Low-temperature fast-firing porcelain tile and preparation method thereof

Abstract

The present application relates to the field of ceramic materials, and discloses a low-temperature fast-fired porcelain tile and a preparation method thereof.The low-temperature fast-fired porcelain tile comprises the following mineral raw materials: clay 10-30%, barren raw material 5-10%, potassium feldspar 30-40%, sodium feldspar 20-30%, wollastonite 0.5-5%, calcined talc 0.5-5%, lithium porcelain stone 0.5-10%, and fluorine-rich waste 0.5-17%; the barren raw material is quartz and / or silicon-rich waste; the fluorine-rich waste contains 10-15 wt% of F; and the silicon-rich waste contains 85-90% of SiO2.The present application introduces a specific proportion of Li2O-Na2O-K2O-CaO-MgO-F multi-component fluxing agent into the raw materials, so that the firing temperature of the porcelain tile is reduced to 1100-1125 ℃, and the performance of the porcelain tile is not inferior to that of the product fired by the traditional method.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of ceramic materials, in particular to a low-temperature fast-fired ceramic tile and a preparation method thereof. BACKGROUND

[0002] With the increasing demand for mineral resources, many important mineral resources have shown an increasingly short trend, which not only brings great pressure to the global environment and ecosystem, but also has a serious impact on various industries. The gradual depletion of resources leads to the continuous rise of energy prices. As a high energy consumer in the traditional industry, the production cost of building ceramics has increased significantly, the product price has risen, and the market competitiveness has declined, which has slowed down the momentum of rapid development of the industry. Therefore, for ceramic enterprises, it is an important problem to solve the high energy consumption problem in the production process.

[0003] There are many ways to save energy and reduce consumption in the production process of building ceramics, such as optimizing the structure of the kiln, reducing heat loss, and improving the thermal insulation performance; establishing a heat recovery system to preheat air and raw materials using waste heat to reduce energy consumption; using more efficient operating equipment to improve efficiency and shorten operating time to achieve the purpose of energy saving and consumption reduction; or developing low-energy, high-performance ceramic products such as thin bricks. In general, it mainly starts from four directions of kiln technology improvement, production process optimization, automation control construction strengthening, and green energy-saving product development. The implementation of these approaches also requires enterprises to have certain financial reserves and technical support. Therefore, the most fundamental and effective way is to achieve low-temperature fast firing of the body.

[0004] In the field of ceramic industry, low-temperature fast firing technology refers to the premise of low temperature and short time firing, and the product performance can be comparable to that of normal production. According to the thermodynamic equilibrium calculation, the energy saving of 10-15% per unit product can be achieved when the firing temperature of ceramic products is reduced by 100℃; the yield can be increased by 10% when the firing time is shortened by 10%, the heat consumption is reduced by 4%, so the social and economic benefits are obvious, and it also conforms to the current development trend of green energy-saving and environmental protection.

[0005] At present, the firing temperature of existing low water absorption ceramic tiles is generally 1150-1250℃, and some even need to reach a higher temperature. Obviously, a large amount of energy is still consumed under the current firing system. In order to achieve low-temperature fast firing of ceramic tile body, in the existing technology, a large amount of alkali metal oxide or alkaline earth metal oxide is directly introduced into the raw materials, the sintering temperature of the product is reduced, but there are still a series of problems such as high firing temperature, poor product performance, and narrow firing temperature range. In particular, when low-temperature firing is combined with rapid firing, the problem becomes more complex, therefore, it is of positive significance to further realize the low-temperature sintering of ceramic tile body and maintain its excellent performance. SUMMARY

[0006] To solve the above technical problems, the present application provides a low-temperature fast-fired porcelain tile and a preparation method thereof. First, the present application introduces a specific proportion of Li2O-Na2O-K2O-CaO-MgO-F multi-component flux in the raw materials, which can reduce the firing temperature of the porcelain tile to 1100-1125℃, while maintaining the performance of the product comparable to that of the product fired by traditional methods. Second, the present application introduces fluorine-rich waste and silicon-rich waste into the raw materials, which not only realizes the high-value recycling of waste, but also significantly improves the bending strength of the body with the fluorine-rich waste and the product performance with the silicon-rich waste.

