KR20190092116A - Apparatus for manufacturing glass - Google Patents

Abstract

The present invention is to provide an apparatus for manufacturing glass comprising a glass supply unit including twill with improved durability by having a protective layer. The apparatus for manufacturing glass comprises a glass supply unit consecutively supplying molten glass to a float bath and adjusting the flow amount of the molten glass supplied by the twill. The twill comprises a first protective layer including platinum and a second protective layer including a metal oxide. The first protective layer is on an area in which the twill comes in contact with the molten glass. The second protective layer is on at least one area of the surface facing the float bath of the twill.

Description

Glass manufacturing apparatus {APPARATUS FOR MANUFACTURING GLASS}

The present invention relates to a glass manufacturing apparatus. More specifically, the present invention relates to a glass manufacturing apparatus including a twill provided with a protective layer to improve durability.

Most panes, including glass substrates for displays, are produced by the float method or the fusion method. Unlike the fusion method, the float method can efficiently manufacture large panes of large area.

This float method is generally performed in a float bath in which molten metal (molten tin, etc.) is stored, forming molten glass into a glass ribbon while continuously supplying and advancing molten glass onto the molten metal, and forming the glass ribbon formed by the molding process. Slow cooling process for slow cooling. At this time, in the process of supplying a molten glass to a float bath, the supply amount of a molten glass can be adjusted using a twill. However, the twill is in direct contact with the molten glass having a high temperature, and is exposed to the reducing atmosphere on the float bath and the SnO airflow, thereby reducing the life of the twill.

Accordingly, there is a need for a technique for improving the durability of the twill used in the process of supplying molten glass into the float bath and extending the life of the twill.

Thus, the present specification is to provide a glass manufacturing apparatus comprising a twill with improved durability.

However, the problem to be solved by the present invention is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.

One embodiment of the present invention, while continuously supplying the molten glass to the float bath, the flow rate of the molten glass supplied by the twill includes a glass supply unit, the twill is a first protective layer comprising platinum and A second protective layer comprising a metal oxide, wherein the first protective layer is provided on at least the region where the twill comes into contact with the molten glass, and the second protective layer has a surface facing the float bath of the twill. It provides the glass manufacturing apparatus provided in at least one area | region.

Twill according to one embodiment of the present invention is excellent in durability, it can have a long life.

According to one embodiment of the present invention, by providing a second protective layer on the first protective layer, it is possible to effectively improve the durability of the twill.

The effects of the present invention are not limited to the above-described effects, and effects that are not mentioned will be clearly understood by those skilled in the art from the present specification and the accompanying drawings.

1 is a view schematically showing a glass manufacturing apparatus according to an embodiment of the present invention.
2a to 2c is a view showing a twill according to an embodiment of the present invention.
3 is a photograph of a sample used to test the gas permeability and the gas diffusivity of the second protective layer according to an embodiment of the present invention.
4 is a view schematically showing a method of experimenting with gas permeability of the second protective layer according to an embodiment of the present invention.
5 is a view schematically showing a method of experimenting with gas diffusion of the second protective layer according to an exemplary embodiment of the present invention.

Throughout this specification, when a part is said to "include" a certain component, it means that it may further include other components, without excluding the other components unless otherwise stated.

Throughout this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

The inventors have found that a twill can be manufactured using refractory materials that can withstand high temperatures, and that the twill's durability can be improved by forming a protective layer containing platinum in the contact area with the molten glass. In addition, when the protective layer containing platinum is exposed to the reducing atmosphere and the tin oxide (SnO) air flow in the float bath, a platinum-tin (PtSn) -based alloy is formed, which lowers the durability of the protective layer or lowers the melting point of the protective layer. Twill's life was shortened. Furthermore, it has been found that by forming an additional protective layer containing a metal oxide on the protective layer containing platinum to prevent the aforementioned phenomenon, it is possible to effectively improve the durability of the twill, thus comprising a glass comprising the twill as follows. The manufacturing apparatus was developed.

Hereinafter, this specification is demonstrated in detail.

One embodiment of the present invention, while continuously supplying the molten glass to the float bath, the flow rate of the molten glass supplied by the twill includes a glass supply unit, the twill is a first protective layer comprising platinum and A second protective layer comprising a metal oxide, wherein the first protective layer is provided on at least the region where the twill comes into contact with the molten glass, and the second protective layer has a surface facing the float bath of the twill. Provided is a glass manufacturing apparatus provided on at least one region.

