Dry coating material for tundish

The dry coating material for tundishes uses inorganic hydrates and alkali silicates/phosphates to enhance strength and reduce odor, addressing heat penetration and contamination issues in conventional materials.

JP2026023139AActive Publication Date: 2026-02-13KROSAKI HARIMA CORP
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Patent Information

Application Number
JP2024124914
Authority / Receiving Office
JP · JP
Patent Type
Applications
Current Assignee / Owner
Filing Date
2024-07-31
Publication Date
2026-02-13
Estimated Expiration
2044-07-31

AI Technical Summary

Technical Problem

Conventional dry coating materials for tundishes face issues with insufficient heat penetration due to insulation, leading to weak coating strength, and phenolic resins cause odor and carbon pickup, affecting steel quality and operating efficiency.

Method used

A dry coating material comprising 3 to 15% of inorganic hydrate powders with a thermal decomposition onset temperature of 40 to 300°C, 0.1 to 10% of powdered alkali silicates or phosphates, and limited phenolic resin (≤0.5%), with the remainder being refractory materials, to enhance strength and reduce odor.

Benefits of technology

The coating material achieves improved strength and eliminates odor, allowing efficient application without long heating times and preventing steel contamination.

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Abstract

To provide a dry coating material for a tundish capable of improving the strength of a construction body and reducing the problem of odor generation.SOLUTION: A dry coating material for a tundish, comprising a total of 3 to 15 mass% of a first binding material which is one or more selected from powders of inorganic hydrates having a thermal decomposition starting temperature of 40 to 300 °C, and a total of 0.1 to 10 mass% of a second binding material which is one or more selected from powdered alkali silicates other than hydrates, powdered alkali sulfates other than hydrates, and powdered alkali phosphates other than hydrates, wherein a content of a phenol resin is 0.5 mass% or less (including 0), and a remainder is mainly a refractory raw material.SELECTED DRAWING: None
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Description

[Technical Field]

[0001] The present invention relates to a dry coating material for a tundish. [Background technology]

[0002] In continuous steel casting, the tundish plays a role in distributing molten steel, uniformly regulating the temperature, and floating up deoxidation products. The refractory lining of the tundish is usually coated with a thin refractory coating, primarily made from basic refractory materials such as magnesia and dolomite, to prevent contamination of the molten steel and protect the lining. This coating is generally applied by spraying or troweling with the addition of water.

[0003] After application, the coating material is heated and dried before use. However, the water added to the coating material cannot be completely removed even by drying, leading to hydrogen pickup caused by the water, which leads to a deterioration in the quality of steel products. Furthermore, when the remaining thickness of the coating material becomes small due to wear and tear, it is dismantled and new coating is applied, but dismantling takes a considerable amount of time and effort because the coating material has burned onto the refractory lining, reducing the operating rate of the tundish.

[0004] Therefore, in recent years, application methods using dry coating materials have been proposed (for example, Patent Documents 1 and 2). In this method, a core is placed in a tundish with a refractory lining, and a dry coating material containing refractory raw materials and a binder is poured between the refractory lining and the core. After filling, the dry coating material is heated from the inside of the core with a gas burner or the like to harden it. Unlike spraying or troweling, this application method using dry coating materials does not add water, and therefore eliminates the problems of hydrogen pickup and seizure mentioned above. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-7317 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-39597 Summary of the Invention [Problem to be solved by the invention]

[0006] Conventional dry coating materials use thermoplastic resins as binders to harden through heating and drying. However, because the heat is applied from the inside through the core, and the dry coating material itself is insulating, the backside of the coating is less likely to receive sufficient heat. Furthermore, due to the operating rate of the tundish, there is currently insufficient time for heating and temperature increase. As a result, dry coating materials are unable to receive sufficient heat during the heating and drying process after application, resulting in insufficient strength of the coating. Unlike refractory linings, the thickness of dry coating materials is generally thin, around 30 to 100 mm, and if the coating strength is insufficient, it is prone to collapse due to impacts received during transport from the tundish.

[0007] Furthermore, phenolic resins are commonly used as thermoplastic resins in dry coating materials. However, when the amount of phenolic resin used is large, the amount of residual carbon increases due to carbonization of the resin, which causes problems with molten steel contamination due to carbon pickup, thereby reducing the effectiveness of dry coating materials in preventing molten steel contamination. Furthermore, thermal decomposition of the phenolic resin during heating generates a strong odor, which is undesirable for the working environment.