[0007] The specific technical solutions of the present application are as follows:

[0008] In a first aspect, the present application provides a low-temperature fast-fired porcelain tile, which comprises the following mineral raw materials in mass percentage: clay 10-30%, barren raw material 5-10%, potassium feldspar 30-40%, sodium feldspar 20-30%, wollastonite 0.5-5%, calcined talc 0.5-5%, lithium porcelain stone 0.5-10%, and fluorine-rich waste 0.5-17%.

[0009] The barren raw material is quartz and / or silicon-rich waste; the fluorine-rich waste and silicon-rich waste are waste produced after lithium mica is extracted for lithium; the fluorine-rich waste contains 10-15wt% of F; and the silicon-rich waste contains 85-90% of SiO2.

[0010] As described in the background art of the present application, in order to achieve low-temperature fast firing, the prior art usually directly introduces a large amount of alkali metal oxide or alkaline earth metal oxide into the raw materials to reduce the sintering temperature of the product, but there are still problems such as high firing temperature (≥1160℃) and poor product performance. Therefore, the present application introduces Li2O-Na2O-K2O-CaO-MgO-F multi-component flux in the raw material formula. Among them, potassium feldspar and sodium feldspar provide K2O and Na2O respectively, wollastonite provides CaO, calcined talc provides MgO, lithium porcelain stone provides Li2O, and fluorine-rich waste provides F.

[0011] The present application finds that, on the basis of selecting the Li2O-Na2O-K2O-CaO-MgO-F multi-component fluxing agent and controlling the total amount and the proportion of each component, the firing temperature can be reduced to 1100-1125℃, and the obtained low-temperature fast-fired ceramic tile has a bending strength ≥45MPa and a water absorption ≤0.07%, which is not inferior to the performance of the product fired by the traditional method. The reason is that we find that, when the total amount of Li2O-Na2O-K2O-CaO-MgO-F is controlled to be 7-14wt% of the total raw materials, and the proportion of each component is controlled to be Li2O:F:CaO = 1:3-15:20-50, the raw materials can co-melt under a condition lower than their own melting temperature, form a low-temperature liquid phase, promote the sintering densification of the body at a low temperature, and thus improve the deformation resistance and other sintering properties.

[0012] In addition, the present application also introduces the fluorine-rich waste and silicon-rich waste (optional) generated after lithium mica is introduced to increase lithium into the formula, on the one hand, achieving high-value recycling of waste; on the other hand, we find that the introduction of fluorine-rich waste can promote the melting process of the body under a low-temperature firing environment, and significantly improve the bending strength of the body. The reason is that fluorine ions have a small ionic radius and strong electronegativity, and can form a low-melting-point glass phase with various metal oxides. At a low temperature, these fluorides can form a liquid phase, promote solid-liquid diffusion and particle rearrangement, and thus achieve densification, providing better fault tolerance and conditions for later product processing; the introduction of silicon-rich waste can partially or completely replace quartz in the traditional formula and enable the body to achieve better low-temperature melting effect, because the silicon-rich waste has a small particle size, a large specific surface energy, and a high sintering activity, and thus further improves the product performance.

[0013] It should be noted that the introduction of the above fluorine-rich waste into any ceramic tile raw material cannot improve the bending strength of the body. During the research and development period of the present application, the fluorine-rich waste was introduced into the ceramic tile raw material for ordinary process firing (firing temperature of 1200℃) in an attempt to obtain similar technical effects, and it was found that the obtained body had foaming phenomenon, increased porosity, and reduced strength, which could not meet the standard requirements of ceramic tiles. The reason is that the F in the fluorine-rich waste can cause the silicon-oxygen bond to break, greatly reduce the high-temperature viscosity of the body, and cause the body to overburn and foam under the ordinary firing process, resulting in performance degradation. Therefore, the introduction of the fluorine-rich waste into the low-temperature (1100-1125℃) fast-fired ceramic tile raw material can obtain unexpected technical effects.