Twill according to one embodiment of the present invention is excellent in durability, it can have a long life.

1 is a view schematically showing a glass manufacturing apparatus according to an embodiment of the present invention. Specifically, FIG. 1 illustrates that molten glass is supplied through the glass supply unit 200 onto the molten metal M stored in the float bath 100, and the molten glass advances onto the molten metal M to the glass ribbon G. Formed and drawn out through the discharge unit 300, the twill 210 is a view showing that to adjust the flow rate of the molten glass supplied to the float bath (100).

According to an exemplary embodiment of the present invention, the glass manufacturing apparatus may be a float glass manufacturing apparatus for manufacturing glass using a float method. Referring to FIG. 1, the glass manufacturing apparatus includes a glass supply unit 200 for supplying molten glass to the float bath 100, a glass supply unit 200, and a twill 210 for adjusting a flow rate of the molten glass. The discharge unit 300 may discharge the glass ribbon G formed on the molten metal M of the float bath 100.

According to one embodiment of the present invention, molten metal may be stored in the float bath. The molten metal stored in the float bath may include a known configuration, and there is no limitation as long as the molten metal used in the float method is used. As an example, the molten metal may include molten tin and / or molten tin alloy. Referring to FIG. 1, molten glass may be supplied onto the molten metal M stored in the float bath 100, and may be moved from one side A to the other side B of the float bath 100. From one side (A) of the float bath 100 to the other side (B), in the process of moving the molten glass on the molten metal (M), a glass ribbon (G) in the form of a ribbon may be formed. That is, the glass ribbon G shape | molded from molten glass can move along the direction of the other side B from one side A of a float bath on a molten metal. Principle and structure of the flow of molten metal in a float bath and the introduction, ribboning, movement, etc. of molten glass are well known by a process using a general float method, and therefore, the detailed description thereof is omitted here.

According to one embodiment of the present invention, the atmosphere on the float bath may consist of a mixed gas of nitrogen and hydrogen. Referring to FIG. 1, a mixed gas of nitrogen and hydrogen may be supplied to the float bath 100 through the gas chamber 400. In addition, the atmosphere of the float bath 100 may be heated to a temperature of about 800 ° C or more and 1300 ° C or less by the heater 500. The type of molten glass supplied to the molten metal phase stored in the float bath is not limited, and may be, for example, alkali free glass or soda lime glass. In addition, two or more lift-out rollers 600 may lift the glass ribbon G and draw out the glass ribbon G from the float bath 100. In addition, the glass manufacturing apparatus may include a driving unit for rotating the lift out roller, and the like, and a lift out roller used in the glass manufacturing apparatus in the art may be used without limitation.

According to one embodiment of the present invention, the glass manufacturing apparatus may include a general configuration of an apparatus for manufacturing glass using the float method. For example, the glass manufacturing apparatus includes a glass supply unit for supplying molten glass onto the molten metal stored in the float bath, a float bath for molding the supplied molten glass into a thin glass ribbon, and a lift out for drawing the glass ribbon from the float bath. It may include a roller portion, a slow cooling portion for slowly cooling the glass ribbon drawn out from the float bath, a processing portion for treating the surface of the slow cooled glass ribbon, or cutting the glass ribbon to a predetermined size.

The glass ribbon is a glass of the previous stage for producing the final glass product, can be removed and moved from the float bath in a semi-solid state. Thereafter, the glass ribbon of the semi-solid state is subjected to a slow cooling step, and may have a solid state as in the final glass state.

According to one embodiment of the present invention, the twill may be formed of a refractory material. Specifically, the twill may be formed of a refractory material that can withstand temperatures of about 1,150 ° C. or more and 1,400 ° C. or less, which is a temperature of the molten glass supplied into the float bath. For example, the refractory may include at least one of ceramic, silica, mullite, cristobalite, and zirconia, but the type of the refractory is not limited.

According to an exemplary embodiment of the present invention, the twill may move in the vertical direction to adjust the flow rate of the molten glass. Specifically, the twill may move up and down along a direction perpendicular to the direction in which the molten glass is supplied, and may move up and down at a predetermined angle in a direction in which the molten glass is supplied.

