WO2014003490A1

WO2014003490A1 - Method for preparing colored foamed glass, and colored foamed glass prepared by said method

Info

Publication number: WO2014003490A1
Application number: PCT/KR2013/005774
Authority: WO
Inventors: 이철태
Original assignee: 단국대학교 산학협력단
Priority date: 2012-06-28
Filing date: 2013-06-28
Publication date: 2014-01-03
Also published as: KR101582710B1; KR20140003795A

Abstract

The present invention provides a method for preparing a foamed glass, wherein a standard foamed glass produced in a conventional black color only is prepared as a foamed glass having white or various colors, thereby showing a function as a heat insulating material, which is the essential function of the conventional black color foamed glass, and being used as an interior material for interior decorating using various colors. The method for preparing a colored foamed glass of the present invention directly produces a standardized foamed glass suitable for a use so as to increase the yield of a final product, and the colored foamed glass can be used as an external heat insulator or an heat insulator for decoration of an outer wall having the function as a heat insulating material by utilizing the intact glassy surface of the colored foamed glass.

Description

Manufacturing method of colored foamed glass and colored foamed glass produced by the method

The present invention relates to a method for producing colored foamed glass and to colored colored glass produced by the method.

Foamed glass is an inorganic glass sintered by mixing a blowing agent in a glass having a special composition that is very finely pulverized, and is generally called cellular glass or multicellular glass. The name is attributed to the structure of the cell with free-standing pores stacked on very thin glass membranes.

Because of its structural properties, foamed glass not only shows excellent effects at low temperature insulation, flame shielding, insulation, sound insulation, and water resistance, but is also lightweight and can be used as an excellent material for structures and buildings.

Foamed glass can be classified into highly functional borosilicate foamed glass and soda-lime foamed glass with low linear thermal expansion coefficient according to its constituents, but foamed glass block and spherical shape depending on the form of final product Or it can be divided into two types of cylindrical foamed glass beads (foamed glass beads). Foam glass block is mainly used as a thermal insulation material of chimneys and stacks, an ethylene plant, a storage tank of liquefied gas and a heat insulating material of general construction, and its use is gradually expanding. In addition, foamed glass beads are mixed with cement rather than used alone, and filled into cement bricks or cement structures to lower the thermal conductivity of cement bricks and structures, thereby imparting and reducing the weight of insulation and insulation of building and civil engineering structures. Used.

Since the foam insulation block which is a conventional thermal insulation material used a carbon foaming agent as a foaming aid, all the foam blocks produced were black. In other words, the existing foam glass block was an excellent inorganic thermal insulation material using a foaming agent having independent bubbles, but because it was all black, it was limited to use as interior insulation material. In addition, the size must be standardized for use in interiors, and therefore a large size foam was produced and then cut to produce a block of the desired size. Therefore, the glass surface was not utilized during the manufacturing process, and many wastes occurred during the standardization process, resulting in process waste. This leads to a decrease in production yield of the final product foam glass block, there was a problem that the manufacturing cost increases.

In addition, in the existing foaming process, since the formwork is whole, it is difficult to separate from the foam after the final cooling, so that the foam is hardly stabilized at 500 ° C to 600 ° C after firing, and the primary foam and the formwork must be separated immediately using a robot arm. There was this. In addition, in the case of the existing foam, since the size of the foam is 600 ~ 800 mm × 600 ~ 800 mm × 200 ~ 250 mm, a slow cooling process of at least 12 hours is required, there was a disadvantage that the initial installation cost for this is enormous.

Therefore, the present inventors while studying the colored foam glass and the economical manufacturing method thereof, appropriately adjust the amount of the carbon foaming agent and add a coloring pigment, and when the glass raw material is charged into the dough molding rather than powder, colored foam glass It was confirmed that can be economically prepared to complete the present invention.

The present invention, 1) mixing the glass powder and the molding binder, foaming aids and coloring pigments, 2) pressing the mixture by pressing or pressing to prepare a molded body in the shape of a block, 3) after drying the block molded body Preheating at 450 ° C. to 800 ° C., 4) foam firing the preheated block at 800 ° C. to 1200 ° C., and 5) quenching and stabilizing the foam fired block at 450 ° C. to 800 ° C. It is to provide a method for producing colored foam glass.

In addition, the present invention is to provide a colored foam glass produced by the above production method.

In order to solve the above problems, 1) mixing the glass powder and the molding binder, foaming aid and coloring pigment, 2) kneading by pressing the mixture or pressing to prepare a molded body in the shape of a block, 3) block molded body Preheating at 450 ° C. to 800 ° C. after drying, 4) foam firing the preheated block at 800 ° C. to 1200 ° C., and 5) quenching and stabilizing the foam calcined block at 450 ° C. to 800 ° C. It provides a method of manufacturing colored foam glass comprising a.