[0014] As a preferred embodiment, the low-temperature fast-fired ceramic tile comprises the following mineral raw materials in mass percentage: clay 18-22%, barren raw material 5-10%, potassium feldspar 30-35%, sodium feldspar 20-25%, wollastonite 0.5-5%, calcined talc 3-5%, lithium porcelain stone 3-9%, and fluorine-rich waste 0.5-10%.

[0015] As preferred, the mass percentage of each chemical composition in the fluorine-rich waste material is: SiO2 0.5-10%, Al2O3 30-50%, Fe2O3 0.3-0.5%, CaO 18-20%, MgO 1-3%, K2O 0-0.1%, TiO2 0-0.1%, P2O5 1-3%, F 10-15%, Cl≤0.5%.

[0016] As preferred, the barren raw material is quartz and / or silicon-rich waste material, the mass percentage of each chemical composition in the silicon-rich waste material is: SiO2 85-90%, Al2O3 2-10%, Fe2O3 0.1-0.3%, CaO 0.1-0.3%, MgO 0-0.1%, K2O 0.2-0.4%, Na2O 1-2%, TiO2 0-0.1%, P2O5 0.2-0.4%.

[0017] As preferred, the chemical composition of the low-temperature fast-fired ceramic tile is: SiO2 56-78%, Al2O3 13-19%, Fe2O3 0.3-0.4%, CaO 1-4%, MgO 1-2%, K2O 3-4%, Na2O 2-3%, TiO2 0.1-0.3%, P2O5 0.1-0.3%, Li2O 0.05-0.15%, F 0.05-2.5%, Cl 0-0.05%.

[0018] In a second aspect, the present application provides a preparation method of the above low-temperature fast-fired ceramic tile, comprising the following steps:

[0019] (1) clay, quartz, potassium feldspar, sodium feldspar, wollastonite, calcined talc, lithium porcelain stone, fluorine-rich waste material, silicon-rich waste material are weighed and mixed uniformly.

[0020] (2) the mineral raw materials are wet ball milled to obtain a slurry.

[0021] (3) the slurry is spray granulated to form a powder.

[0022] (4) the powder after aging is dry pressed to form a green body.

[0023] (5) the green body is fired at 1100-1125℃ for 40-75min to obtain a low-temperature fast-fired ceramic tile.

[0024] The method can be fired at a low temperature of 1100-1125℃, and the product performance is not inferior to that of the product fired by the traditional method.

[0025] As preferred, in step (2), the mass ratio of the mineral raw material, the ball stone and the water in the wet ball milling is 1:1.8-2.2:0.6-1.2.

[0026] As preferred, in step (2), the particle size of the slurry is controlled within 250 mesh, and the residual amount is within 0.5%.

[0027] As preferred, in step (3), the water content of the powder is 6-7 wt%.

[0028] As preferred, in step (4), the aging is performed by standing the powder at room temperature for more than 24 h.

[0029] Compared with the prior art, the present application has the following technical effects:

[0030] (1) The present application introduces a specific proportion of Li2O-Na2O-K2O-CaO-MgO-F multi-component fluxing agent in the formula, which can make the performance of the low-temperature fast-fired porcelain tile not inferior to that of the product fired by the traditional method on the basis of reducing the firing temperature to 1100-1125℃ (the low-temperature fast-fired porcelain tile obtained by the present application has a bending strength ≥40 MPa and a water absorption ≤0.1%).