[0008] Therefore, the problem to be solved by the present invention is to provide a dry coating material for a tundish that can improve the strength of the applied body and reduce the problem of odor generation. [Means for solving the problem]

[0009] According to one aspect of the present invention, there is provided the following dry coating material for a tundish. A dry coating material for tundishes, comprising a total of 3 to 15 mass% of a first binder which is one or more types selected from inorganic hydrate powders having a thermal decomposition onset temperature of 40 to 300°C, and a total of 0.1 to 10 mass% of a second binder which is one or more types selected from powdered alkali silicates other than hydrates, powdered alkali sulfates other than hydrates, and powdered alkali phosphates other than hydrates, and the content of phenolic resin is 0.5 mass% or less (including 0), with the remainder being mainly refractory raw materials.

[0010] Here, the thermal decomposition onset temperature is the temperature at which water of crystallization begins to be released due to the thermal decomposition of an inorganic hydrate, and is the temperature at which weight begins to decrease in a TG curve obtained by measurement using a thermogravimetric differential thermal analyzer (TG-DTA). [Effects of the Invention]

[0011] The dry coating material for a tundish of the present invention can improve the strength of the applied body and reduce the problem of odor generation. DETAILED DESCRIPTION OF THE INVENTION

[0012] One of the technical features of the dry coating material for tundishes of the present invention (hereinafter simply referred to as "dry coating material") is the use of a first binder, which is one or more inorganic hydrate powders having a thermal decomposition onset temperature of 40 to 300°C, in combination with a second binder, which is one or more powdered alkali silicates other than hydrates, powdered alkali sulfates other than hydrates, and powdered alkali phosphates other than hydrates. Specifically, in the dry coating material of the present invention, the second binder, which is one or more powdered alkali silicates other than hydrates, powdered alkali sulfates other than hydrates, and powdered alkali phosphates other than hydrates, dissolves in the crystallization water released by the thermal decomposition of the first binder, which is one or more inorganic hydrate powders having a thermal decomposition onset temperature of 40 to 300°C, and hardens as dehydration and polymerization proceed. This improves the strength of the applied structure.

[0013] In the dry coating material of the present invention, the first binder is one or more inorganic hydrate powders having a thermal decomposition onset temperature of 40 to 300°C. Inorganic hydrates with a thermal decomposition onset temperature lower than 40°C may begin to decompose in high-temperature environments, such as summer, potentially solidifying the material before application. On the other hand, inorganic hydrates with a thermal decomposition onset temperature higher than 300°C require heating at high temperatures, which may result in deformation of the core. Furthermore, because the core temperature does not decrease in a short time, a long waiting time is required before the core can be removed, i.e., before the frame can be removed. From the perspective of reducing waiting time, it is preferable that the inorganic hydrate used as the first binder has a thermal decomposition onset temperature of 40 to 200°C.

[0014] The inorganic hydrate used as the first binder in the dry coating material of the present invention is not particularly limited as long as it has a thermal decomposition onset temperature of 40 to 300°C and functions as a binder, and for example, silicates, phosphates, and sulfates commonly used as binders for monolithic refractories can be used, which have a thermal decomposition onset temperature of 40 to 300°C. Specific examples include one or more selected from Na2SiO3·4H2O, Na2SiO3·5H2O, Na2SiO3·6H2O, Na2SiO3·9H2O, Na3PO4·12H2O, Na3PO4·6H2O, Na3PO4·7H2O, MgSO4·7H2O, and KH2PO4·3H2O.

[0015] In the dry coating material of the present invention, the content of the first binder is 3 to 15% by mass. If the content of the first binder is less than 3% by mass, the amount of crystallization water released by thermal decomposition is insufficient, making it impossible to obtain sufficient strength of the applied product. If the content of the first binder is more than 15% by mass, the amount of crystallization water released by thermal decomposition is excessive, reducing the dense structure and making it impossible to obtain sufficient strength of the applied product. From the perspective of improving the strength of the applied product, the content of the first binder is preferably 5 to 10% by mass.

[0016] In the dry coating material of the present invention, the content of the second binder is 0.1 to 10% by mass. If the content of the second binder is less than 0.1% by mass, the bonding ability is insufficient, making it impossible to obtain sufficient strength of the applied structure. If the content of the second binder is more than 10% by mass, a large amount of low-melting-point substances is produced, which reduces the ease of core removal, i.e., the ease of frame removal, and also reduces corrosion resistance. From these perspectives, the content of the second binder is preferably 1 to 5% by mass.