Step 1) is to prepare a mixture for the production of colored foam glass. At this time, the type of glass is not limited, and both low melting soda lime glass and high melting point aluminum-containing borosilicate glass are applicable. In the case of low melting glass, the application of the technology of the present invention is much easier, and in the embodiment of the present invention, high melting point waste LCD glass powder is used.

In step 1), waste LCD glass powder ground to an average size of 28 μm to 104 μm may be used. When the average glass powder is 104 µm or larger, the specific surface area of the glass powder is small, so that a high amount of foaming aid is required, and the firing temperature of the foaming process is high. In addition, since the density is high, the weight is reduced. If the size of the glass powder is 28 ㎛ or less, there is an advantage that low addition of the foaming aid is possible and the firing temperature of the foaming process is also lowered, but it has a disadvantage that it is uneconomical because it takes a lot of cost to finely crush the glass powder. .

The molding binder used in step 1) is a substance added to increase the strength of the product by imparting elasticity and adhesiveness to the sample when molding the powder. This serves as a binder in the molding process, and also serves to prevent the block molding from blowing into the walls of the foaming furnace during the foaming process. Clays such as kaolin are mainly used, and preferred molding binders include, but are not limited to, PVA, starch, water glass, kaolin powder, basalt powder and bentonite powder.

The content of the binder of step 1) is preferably 30% by weight or less based on the total mixture. When the content of the binder exceeds 30% by weight, the content of the binder having a high melting point is increased compared to the glass powder, thereby reducing the foaming efficiency.

The foaming aid of step 1) is a material that helps foaming, and preferred foaming aids include carbon black, sulfate, carbonate, and the like. At this time, carbon black, sulfate, carbonate can be used alone or in combination of two or more. The preferred amount of the foaming aid is 0.01 to 0.4 parts by weight of carbon black, 0.01 to 4.0 parts by weight of sulfate, and 0.01 to 5.0 parts by weight of carbonate based on 100 parts by weight of the glass powder and the molding binder mixed powder.

If the content of carbon black is less than 0.01 parts by weight, foaming of the foam glass is not sufficiently achieved, and if it exceeds 0.4 parts by weight, the over-foaming proceeds to form open pores, increase the water absorption rate, decrease the thermal conductivity as well as foam Inhibiting the color reaction of the to form a black foam.

If the content of sulfate is 0.01 parts by weight or less, it does not contribute to the foaming of the foam glass at all, and it does not play a role of replenishing the insufficient carbon content. If it exceeds 4.0 parts by weight, the over-exposure proceeds to form open pores and increase the water absorption rate. Degree decreases.

When the content of carbonate is less than 0.01 parts by weight, it is difficult to express the complementary function of the insufficient carbon foaming agent, and when it exceeds 5.0 parts by weight, the over-foaming proceeds to form open pores, increase the water absorption rate and decrease the thermal conductivity.

The coloring pigment of step 1) is oxidized or decomposed in the glass mixture to give a desired color. If no coloring pigment is added, the foam glass is completely white. At this time, a variety of color pigments can be used according to the desired color, and available color pigments are not limited to a specific kind as long as it is a known inorganic pigment that is stable at high temperatures. That is, a well-known inorganic pigment corresponding to a desired color can be arbitrarily selected and used. However, when a certain amount of the coloring inorganic pigment is added, it is very important to determine the amount of the additive amount used since it directly affects the foaming, such as inhibiting the foaming.

In the examples of the present invention, chromium trioxide, cobalt-based compounds, or copper compounds were used as coloring agents. Chromium trioxide, also called chromic anhydride, is a red needle crystal. The foamed glass becomes green when the mixture is added with chromium trioxide. When the cobalt-based compound is added, the foamed glass is blue, and when the copper compound is added, the foamed glass is red.

The coloring pigment content is preferably 0.001 to 5.0 parts by weight. If the content of the coloring pigment is 0.001 parts by weight or less, the amount of pigment is insufficient to obtain sufficient color development, and if the content of the coloring pigment is 5.0 parts by weight or more, not only can the foaming be lowered due to the large amount of pigment, but too strong color appears. Can be.

Water may be added during the mixing process of step 1). At this time, the amount of water added is preferably 2% by weight or more based on the total mixture. If the amount of water is 2% by weight or less, it may be difficult to prepare the block molded body in step 2) because the amount of water is not enough to knead and the dough prepared does not have sufficient fluidity.