[0031] (2) The present application introduces the fluorine-rich waste and silicon-rich waste produced after lithium mica is used to extract lithium, which realizes the high-value recycling of waste on the one hand; on the other hand, it is found that the introduction of the fluorine-rich waste can promote the melting process of the body in a low-temperature firing environment and significantly improve the bending strength of the body, providing better fault tolerance and conditions for the later product processing; the introduction of the silicon-rich waste can partially or completely replace quartz in the traditional formula and make the body achieve better low-temperature melting effect, thereby further improving the product performance. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 is a scanning electron microscope image of the low-temperature fast-fired porcelain tile of Example 1;

[0033] Figure 2 is a scanning electron microscope image of the low-temperature fast-fired porcelain tile of Example 3;

[0034] Figure 3 is a scanning electron microscope image of the low-temperature fast-fired porcelain tile of Example 5. DETAILED DESCRIPTION

[0035] The present application will be further described below in combination with examples.

[0036] A low-temperature fast-fired ceramic tile comprises the following mineral raw materials in mass percentage: clay 10-30%, barren raw material 5-10%, potassium feldspar 30-40%, sodium feldspar 20-30%, wollastonite 0.5-5%, calcined talc 0.5-5%, petalite 0.5-10%, fluorine-rich waste 0.5-17%.

[0037] The barren raw material is quartz and / or silicon-rich waste; the fluorine-rich waste and silicon-rich waste are waste produced after lithium extraction from lepidolite ore; the fluorine-rich waste contains 10-15wt% of F; and the silicon-rich waste contains 85-90% of SiO2.

[0038] Preferably, the low-temperature fast-fired ceramic tile has the following chemical composition: SiO2 56-78%, Al2O3 13-19%, Fe2O3 0.3-0.4%, CaO 1-4%, MgO 1-2%, K2O 3-4%, Na2O 2-3%, TiO2 0.1-0.3%, P2O5 0.1-0.3%, Li2O 0.05-0.15%, F 0.05-2.5%, and Cl 0-0.05%.

[0039] Preferably, the low-temperature fast-fired ceramic tile comprises the following mineral raw materials in mass percentage: clay 18-22%, barren raw material 5-10%, potassium feldspar 30-35%, sodium feldspar 20-25%, wollastonite 0.5-5%, calcined talc 3-5%, petalite 3-9%, and fluorine-rich waste 0.5-10%.

[0040] Preferably, the fluorine-rich waste has the following chemical composition in mass percentage: SiO2 0.5-10%, Al2O3 30-50%, Fe2O3 0.3-0.5%, CaO 18-20%, MgO 1-3%, K2O 0-0.1%, TiO2 0-0.1%, P2O5 1-3%, F 10-15%, and Cl≤0.5%.

[0041] Preferably, the silicon-rich waste has the following chemical composition in mass percentage: SiO2 85-90%, Al2O3 2-10%, Fe2O3 0.1-0.3%, CaO 0.1-0.3%, MgO 0-0.1%, K2O 0.2-0.4%, Na2O 1-2%, TiO2 0-0.1%, and P2O5 0.2-0.4%.

[0042] A method for preparing the low-temperature fast-fired ceramic tile comprises the following steps:

[0043] (1) weigh clay, quartz, potassium feldspar, sodium feldspar, wollastonite, calcined talc, petalite, fluorine-rich waste, and silicon-rich waste, and mix them uniformly.

[0044] (2) wet ball milling the above mineral raw materials to obtain a slurry; wherein the mass ratio of the mineral raw materials, the ball stones and water is preferably 1:1.8-2.2:0.6-1.2; and the particle size of the slurry is controlled to be within 0.5% of the amount of residue on a 250-mesh sieve.

[0045] (3) spray granulating the slurry to form a powder (with a water content of preferably 6-7 wt%).

[0046] (4) aging the powder (preferably at room temperature for 24 h or more) and then dry-pressing to obtain a green body.

[0047] (5) firing the green body at 1100-1125°C for 40-75 min to obtain a low-temperature fast-fired ceramic tile.

[0048] (I) Effect of different proportions of Li2O-Na2O-K2O-CaO-MgO-F multi-component fluxes on the properties of the products

[0049] The amounts of each mineral raw material (clay, potassium feldspar, sodium feldspar, quartz, wollastonite, calcined talc, and lepidolite) in each test example were determined according to the chemical composition of the body in Table 1.