[0017] Among the second binders, examples of powdered alkali silicates other than hydrates include sodium silicate, potassium silicate, and calcium silicate. Examples of alkali sulfates other than hydrates include sodium sulfate, potassium sulfate, calcium sulfate, and magnesium sulfate. Examples of alkali phosphates other than hydrates include sodium hexametaphosphate, sodium pyrophosphate, sodium tetrapolyphosphate, sodium tripolyphosphate, sodium ultraphosphate, potassium phosphate, lithium phosphate, calcium phosphate, magnesium phosphate, and aluminum phosphate.

[0018] In the present invention, the content of phenolic resin, which has been used as a binder in conventional dry coating materials, is limited to 0.5% by mass or less (including 0). As the phenolic resin content increases, the residual carbon content increases due to resin carbonization, causing problems with molten steel contamination due to carbon pickup, and the effectiveness of dry coating materials in preventing molten steel contamination is diminished. Furthermore, phenolic resin generates a strong odor due to thermal decomposition during heating, which is undesirable for the working environment. From these perspectives, the lower the phenolic resin content, the better, and 0 is most preferable. When phenolic resin is used, it should be in powder or flake form.

[0019] In the dry coating material of the present invention, the remainder, other than the first binder, second binder, and phenolic resin, is primarily refractory materials, similar to conventional dry coating materials. Examples include magnesia, magnesite, dolomite, calcia, alumina, silica, and combinations thereof. From the viewpoint of preventing molten steel contamination, it is preferable to primarily use basic refractory materials such as magnesia, magnesite, dolomite, and calcia. Furthermore, recycled refractories primarily composed of these basic materials may also be used. The particle size may be, for example, a maximum of 1 to 4 mm, and may be appropriately adjusted to coarse, medium, or fine particles.

[0020] In the dry coating material of the present invention, the balance may contain organic short fibers, organic wetting agents, organic hardening agents, etc., as needed. Specific examples of organic short fibers include vinylon fibers, polyethylene fibers, polypropylene fibers, cellulose, and cotton waste. Specific examples of organic wetting agents include coal and petroleum oils, vegetable oils, and animal oils. Specific examples of organic hardening agents include lactams, acetanilides, and alkylphenols. However, in the dry coating material of the present invention, the balance is primarily a fire-resistant raw material. Here, "primarily" refers to a content of 70% by mass or more relative to the remainder (100% by mass).

[0021] The application of the dry coating material of the present invention is similar to that of conventional dry coating materials and is carried out on tundishes newly lined with refractory or on used tundishes. For used tundishes, the dry coating material is applied after removing any remaining dry coating material. Specifically, a core is placed inside the tundish, and the dry coating material of the present invention is poured into the gap between the refractory lining and the core to fill it. During filling, it is preferable to apply vibrations using a vibrator attached to the core, as in conventional methods, to improve the packing rate of the dry coating material. The preferred thickness of the dry coating material is 20 to 60 mm. Next, the core is heated from the inside with a gas burner or the like to a surface temperature of approximately 400°C, hardened, and then the core is removed. [Example]

[0022] Examples of the present invention and comparative examples are shown below. Various tests were conducted using dry coating materials with the compositions shown in Table 1. In each example, the refractory raw material was magnesia. Its particle size was 4.0 mm or less on a JIS sieve. The thermal decomposition onset temperatures of the inorganic hydrates used as the first binder were 40°C for Na2SiO3·9H2O, 60°C for Na3PO4·6H2O, and 70°C for MgSO4·7H2O.