According to an exemplary embodiment of the present invention, the first protective layer may be provided on at least the region where the twill is in contact with the molten glass. Specifically, the first protective layer may be provided on an area in which the molten glass is in contact with each other of the entire area of the twill body, and may be provided on other areas. By providing a 1st protective layer on the area | region of the said twill which a molten glass contacts at least, the said twill main body can be protected from a molten glass, and the durability of the said twill can be improved. In addition, by providing the first protective layer on the surface of the twill formed of the refractory, it is possible to improve the surface quality of the glass produced. Specifically, by providing the first protective layer having a smooth surface on the area of the twill in contact with the molten glass, the surface quality of the molten glass in contact with the twill can be prevented from being lowered. Through this, it is possible to improve the surface quality of the glass product finally produced.

According to an exemplary embodiment of the present invention, the first protective layer may be provided on the entire area of the twill below the height at which the molten glass supplied is in contact with the twill. When the twill moves in a vertical direction to control the flow rate of the molten glass supplied to the float bath, a first protective layer may be provided on a twill region below a height at which the molten glass contacts the twill. . By providing the first protective layer on the above-described region, the durability of the twill can be improved and the manufacturing cost of the twill can be reduced.

According to an exemplary embodiment of the present invention, the first protective layer may include at least one of platinum, an alloy of platinum and gold, an alloy of platinum and rhodium, platinum having dispersedly strengthened ceramic particles, and an alloy of platinum and rhodium dispersedly reinforced with ceramic particles. It may include one. By providing a first protective layer containing the aforementioned materials on the surface of the twill, the durability of the twill can be effectively improved, and the surface quality of the glass to be produced can be improved. In addition, as a method of providing the first protective layer on the surface of the twill, a method known in the art may be used. For example, a clad including the above-described material may be processed and coated on the twill to provide the first protective layer on the twill.

2a to 2c is a view showing a twill according to an embodiment of the present invention. Specifically, FIG. 2A illustrates a second protective layer 212 provided on all of the surfaces of the first protective layer 211 provided on the other surface F ₂ and the side surface of the twill 210 according to an embodiment of the present invention. The twill 211 is shown. 2B illustrates a second protective layer 212 provided on all surfaces of the first protective layer 211 provided on the other surface F ₂ of the twill 211 according to another embodiment of the present invention, and the twill 210 is provided. The twill 210 is provided with a second protective layer 212 on a portion of the surface of the first protective layer 211 provided on the side of). 2C illustrates a twill provided with a second protective layer 212 on a portion of a surface of the first protective layer 211 provided on the other surface F ₂ and the side of the twill 211 according to another embodiment of the present invention. 210 is shown.

Nitrogen gas and hydrogen gas may remain on the float bath. In addition, when tin is used as the molten metal stored in the float bath, oxygen remaining in the float bath and molten tin may react to generate tin oxide (SnO) gas. When the first protective layer including platinum is exposed to nitrogen gas, hydrogen gas, and tin oxide gas remaining on the float bath, the surface of the first protective layer may be cracked or cracked. In addition, a platinum tin (PtSn) -based alloy is formed on the surface of the first protective layer, so that the melting point of the first protective layer is lowered, and the first protective layer is peeled off, thereby deteriorating durability of the twill. . Referring to FIG. 1, of the twill F ₁ facing the side to which the molten glass is supplied and the twill other face F ₂ facing the float bath 100, the twill other face F _{2 is} connected to the float bath. This may correspond to a surface that is likely to be exposed to the remaining nitrogen gas, hydrogen gas, and tin oxide gas, so that the problem of deterioration of the durability of the twill may be severe.

According to an exemplary embodiment of the present invention, the second protective layer may be provided on at least one region of the surface facing the float bath of the twill. Specifically, the second protective layer may be provided on at least one region of the first protective layer provided on the surface facing the float bath of the twill. That is, according to one embodiment of the present invention, by providing a second protective layer on the first protective layer formed on the other surface of the twill which is likely to be exposed to the gas remaining in the float bath, the first protective layer is described above Exposure to one gas can be effectively prevented. Through this, it is possible to further improve the durability of the twill.

In addition, referring to Figures 2a to 2c, by providing a second protective layer on the first protective layer provided on the side of the twill, it is possible to improve the durability of the twill. Furthermore, by forming the second protective layer on the twill body not provided with the first protective layer, durability of the twill can be improved.