Step 2) is a step of pressing the mixture of step 1) by kneading or pressing to produce a block-shaped molded body. Compared with conventionally charged foam glass raw material in the form of powder, when the charge in the form of the dough of step 2) increases the mechanical strength of the glass surface of the prepared foam glass, minimizing the occurrence of stub during the manufacturing process. In addition, since the raw glass is charged in the form of a molded body, not in a powder state, the fusion of the formwork and the foam after foaming is not strong and there is an advantage that it can be easily separated after foaming.

At this time, the thickness of the block molded body is preferably a size that the thickness of the foam after foaming does not exceed 12 cm. If the thickness of the foam exceeds 12 cm, because the slow cooling time is long, a huge intermediate storage facility is required, there is a disadvantage that the cost is expensive. Therefore, the preferred size of the block molded body before the foaming process is 250-350 mm x 250-350 mm x 10-120 mm in height. Maintaining the length of the horizontal and vertical at least 25cm or more is not absolute for the convenience of work when using the colored foam glass as the final product, but if the size is small, the work efficiency is lowered when used.

Step 3) is a step of preheating the block molded body at 450 ℃ to 800 ℃. At this time, the block molded body is placed in the formwork for preheating, and the block molded body should be dried to dry the surface moisture before being immersed.

In the step 3) it is preferable to apply a release agent inside the formwork in order to facilitate the separation of the block molded body and the formwork later. The release agent is a drug that is applied to the inner surface of the die in advance in order to facilitate demolding, and includes magnesia powder, alumina powder, and carbon powder. At this time, it is preferable to apply at least one release agent selected from the group consisting of magnesia powder, alumina powder and carbon powder.

Preheating in step 3) is preferably performed at 450 ℃ to 800 ℃. Through the preheating step, the phenomenon in which the foamed glass forms a thick shell is suppressed. If the preheating temperature is lower than 450 ℃ swelling to the outside is suppressed, as a result, the foaming state is badly bad or foaming does not occur. In addition, when the preheating temperature is higher than 800 ° C., the dense structure of the glass is destroyed due to the thermal shock and the mechanical strength of the foam glass is lowered.

Step 4) is foaming of the preheated block molded body at 800 ° C to 1200 ° C. If the foaming temperature is less than 800 ℃ foaming does not occur properly, if the foaming temperature exceeds 1200 ℃ due to the loss of dense pore wall, the pores are large, the cavity is generated, the uniform porous structure of the glass is not achieved. As a result, it is difficult to produce high quality foam glass which is economical and practical.

Step 5) is a step of quenching the foam fired block molded product at 450 ℃ to 800 ℃. Since the foamed glass is in a softened or molten state as a whole, the stabilization of the foam structure is required, which is achieved by quenching the foamed glass at 450 ° C to 800 ° C. If the quenching temperature is less than 450 ℃, thermal stress which causes cracking of the foam glass due to the thermal shock occurs, and if the quenching temperature is higher than 800 ℃, the foamed glass is difficult to maintain the shape of the foam can not expect the effect of shape stabilization .

The present invention provides a colored foamed glass and a method of manufacturing the same, the colored foamed glass according to the present invention has been produced in black only, so that the foamed glass, which could not be used as an exterior material, can be used as an exterior material. In addition, by improving the existing non-economical and low production yield production method, it does not produce a lot of rust and short cooling time provides an economical method for producing colored foamed glass.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited by the examples.

실시예 1: 백색 발포유리블록의 제조Example 1 Preparation of White Foam Glass Block

80 parts by weight of the waste LCD glass powder, whose average size was pulverized to 44 μm or less, and 20 parts by weight of kaolin crushed to 44 μm or less as a molding binder were mixed. Carbon black, sulfate, and carbonate were added to the mixture as a foaming aid and mixed. The content of each foaming aid was 0.3 parts by weight of carbon black, 2.0 parts by weight of sulfate, and 4.0 parts by weight of carbonate based on 100 parts by weight of the mixed powder of waste LCD glass powder and kaolin.

The raw material powder mixture was kneaded and pressurized by adding water of such dough to prepare a block molded product having a size of 300 mm x 300 mm x 30 mm in height. The prepared block molded product was dried to dry the surface moisture. Thereafter, the block molded body was placed in a formwork coated with MgO powder release agent on the inner wall, and placed in a turnnel kiln. The turnnel kiln is a drying and preheating part in the range of the temperature of the inlet portion 650 ℃, the foam firing portion adjusted to a temperature of 980 ℃ in the center and It consists of a cooling part which makes it stabilize by quenching at the temperature of 500 degreeC.

The block molded body was foamed and fired for a predetermined time in the foam firing part in the turnnel kiln, and then passed through the cooling part to the outside of the turnnel kiln, and the formwork was immediately separated to obtain a white foam glass block. The white foam glass block thus prepared had a density of 0.23 g / cm ³ .

