High strength sintered tile and method of making same

Abstract

The application discloses a kind of high-strength sintered tile and preparation method thereof, comprising the following steps: tetra-n-butyl titanate, tetra-n-butyl zirconate, silane coupling agent, catalyst are added in ethanol aqueous solution, after aging, chopped basalt fiber is added, drying, calcination, and modified basalt fiber is obtained;50-60 parts of waste residue, 10-20 parts of waste soil, 5-10 parts of modified basalt fiber, 10-20 parts of bentonite, 15-20 parts of clay, 10-20 parts of feldspar, 5-10 parts of water are mixed uniformly to obtain slurry;The slurry is injected into the mold and shaped, and the sintered tile is obtained after sintering.The preparation method is treated by secondary calcination, which promotes densification and reduces the problem of high water absorption caused by waste residue and waste soil in the raw materials;At the same time, the modified basalt fiber is mixed, which further improves the mechanical properties and water absorption of the sintered tile.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of building materials, and particularly relates to a high-strength sintered tile and a preparation method thereof. BACKGROUND

[0002] The sintered tile is a plate-shaped or block-shaped sintered product for covering and decorating the roof of a building, which is made of clay or other inorganic non-metallic raw materials and processed through molding and sintering. With the rapid growth of the current building material market in China, the sintered tile occupies an important position in the market due to its unique performance and beautiful appearance, and the annual demand continues to rise, and the market capacity continues to expand. At the same time, the acceleration of urbanization and the promotion of rural housing renovation further expand the demand market.

[0003] With the requirement of sustainable development, the raw materials of the sintered tile are developing from single clay to multiple raw material types, including shale, river silt, coal gangue, fly ash, industrial waste, etc. in order to reduce the consumption of natural resources and the pressure of waste on the environment. In particular, the technology of preparing sintered bricks and tiles with a large amount of coal gangue, fly ash, mine waste soil, mine waste slag, tailings, etc. has matured and has also been industrialized. However, the porosity of the mine waste slag and waste soil will generally cause the water absorption rate of the sintered tile to be generally high, and the impurities in the waste slag and waste soil will reduce the density of the sintered tile, resulting in that the mechanical strength of the sintered tile is generally lower than that of the traditional clay tile. Therefore, how to further improve the mechanical properties and water absorption rate of the waste slag and waste soil-based sintered tile still needs further research. SUMMARY

[0004] In order to overcome the shortcomings of the prior art, the first object of the present application is to provide a high-strength sintered tile.

[0005] The second object of the present application is to provide a preparation method of the high-strength sintered tile.

[0006] The object of the present application is achieved by the following technical solutions:

[0007] The present application provides a preparation method of a high-strength sintered tile, comprising the following steps:

[0008] (1) Tetra-n-butyl titanate, tetra-n-butyl zirconate, silane coupling agent and catalyst are added to an aqueous solution of ethanol, and after aging at room temperature, chopped basalt fibers are added, heated, and then dried and calcined to obtain modified basalt fibers;

[0009] (2) 50-60 parts of waste slag, 10-20 parts of waste soil, 5-10 parts of the modified basalt fibers of step (1), 10-20 parts of bentonite, 15-20 parts of clay, 10-20 parts of feldspar and 5-10 parts of water are uniformly mixed to obtain a slurry;

[0010] (3) injecting the slurry of step (2) into a mold, standing for molding, drying, and sintering to obtain high-strength sintered tiles.

[0011] Preferably, in step (1), the amounts of tetrabutyl titanate, tetrabutyl zirconate, silane coupling agent, catalyst, aqueous solution of ethanol, and chopped basalt fibers are 2-4 g, 2-4 g, 0.5-1.5 g, 5-15 g, 80-100 mL, and 10-20 g, respectively.

[0012] Preferably, in step (1), the catalyst is 0.05-0.08 mol / L hydrochloric acid; the mass ratio of ethanol to water in the aqueous solution of ethanol is 1: (1.5-2); and the silane coupling agent is γ-aminopropyl triethoxysilane or vinyl triethoxysilane.

[0013] Preferably, in step (1), the aging time at room temperature is 10-15 h; the heating temperature is 40-50℃, and the heating time is 40-60 min; and the calcination temperature is 350-370℃, and the calcination time is 3-5 h.