2A to 2C, in consideration of the conditions under which the twill is provided, various regions in which the second protective layer is provided may be set. Specifically, by forming a second protective layer only on the area of the first protective layer that is likely to be exposed to the gas remaining on the float bath, to protect the first protective layer, and at the same time reduce the manufacturing cost of the twill Can be saved.

According to an exemplary embodiment of the present invention, the second protective layer may be provided on the outermost layer of the twill region not in contact with the molten glass. Specifically, the second protective layer may not be provided on a region of the first protective layer that is in contact with the molten glass. Referring to FIG. 2C, a second protective layer may not be provided on the first protective layer in a region of the lower surface F ₂ of the twill contacting the molten glass. According to the composition and temperature conditions of the molten glass, when the second protective layer is directly bonded to the molten glass, carbon dioxide (CO ₂ ) gas is generated, bubbles may be generated on the molten glass. Therefore, in consideration of the composition, temperature conditions, and the like of the molten glass, the second protective layer can be provided on the first protective layer so that the second protective layer and the molten glass do not directly contact each other.

According to one embodiment of the present invention, a method for preparing a protective layer in the art may be used as a method of providing the second protective layer on the first protective layer. For example, by using a thermal spraying coating method, the second protective layer may be easily provided on the first protective layer.

According to an exemplary embodiment of the present invention, the thickness of the second protective layer may be 100 μm or more and 1000 μm or less. Specifically, the thickness of the second protective layer is 150 μm or more and 900 μm or less, 300 μm or more and 700 μm or less, 450 μm or more and 550 μm or less, 100 μm or more and 350 μm or less, 400 μm or more and 650 μm or less, or 750 μm or more 900 μm or less. By adjusting the thickness of the second protective layer in the above-described range, it is possible to effectively prevent the first protective layer from being exposed to nitrogen gas, hydrogen gas and tin oxide gas on the float bath.

According to an exemplary embodiment of the present invention, the second protective layer may include at least one of zirconium oxide, titanium oxide, hafnium oxide, tulium oxide, and yttria stabilized zirconia. For example, the second protective layer may include a mixture of zirconium oxide and hafnium oxide. By providing the second passivation layer including the above-described material on the first passivation layer, the first passivation layer may be effectively prevented from being exposed to the gas remaining on the float bath. However, the material included in the second protective layer is not limited, and any material capable of protecting the first protective layer from gases remaining on the float bath may be used without limitation.

According to an exemplary embodiment of the present invention, the second protective layer may have a thermal expansion coefficient of 5 μm / m · K or more and 15 μm / m · K or less at a temperature of 500 ° C. or more and 1,500 ° C. or less. Specifically, in the above temperature range, the thermal expansion coefficient of the second protective layer is 8 μm / m · K or more and 14 μm / m · K or less, 10 μm / m · K or more and 12 μm / m · K or less, 6 μm / m · K or more, 10 μm / m · K or less, or 11 μm / m · K or more and 14 μm / m · K or less. By adjusting the thermal expansion coefficient of the second protective layer within the above-described range, it is possible to effectively suppress the peeling of the second protective layer from the first protective layer in the course of the operation of the twill.

3 is a photograph of a sample used to test the gas permeability and the gas diffusivity of the second protective layer according to an embodiment of the present invention. Specifically, FIG. 3A is a photograph of a sample without the second protective layer, and FIG. 3B is a photograph of a sample with the second protective layer.

As shown in FIG. 3A, six cylindrical samples formed of a mixture of mullite, cristobalite, and silica and having a diameter of 14 mm and a length of 23 mm were prepared. A zirconium oxide was coated to a thickness of 200 μm on the top surfaces of three cylindrical samples by a spray coating method to prepare a sample as shown in FIG. 3B. That is, three samples (sample A) without the second coating layer and samples (sample B) with the second coating layer were prepared.

4 is a view schematically showing a method of experimenting with gas permeability of the second protective layer according to an embodiment of the present invention.

On the experimental apparatus set as shown in FIG. 4, the upper surface of the sample A is provided at the valve side, and the valve is adjusted to change the flow rate of the air passing through the sample for each pressure of air in the space where the sample is provided. The gas permeability experiment was conducted by measuring. At this time, the gas permeability experiment was conducted at a temperature of 25 ℃.

The same experiment was conducted on the remaining two sample Sample A. In addition, the upper surface with the second protective layer of Sample B was placed on the valve side, and gas permeability experiments were conducted for three Samples B in the same manner as described above. Permeability of Sample A and Sample B was calculated through the following equation.