실시예 2: 녹색 발포유리블록의 제조Example 2: Preparation of Green Foam Glass Block

80 parts by weight of the waste LCD glass powder, whose average size was pulverized to 44 μm or less, and 20 parts by weight of kaolin crushed to 44 μm or less as a molding binder were mixed. Carbon black, sulfate, and carbonate were added to the mixture as a foaming aid and mixed. The content of each foaming aid was 0.3 parts by weight of carbon black, 2.0 parts by weight of sulfate, and 4.0 parts by weight of carbonate based on 100 parts by weight of the mixed powder of waste LCD glass powder and kaolin. To the mixture was added 2.0 parts by weight of chromium trioxide as a coloring pigment and mixed.

The block molded product was foamed and fired for a predetermined time in the foam firing part in the turnnel kiln, and then passed through the cooling part to the outside of the turnnel kiln, and the formwork was immediately separated to obtain a green foam glass block. The green foam glass block thus prepared had a density of 0.31 g / cm ³ .

실시예 3: 청색 발포유리블록의 제조Example 3: Preparation of Blue Foamed Glass Block

80 parts by weight of the waste LCD glass powder, whose average size was pulverized to 44 μm or less, and 20 parts by weight of kaolin crushed to 44 μm or less as a molding binder were mixed. Carbon black, sulfate, and carbonate were added to the mixture as a foaming aid and mixed. The content of each foaming aid was 0.3 parts by weight of carbon black, 2.0 parts by weight of sulfate, and 4.0 parts by weight of carbonate based on 100 parts by weight of the mixed powder of waste LCD glass powder and kaolin. To the mixture was added 2.0 parts by weight of a cobalt compound as a coloring pigment and mixed.

The block molded body was foamed and fired for a predetermined time in the foam firing part in the turnnel kiln, and then passed through the cooling part to the outside of the turnnel kiln, and the formwork was immediately separated to obtain a blue foam glass block. The density of the blue foam glass block thus prepared was 0.28 g / cm ³ .

실시예 4: 적색 발포유리블록의 제조Example 4 Preparation of Red Foam Glass Block

80 parts by weight of the waste LCD glass powder, whose average size was pulverized to 44 μm or less, and 20 parts by weight of kaolin crushed to 44 μm or less as a molding binder were mixed. Carbon black, sulfate, and carbonate were added to the mixture as a foaming aid and mixed. The content of each foaming aid was 0.3 parts by weight of carbon black, 2.0 parts by weight of sulfate, and 4.0 parts by weight of carbonate based on 100 parts by weight of the mixed powder of waste LCD glass powder and kaolin. 2.0 parts by weight of the copper compound was added to the mixture as a coloring pigment and mixed.

The block molded product was foamed and fired for a predetermined time in the foam firing part in the turnnel kiln, and then passed through the cooling part to the outside of the turnnel kiln, and the formwork was immediately separated to obtain a red foam glass block. The red foam glass block thus prepared had a density of 0.25 g / cm ³ .

Claims

1) mixing the glass powder with a molding binder, a foaming aid and a coloring pigment;

2) pressing the mixture to kneading or pressing to prepare a molded body in a block shape;

3) drying the block molded product followed by preheating at 450 ° C to 800 ° C;

4) foam firing the preheated block molded body at 800 ° C. to 1200 ° C .; And

5) A method for producing colored foamed glass comprising the step of rapidly quenching the foamed block molded product at 450 ° C to 800 ° C.

The method of claim 1, wherein the glass powder of step 1) is a waste LCD glass powder ground to an average size of 28 ㎛ to 104 ㎛.

The method of claim 1, wherein the molding binder of step 1) is any one selected from the group consisting of PVA, starch, water glass, kaolin powder, basalt powder, and bentonite powder.

The method of claim 1, wherein the content of the binder of step 1) is 30% by weight or less based on the total mixture.

According to claim 1, wherein the foaming aid of step 1) is added to 0.01 to 0.4 parts by weight of carbon black, 0.01 to 4.0 parts by weight of sulfate, 0.01 to 5.0 parts by weight of carbonate based on 100 parts by weight of the glass powder and the molding binder mixed powder Method for producing a colored foam glass, characterized in that.

The method of claim 1, wherein the coloring pigment of step 1) is any one selected from the group consisting of chromium trioxide, cobalt-based compounds, and copper compounds.

The method of claim 6, wherein the coloring pigment content of step 1) is 0.001 to 5.0 parts by weight.

The method of claim 1, wherein water is added during the mixing process of step 1).

The method of claim 8, wherein the water content is at least 2% by weight based on the total mixture.

The method of claim 1, wherein the size of the block molded body of step 2) is 250-350 mm x 250-350 mm x 10-120 mm in height.

Colored foamed glass produced by the method of any one of claims 1 to 10.