[0014] Preferably, in step (1), the length of the chopped basalt fibers is 3-10 mm, and the diameter is 5-15 μm.

[0015] Preferably, in step (2), the waste residue is a mine waste residue with a chemical composition of SiO2≥55 wt% and Al2O3≥15 wt%, and the waste soil is a mine waste soil with a chemical composition of SiO2≥50 wt% and Al2O3≥10 wt%.

[0016] Preferably, in step (3), the drying temperature is 100-110℃, and the drying time is 12-24 h; and the sintering conditions are sintering at 600-700℃ for 0.5-1 h, and then sintering at 1150-1200℃ for 2-3 h.

[0017] The application provides a high-strength sintered tile prepared according to the preparation method of the high-strength sintered tile.

[0018] Compared with the prior art, the application has the following effects:

[0019] This invention provides a high-strength sintered tile by introducing modified basalt fibers into the raw material composition. The modified basalt fibers have a composite coating of zirconium oxide and titanium oxide on their surface, which increases the surface roughness of the basalt fibers. When the tile body is damaged, this effectively reduces the movement of basalt fibers within the sintered tile, increases the bonding tightness between the basalt fibers and the sintered tile, improves hydrophobicity, and reduces the water absorption rate of waste residue and waste soil-based sintered tiles. Simultaneously, it improves stability, generating thermally stable Ti-O-Al bonds during sintering to enhance the tile's mechanical properties. Furthermore, during high-temperature sintering, zirconium oxide transforms from a tetragonal phase to a monoclinic phase, accompanied by volume expansion, further improving the density of waste residue and waste soil-based sintered tiles and enhancing their structural strength.

[0020] This invention provides a method for preparing high-strength sintered tiles. Through a secondary calcination process, densification is promoted, reducing the high water absorption rate caused by waste residue and soil in the raw materials. Simultaneously, modified basalt fibers are incorporated to further improve the mechanical properties and water absorption rate of the sintered tiles. This preparation method is simple and suitable for industrial production and widespread application. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the preparation method of the present invention.

[0022] Figure 2 This is a scanning electron microscope image of the modified basalt fiber obtained in Example 1 of the present invention. Detailed Implementation

[0023] The present invention will be further described in detail below with reference to embodiments, but the implementation of the present invention is not limited thereto. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in this technical field. Test methods in the following embodiments that do not specify specific experimental conditions are generally performed according to conventional experimental conditions or experimental conditions recommended by the manufacturer. Unless otherwise specified, the reagents and raw materials used in the present invention are commercially available.

[0024] In this embodiment of the invention, the length of the short-cut basalt fiber is 3-10 mm and the diameter is 5-15 μm; the waste residue is mine waste residue, with a chemical composition of 65 wt% SiO2 and 20 wt% Al2O3; the waste soil is mine waste soil, with a chemical composition of 51 wt% SiO2 and 12 wt% Al2O3.

[0025] Example 1

[0026] This embodiment provides a method for preparing high-strength sintered tiles. Figure 1 This is a schematic diagram of the preparation method of the present invention.

[0027] The preparation method of high-strength sintered tiles in this embodiment includes the following steps:

[0028] (1) Tetrabutyl titanate, tetrabutyl zirconate, silane coupling agent (γ-aminopropyltriethoxysilane), and catalyst (0.07 mol / L hydrochloric acid) were added to an aqueous solution of ethanol (the mass ratio of ethanol to water was 1:2), aged at room temperature for 12 h, and then short-cut basalt fibers were added. The ratio of tetrabutyl titanate, tetrabutyl zirconate, silane coupling agent, catalyst, aqueous solution of ethanol, and short-cut basalt fibers was 3 g: 3 g: 1.0 g: 10 g: 90 mL: 15 g. The mixture was heated at 45 °C for 50 min, dried, and then calcined at 360 °C for 4 h to obtain modified basalt fibers. Figure 2 This is a scanning electron microscope image of the modified basalt fiber obtained in this embodiment.

[0029] (2) According to the mass fraction, 55 parts of waste residue, 15 parts of waste soil, 8 parts of modified basalt fiber from step (1), 15 parts of bentonite, 18 parts of clay, 15 parts of feldspar, and 8 parts of water are mixed evenly to obtain a slurry.