[0050] The raw materials of the body also included 0.2 wt% of a water-reducing agent.

[0051] The specific preparation steps of the body were as follows:

[0052] (1) weighing the raw materials and wet ball milling (material: ball stone: water = 1:2:1.2) to obtain a slurry; the particle size of the slurry was controlled to be within 0.5% of the amount of residue on a 250-mesh sieve;

[0053] (2) spray granulating the above slurry to form a powder with a water content of 6-7 wt%;

[0054] (3) dry-pressing the above powder after aging at room temperature for 24 h to obtain a green body;

[0055] (4) firing the above green body in a kiln at a calcination temperature of 1110°C for 40 min to obtain a low-temperature fast-fired ceramic tile product.

[0056] Table 1: Chemical composition of the body in each test example (%)

[0057] Number SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O Li2O P2O5 TiO2 F Test Example 1 70.64 19.38 0.31 0.75 1.81 3.56 2.71 0.04 0.16 0.2 0.44 Test Example 2 70.02 18.92 0.31 1.83 1.81 3.56 2.71 0.04 0.16 0.2 0.44 Test Example 3 69.97 18.11 0.31 2.69 1.81 3.56 2.71 0.04 0.16 0.2 0.44 Test Example 4 69.86 18.29 0.31 2.64 1.81 3.56 2.71 0.02 0.16 0.2 0.44 Test Example 5 69.56 18.51 0.31 2.64 1.81 3.56 2.71 0.10 0.16 0.2 0.44 Test Example 6 69.37 18.62 0.31 2.64 1.81 3.56 2.71 0.18 0.16 0.2 0.44 Test Example 7 69.84 18.44 0.32 2.68 1.81 3.56 2.71 0.08 0.16 0.2 0.2 Test Example 8 69.47 18.21 0.32 2.68 1.81 3.56 2.71 0.08 0.16 0.2 0.8 Test Example 9 69.03 18.05 0.32 2.68 1.81 3.56 2.71 0.08 0.16 0.2 1.4

[0058] The performance parameters of the fired products of the body in each test example are shown in Table 2.

[0059] Table 2: Performance indicators of the ceramic tile products obtained in each test example

[0060]

[0061] It can be seen from the test examples 1-9 that the amount and ratio of the different flux components (especially Li2O:F:CaO) need to be controlled within a reasonable range, and should not be too high or too low, otherwise the performance of the product will be affected. Specifically, CaO helps to improve the whiteness and strength of the body, and excessive CaO content will cause the melting point of the sintered body to decrease, resulting in a narrow sintering temperature range, and may also cause uneven reaction with other raw materials, forming cracks and pore structure; and insufficient CaO content will cause the body to need to reach a higher firing temperature to achieve densification. Li2O as a flux can lower the sintering temperature of the body, promote the bonding and densification between the grains. Too low content will cause the body to be difficult to sinter, and a higher firing temperature is needed to achieve densification; too high Li2O content will cause overfiring in a low temperature environment, causing the sintering performance of the body to decrease, or causing the body to shrink greatly due to the change in thermal expansion coefficient during the firing process, thereby causing cracking, deformation and other defects.

[0062] The F content has the most significant effect on the strength of the body, and a small amount of F can slightly improve the mechanical strength of the body; an appropriate amount of F can form a eutectic with other alkali metal oxides, promote low-temperature sintering densification of the body, and greatly improve the sintering performance, while excessive F can cause the body to flow more during sintering, causing excessive shrinkage and even cracking, increasing the porosity, and forming internal structural defects, which reduces the performance.

[0063] In summary, after more test tests, it is found that when the total amount of Li2O-Na2O-K2O-CaO-MgO-F is controlled at 7-14wt% of the total raw materials, and at the same time Li2O:F:CaO=1:3-15:20-50, the performance of the product is best. (II) Specific embodiments

[0065] Example 1

[0066] The low-temperature fast-fired porcelain tile of this example is composed of the following mineral raw materials by weight: clay 22 parts, potassium feldspar 33 parts, sodium feldspar 22 parts, quartz 8 parts, wollastonite 3 parts, calcined talc 4 parts, lithium porcelain stone 8 parts.

