70: vacuum chamber
200: high pressure providing device
300: vacuum providing device
400: fixing device

Claims (12)

20-50% by weight quartzite with particles smaller than 100 μm, 15-40% by weight feldspar, 25-55% by weight clay, 0.1-15% by weight silica sand with 200 μm-2 mm thick particles, zeolite 0.1 which is a porous crystal -10% by weight, feldspar 0.1-5% by weight, 0.1-5% by weight of cordierite having heat resistance, 0.1-5% by weight of magnesium aluminate (MgAl ₂ O ₄ ), 0.1-5% by weight of mullite, zirconia As a breathable porcelain holding composition comprising 0.1 to 5% by weight of (ZrO ₂ ) and 0.1 to 5% by weight of petalite,
The clay is made of 2 to 50% by weight of the swellable clay with respect to the total content of the clay,
The swellable clay is made of a layered clay containing water molecules between the layers,
The porcelain is a porcelain porcelain, blue porcelain or powder duster composition characterized in that the breathable porcelain.
The breathable porcelain holding composition according to claim 1, wherein the swellable clay is made of a layered clay containing an exchange cation together with a water molecule between layers.
The breathable porcelain composition according to claim 1, wherein the swellable clay is made of layered clay in which water molecules in the layer are partially exchanged with organic material to form a clay-organic complex.
According to claim 1, The swellable clay is breathable magnetic, characterized in that made of one or more layered clay selected from bentonite, montmorillonite, saponite, hectorite, Weidelite, halosite, vermiculite, soconite and nontronite Body composition for.
The breathable porcelain composition according to claim 1, wherein the zeolite contains an exchangeable cation in a crystal structure and a part of the cation is substituted with an anion to exhibit antimicrobial properties.
delete delete delete delete delete delete 20-50% by weight of quartzite having particles smaller than 100 μm, 15-40% by weight of feldspar, 25-55% by weight of clay, 0.1-10% by weight of zeolite as a porous crystal, 0.1-5% by weight of feldspar, cordier with heat resistance 0.1 to 5% by weight of light, 0.1 to 5% by weight of magnesium aluminate (MgAl ₂ O ₄ ), 0.1 to 5% by weight of mullite, 0.1 to 5% by weight of zirconia (ZrO ₂ ) and 0.1 to 5% by weight of petalite Pulverizing a starting material comprising a;
Mixing 0.1 to 15% by weight of silica sand having coarse particles of 200 μm to 2 mm to the pulverized starting material;
Molding and drying the starting material mixed with the silica sand into a desired shape; And
Baking the molded starting material at a temperature of 900-1200 ° C. to form a breathable porcelain,
The clay is made of 2 to 50% by weight of the swellable clay with respect to the total content of the clay,
The swellable clay is made of a layered clay containing water molecules between the layers,
The porcelain is a porcelain porcelain, blue porcelain or powder blue dust manufacturing method, characterized in that the porcelain.

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