[0030] (3) The slurry from step (2) is injected into the mold, allowed to stand and form, dried at 110℃ for 18 hours, then heated to 650℃ for 1 hour, and then sintered at 1200℃ for 2.5 hours to obtain high-strength sintered tiles.

[0031] This embodiment also provides a high-strength sintered tile prepared by the above-described preparation method.

[0032] Example 2

[0033] This embodiment provides a method for preparing high-strength sintered tiles, including the following steps:

[0034] (1) Tetrabutyl titanate, tetrabutyl zirconate, silane coupling agent (vinyltriethoxysilane), and catalyst (0.08 mol / L hydrochloric acid) were added to an aqueous solution of ethanol (the mass ratio of ethanol to water was 1:2), aged at room temperature for 15 h, and then short-cut basalt fibers were added. The ratio of tetrabutyl titanate, tetrabutyl zirconate, silane coupling agent, catalyst, aqueous solution of ethanol, and short-cut basalt fibers was 4 g: 4 g: 1.5 g: 15 g: 100 mL: 20 g. The mixture was heated at 50 °C for 40 min, dried, and then calcined at 370 °C for 3 h to obtain modified basalt fibers.

[0035] (2) According to the mass fraction, 60 parts of waste residue, 20 parts of waste soil, 10 parts of modified basalt fiber from step (1), 20 parts of bentonite, 20 parts of clay, 20 parts of feldspar, and 10 parts of water are mixed evenly to obtain a slurry.

[0036] (3) Inject the slurry from step (2) into the mold, let it stand to form, dry it at 110℃ for 12 hours, then heat it to 700℃ for 0.5 hours, and then sinter it at 1200℃ for 2 hours to obtain high-strength sintered tiles.

[0037] This embodiment also provides a high-strength sintered tile prepared by the above-described preparation method.

[0038] Example 3

[0039] This embodiment provides a method for preparing high-strength sintered tiles, including the following steps:

[0040] (1) Tetrabutyl titanate, tetrabutyl zirconate, silane coupling agent (γ-aminopropyltriethoxysilane), and catalyst (0.05 mol / L hydrochloric acid) were added to an aqueous solution of ethanol (the mass ratio of ethanol to water was 1:1.5), aged at room temperature for 10 h, and then short-cut basalt fibers were added. The ratio of tetrabutyl titanate, tetrabutyl zirconate, silane coupling agent, catalyst, aqueous solution of ethanol, and short-cut basalt fibers was 2 g: 2 g: 0.5 g: 5 g: 80 mL: 10 g. The mixture was heated at 40 °C for 60 min, dried, and then calcined at 350 °C for 5 h to obtain modified basalt fibers.

[0041] (2) According to the mass fraction, 50 parts of waste residue, 10 parts of waste soil, 5 parts of modified basalt fiber from step (1), 10 parts of bentonite, 15 parts of clay, 10 parts of feldspar, and 5 parts of water are mixed evenly to obtain a slurry.

[0042] (3) Inject the slurry from step (2) into the mold, let it stand to form, dry it at 100℃ for 24 hours, then heat it to 600℃ for 1 hour, and then sinter it at 1150℃ for 3 hours to obtain high-strength sintered tiles.

[0043] This embodiment also provides a high-strength sintered tile prepared by the above-described preparation method.

[0044] Comparative Example 1

[0045] The difference between this comparative example and Example 1 is that the modified basalt fiber is replaced with a direct mixture of chopped basalt fiber, zirconium oxide and titanium oxide, with a mass ratio of chopped basalt fiber, zirconium oxide and titanium oxide of 15:1:1.

[0046] Comparative Example 2

[0047] The difference between this comparative example and Example 1 is that tetrabutyl titanate is omitted.

[0048] Comparative Example 3

[0049] The difference between this comparative example and Example 1 is that tetrabutyl zirconate is omitted.

[0050] Test case

[0051] 1. The bulk density of the sintered tiles obtained in Examples 1-3 and Comparative Examples 1-3 of the present invention was determined using the drainage method, and the results are shown in Table 1.

[0052] 2. The flexural strength of the sintered tiles obtained in Examples 1-3 and Comparative Examples 1-3 of the present invention was measured using the three-point bending method. The results are shown in Table 1.