[0067] The raw materials of the body also contain a water reducing agent 0.2wt%.

[0068] The chemical composition of the body is shown in Table 3, and the specific preparation steps of the body are as follows:

[0069] (1) Weigh the raw materials and perform wet ball milling (material: ball stone: water = 1:2:0.6) to obtain a slurry; the particle size of the slurry is controlled to be within 0.5% of the 250 mesh screen residue;

[0070] (2) the slurry is spray granulated to form a powder with a water content of 6-7 wt%;

[0071] (3) the powder is dry-pressed to form a green body after standing for 24 h at room temperature;

[0072] (4) the green body is placed in a kiln and fired at a calcination temperature of 1100°C for 50 min to obtain a low-temperature fast-fired porcelain tile product.

[0073] Example 2

[0074] The low-temperature fast-fired porcelain tile of this example is composed of the following mineral raw materials by weight: clay 22 parts, potassium feldspar 33 parts, sodium feldspar 22 parts, quartz 8 parts, wollastonite 3 parts, calcined talc 4 parts, spodumene 4 parts, and fluorine-rich waste 4 parts.

[0075] The mass percentages of the chemical components in the fluorine-rich waste are as follows: SiO2 9.68%, Al2O3 49.52%, Fe2O3 0.48%, CaO 19.90%, MgO 2.88%, K2O 0.07%, TiO2 0.02%, P2O5 2.60%, and F 14.85%.

[0076] The raw materials of the green body further include 0.2 wt% of a water reducing agent.

[0077] The chemical composition of the green body is shown in Table 3, and the specific preparation steps of the green body are as follows:

[0078] (1) the raw materials are weighed and wet ball-milled (material: ball stone: water = 1:2:1.2) to obtain a slurry; the particle size of the slurry is controlled to have a residue of 0.5% or less on a 250-mesh sieve;

[0079] (2) the slurry is spray granulated to form a powder with a water content of 6-7 wt%;

[0080] (3) the powder is dry-pressed to form a green body after standing for 24 h at room temperature;

[0081] (4) the green body is placed in a kiln and fired at a calcination temperature of 1100°C for 50 min to obtain a low-temperature fast-fired porcelain tile product.

[0082] Example 3

[0083] The low-temperature fast-fired porcelain tile of this example is composed of the following mineral raw materials by weight: clay 22 parts, potassium feldspar 33 parts, sodium feldspar 22 parts, silicon-rich waste 8 parts, wollastonite 3 parts, calcined talc 4 parts, spodumene 4 parts, and fluorine-rich waste 4 parts.

[0084] The mass percentage of each chemical composition in the fluorine-rich waste material is: SiO2 9.68%, Al2O3 49.52%, Fe2O3 0.48%, CaO 19.90%, MgO 2.88%, K2O 0.07%, TiO2 0.02%, P2O5 2.60%, and F 14.85%.

[0085] The mass percentage of each chemical composition in the silicon-rich waste material is: SiO2 89.52%, Al2O3 8.04%, Fe2O3 0.13%, CaO 0.26%, MgO 0.05%, K2O 0.26%, Na2O 1.38%, TiO2 0.03%, and P2O5 0.33%.

[0086] The raw material of the green body further comprises 0.2wt% of water reducing agent.

[0087] The chemical composition of the green body is shown in Table 3, and the specific preparation steps of the green body are as follows:

[0088] (1) The raw material is weighed and wet ball-milled (material: ball stone: water = 1:2:1.2) to obtain a slurry; the particle size of the slurry is controlled to be within 0.5% of the sieve residue of 250 mesh;

[0089] (2) The slurry is spray granulated to obtain a powder with a water content of 6-7wt%;

[0090] (3) The powder is dry-pressed after standing for 24h at room temperature to obtain a green body;

[0091] (4) The green body is placed in a kiln and fired at a calcination temperature of 1100°C for 50min to obtain a low-temperature fast-fired porcelain tile product.