[0023] [Table 1]

[0024] The test methods for the various tests are as follows: <Odor> For odor, a sensory evaluation was conducted to determine the degree of odor generated when a specified amount of dry coating material was placed on a brick heated to 300°C. The odor was evaluated on a three-point scale, with ○ (excellent) if almost no odor was detected, △ (good) if a slight odor was detected, and × (bad) if an odor was detected. A rating of ○ (excellent) or △ (good) was considered a pass. <Out-of-frame nature> To evaluate the mold removal properties, the dry coating material was filled into a metal mold with inner dimensions of 40 x 40 x 160 mm, which is intended to hold a core, and the mold was left in an atmosphere at 300°C for three hours, after which the mold was lightly struck with a plastic hammer to remove it. The results were evaluated on a three-point scale: ○ (excellent) if the mold came off after 0 to 5 strikes, △ (good) if the mold came off after 6 to 10 strikes, and × (poor) if the mold came off after 11 or more strikes, with ○ (excellent) or △ (good) being considered a pass. <Bending strength> The bending strength was measured in accordance with the provisions of JIS R 1601 using test pieces that had been filled with the dry coating material in a metal frame and then heated to 300°C, as in the above-mentioned test for frame removal. The bending strength was evaluated on a three-point scale: ○ (excellent) for 1.0 MPa or more, △ (good) for 0.5 to less than 1.0 MPa, and × (poor) for less than 0.5 MPa, with ○ (excellent) or △ (good) being considered a pass. <Apparent porosity> The apparent porosity was measured in accordance with the provisions of JIS R 2205 using test pieces that had been filled with the dry coating material in a metal frame and then heated to 300°C, as in the above-mentioned test for frame removal. The apparent porosity was evaluated on a three-level scale: ○ (excellent) for 10% or more but less than 30%, △ (good) for 30% or more but less than 40%, and × (poor) for 40% or more, with ○ (excellent) or △ (good) being considered a pass. <Overall rating> The overall evaluation was made on a three-point scale based on the evaluation results of odor, ease of removal from the frame, bending strength, and apparent porosity. Specifically, if all evaluation results were ◯, it was evaluated as ◯ (excellent); if at least one evaluation result was △ and there were no × evaluation results, it was evaluated as △ (good); if at least one evaluation result was ×, it was evaluated as × (bad); and if ○ (excellent) or △ (good), it was evaluated as passing.

[0025] As shown in the test results in Table 1, all of the dry coating materials according to the examples passed the odor evaluation. As a result, the problem of odor generation is resolved, making it possible to improve the construction environment. In the evaluation of the mold removal property, all of the dry coating materials according to the examples passed the test. As a result, the core can be removed from the mold without causing the applied structure to collapse. All of the dry coating materials in the examples have sufficient strength and density when heated and dried at 300°C. This can also be confirmed by measuring bending strength and apparent porosity. As a result, the applied body strength can be obtained without waiting for sufficient heating or long drying times, and the short heating and drying times required for dry coating materials are possible.

[0026] Comparative Example 1 does not contain a first binder. Comparative Example 2 contains a first binder, but its content is below the lower limit specified in the present invention. On the other hand, Comparative Example 3 has a first binder content above the upper limit specified in the present invention. The dry coating materials according to Comparative Examples 1 to 3 do not exhibit sufficient strength and density in measurements of bending strength and apparent porosity.

[0027] Comparative Example 4 does not contain a second binder. Comparative Example 5 contains a second binder, but the content is below the lower limit specified in the present invention. The dry coating materials of Comparative Examples 4 and 5 do not achieve sufficient strength in the bending strength measurement. On the other hand, the content of the second binder of Comparative Example 6 exceeds the upper limit specified in the present invention. The dry coating material of Comparative Example 6 was evaluated as being poor in terms of frame removal ability.

[0028] In Comparative Example 7, the content of the phenol resin exceeds the upper limit specified in the present invention. The dry coating material of Comparative Example 7 was evaluated as poor in odor.

Claims

1. A dry coating material for a tundish, comprising a total of 3 to 15 mass% of a first binder which is one or more types selected from inorganic hydrate powders having a thermal decomposition onset temperature of 40 to 300°C, and a total of 0.1 to 10 mass% of a second binder which is one or more types selected from powdered alkali silicates other than hydrates, powdered alkali sulfates other than hydrates, and powdered alkali phosphates other than hydrates, and the content of a phenolic resin is 0.5 mass% or less (including 0), with the remainder being mainly a refractory raw material.

2. The dry coating material for a tundish according to claim 1, wherein the content of the first binder is 5 to 10 mass% in total, and the content of the second binder is 1 to 5 mass% in total.

3. The dry coating material for a tundish according to claim 1 or 2, wherein the inorganic hydrate has a thermal decomposition starting temperature of 40 to 200°C.

Citation Information

Patent Citations

  • Dry-type tundish coating material and working method therefor

    JP2006007317A

  • Dry coating material

    JP2013039597A