[Equation 1]

In Equation 1, μ is the permeability of the sample, δ is the thickness of the sample, η is the viscosity of the air, p is the absolute pressure of the air, V is the volume of air passing through the sample, A is the sample top surface and the cross-section and, p ₁ is the absolute pressure of the air supplied to the sample, p ₂ is the absolute pressure of the air that has passed through the sample, t is the time for the air through the sample.

5 is a view schematically showing a method of experimenting with gas diffusion of the second protective layer according to an exemplary embodiment of the present invention.

For gas diffusion experiments, helium (He) gas with average free path similar to that of hydrogen gas was conducted due to the explosion risk of hydrogen (H ₂ ) gas. On the experimental apparatus set as shown in FIG. 5, the upper surface of Sample A was provided at the valve side, and the valve was adjusted to fill helium gas at a pressure of 1 atm inside the experimental apparatus. Thereafter, the initial pressure (P _a ) in the sample was measured, the pressure drop in the experimental apparatus was observed to confirm that the equilibrium state was reached, and then the gas diffusion degree experiment was conducted by measuring the pressure (P _b ). . The gas diffusivity of the sample corresponds to P _b minus P _a . The same experiment was conducted on the remaining two sample Sample A. In addition, the upper surface with the second protective layer of Sample B was placed on the valve side, and the gas diffusion degree experiments were conducted for three Samples B in the same manner as described above.

The results of the gas permeability experiment and the gas diffusivity experiment for the six samples are shown in Table 1 below.

Sample A Sample B Reduction Gas permeability
(nPm) Gas diffusivity
(mmWG) Gas permeability
(nPm) Gas diffusivity
(mmWG) Gas permeability
(%) Gas diffusivity
(%) Experiment 1 0.72 86.8 0.54 36.6 25 58 Experiment 2 2.33 17.6 1.97 13.9 15 21 Experiment 3 2.27 31.2 2.14 14.9 6 52 Average 1.77 45.20 1.55 21.80 13 52

Referring to Table 1, it can be seen that the gas diffusion and gas permeability of the sample B with the second protective layer according to an embodiment of the present invention is reduced compared to the sample A without the second protective layer. there was. That is, it was confirmed that by providing the second protective layer, the refractory can be effectively suppressed from being exposed to air and helium.

Thus, by providing a second protective layer on the first protective layer formed on the twill of the glass manufacturing apparatus according to an embodiment of the present invention, the first protective layer is exposed to the gas remaining in the float bath It can be seen that this can be effectively suppressed.

100: float bath
200: glass supply
210: twill
211: first protective layer
212: second protective layer
300: discharge part
400: gas chamber
500: heater
600: lift out roller

Claims (8)

Continuously supplying molten glass to the float bath, the flow rate of the molten glass supplied by the twill includes a glass supply portion,
The twill comprises a first protective layer comprising platinum and a second protective layer comprising metal oxide;
The first protective layer is provided on at least the region where the twill comes into contact with the molten glass,
And the second protective layer is provided on at least one region of the surface facing the float bath of the twill. The method according to claim 1,
The said 1st protective layer is a glass manufacturing apparatus provided with the whole area | region of the said twill below the height which the said molten glass supplied contact | connects the said twill. The method according to claim 1,
The second protective layer is provided in the outermost layer of the twill region not in contact with the molten glass. The method according to claim 1,
The thickness of the said 2nd protective layer is 100 micrometers or more and 1000 micrometers or less. The method according to claim 1,
And the second protective layer comprises at least one of zirconium oxide, titanium oxide, hafnium oxide, tulium oxide, and yttria stabilized zirconia. The method according to claim 1,
The said 2nd protective layer is a glass manufacturing apparatus whose thermal expansion coefficient is 5 micrometers / m * K or more and 15 micrometers / m * K or less at the temperature of 500 degreeC or more and 1,500 degrees C or less. The method according to claim 1,
Wherein the first protective layer comprises at least one of platinum, an alloy of platinum and gold, an alloy of platinum and rhodium, platinum that is dispersed and strengthened ceramic particles, and an alloy of platinum and rhodium that are dispersed and reinforced ceramic particles. Device. The method according to claim 1,
The twill is moved in the vertical direction to control the flow rate of the molten glass.

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