[0053] 3. The water absorption rate and water resistance of the sintered tiles obtained in Examples 1-3 and Comparative Examples 1-3 of this invention were determined according to GB / T36584-2018 "Test Methods for Roofing Tiles". The results are shown in Table 1.

[0054] 4. The frost resistance of the sintered tiles obtained in Examples 1-3 and Comparative Examples 1-3 of this invention was determined according to GB / T36584-2018 "Test Methods for Roofing Tiles". After 15 freeze-thaw cycles, the samples were observed to see whether they peeled off, chipped corners, chipped edges and increased cracks. The results are shown in Table 1.

[0055] Table 1

[0056]

[0057] As shown in Table 1, the sintered tiles obtained in Examples 1-3 of this invention have higher bulk density and lower water absorption than those in Comparative Examples 1-3, exhibiting better mechanical properties and freeze-thaw resistance. The reason for this is that this invention introduces modified basalt fibers into the raw material composition. The modified basalt fibers form a composite coating of zirconium oxide and titanium oxide on their surface, which increases the surface roughness of the basalt fibers. When the tile body is damaged, this effectively reduces the movement of basalt fibers within the sintered tile, increases the bonding tightness between the basalt fibers and the sintered tile, improves hydrophobicity, and reduces the water absorption of waste residue and waste soil-based sintered tiles. Simultaneously, it improves stability, generating thermally stable Ti-O-Al bonds during sintering, thus enhancing the mechanical properties of the tile. Furthermore, during high-temperature sintering, zirconium oxide transforms from a tetragonal phase to a monoclinic phase, accompanied by volume expansion, further improving the density of waste residue and waste soil-based sintered tiles and enhancing their structural strength.

[0058] The above embodiments are merely preferred embodiments of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention shall fall within the scope of protection claimed by the present invention.

Claims

1. A method for preparing high-strength sintered tiles, characterized in that, Includes the following steps: (1) Tetrabutyl titanate, tetrabutyl zirconate, silane coupling agent and catalyst are added to an aqueous solution of ethanol, aged at room temperature, then chopped basalt fiber is added, heated and treated, then dried and calcined to obtain modified basalt fiber. In step (1), the room temperature aging time is 10-15h; the heating treatment temperature is 40-50℃ and the time is 40-60min; the calcination temperature is 350-370℃ and the time is 3-5h; the ratio of tetrabutyl titanate, tetrabutyl zirconate, silane coupling agent, catalyst, aqueous solution of ethanol, and short-cut basalt fiber is 2-4g: 2-4g: 0.5-1.5g: 5-15g: 80-100mL: 10-20g; (2) According to the mass parts, mix 50-60 parts of waste residue, 10-20 parts of waste soil, 5-10 parts of modified basalt fiber from step (1), 10-20 parts of bentonite, 15-20 parts of clay, 10-20 parts of feldspar, and 5-10 parts of water evenly to obtain a slurry. (3) Inject the slurry from step (2) into the mold, let it stand to form, dry it and then sinter it to obtain a high-strength sintered tile; In step (3), the sintering conditions are: sintering at 600-700℃ for 0.5-1h, and then sintering at 1150-1200℃ for 2-3h.

2. The method for preparing high-strength sintered tiles according to claim 1, characterized in that, In step (1), the catalyst is 0.05-0.08 mol / L hydrochloric acid; the mass ratio of ethanol to water in the aqueous solution of ethanol is 1:(1.5-2); and the silane coupling agent is γ-aminopropyltriethoxysilane or vinyltriethoxysilane.

3. The method for preparing high-strength sintered tiles according to claim 1, characterized in that, In step (1), the length of the short-cut basalt fiber is 3-10 mm and the diameter is 5-15 μm.

4. The method for preparing high-strength sintered tiles according to claim 1, characterized in that, In step (2), the waste residue is mine waste residue with a chemical composition of SiO2≥55wt% and Al2O3≥15wt%; the waste soil is mine waste soil with a chemical composition of SiO2≥50wt% and Al2O3≥10wt%.

5. The method for preparing high-strength sintered tiles according to claim 1, characterized in that, In step (3), the drying temperature is 100-110℃ and the time is 12-24h.

6. A high-strength sintered tile, characterized in that, The high-strength sintered tile is prepared according to any one of claims 1-5.

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