[0092] Example 4

[0093] The low-temperature fast-fired porcelain tile of the present example is composed of the following mineral raw materials by weight: clay 22 parts, potassium feldspar 31 parts, sodium feldspar 20 parts, quartz 8 parts, wollastonite 3 parts, calcined talc 4 parts, lithium porcelain stone 8 parts, and fluorine-rich waste material 4 parts.

[0094] The mass percentage of each chemical composition in the fluorine-rich waste material is: SiO2 9.68%, Al2O3 49.52%, Fe2O3 0.48%, CaO 19.90%, MgO 2.88%, K2O 0.07%, TiO2 0.02%, P2O5 2.60%, and F 14.85%.

[0095] The raw material of the green body further comprises 0.2wt% of water reducing agent.

[0096] The chemical composition of the green body is shown in Table 3, and the specific preparation steps of the green body are as follows:

[0097] (1) The raw materials are weighed and wet ball-milling is performed (material: ball stone: water = 1:2:1.2) to obtain a slurry; the particle size of the slurry is controlled to be within 0.5% of the amount of a 250-mesh sieve;

[0098] (2) The slurry is spray granulated to produce a powder with a moisture content of 6-7wt%;

[0099] (3) The powder is dry-pressed after standing for 24h at room temperature to obtain a green body;

[0100] (4) The green body is placed in a kiln and fired at a calcination temperature of 1125°C for 40min to obtain a low-temperature fast-fired porcelain tile product.

[0101] Example 5

[0102] The low-temperature fast-fired porcelain tile of this example is composed of the following mineral raw materials by weight: clay 22 parts, potassium feldspar 31 parts, sodium feldspar 20 parts, silicon-rich waste 6.6 parts, wollastonite 3 parts, calcined talc 4 parts, lithium porcelain stone 5.4 parts, and fluorine-rich waste 8 parts.

[0103] The mass percentages of the chemical compositions in the fluorine-rich waste are as follows: SiO2 9.68%, Al2O3 49.52%, Fe2O3 0.48%, CaO 19.90%, MgO 2.88%, K2O 0.07%, TiO2 0.02%, P2O5 2.60%, and F 14.85%.

[0104] The mass percentages of the chemical compositions in the silicon-rich waste are as follows: SiO2 89.52%, Al2O3 8.04%, Fe2O3 0.13%, CaO 0.26%, MgO 0.05%, K2O 0.26%, Na2O 1.38%, TiO2 0.03%, and P2O5 0.33%.

[0105] The raw materials of the green body further comprise 0.2wt% of a water reducing agent.

[0106] The chemical composition of the green body is shown in Table 3, and the specific preparation steps of the green body are as follows:

[0107] (1) The raw materials are weighed and wet ball-milling is performed (material: ball stone: water = 1:2:1.2) to obtain a slurry; the particle size of the slurry is controlled to be within 0.5% of the amount of a 250-mesh sieve;

[0108] (2) The slurry is spray granulated to produce a powder with a moisture content of 6-7wt%;

[0109] (3) The powder is dry-pressed after standing for 24h at room temperature to obtain a green body;

[0110] (4) The green body is placed in a kiln, and a low-temperature fast-fired porcelain tile product is obtained after firing at a calcining temperature of 1125°C for 50 min.

[0111] Example 6

[0112] The low-temperature fast-fired porcelain tile of the present example is composed of the following mineral raw materials by weight: clay 21 parts, potassium feldspar 30 parts, sodium feldspar 20 parts, quartz 8 parts, wollastonite 2 parts, calcined talc 3 parts, petalite 8 parts, and fluorine-rich waste 8 parts.

[0113] The mass percentages of the chemical components in the fluorine-rich waste are as follows: SiO2 9.68%, Al2O3 49.52%, Fe2O3 0.48%, CaO 19.90%, MgO 2.88%, K2O 0.07%, TiO2 0.02%, P2O5 2.60%, and F 14.85%.

[0114] The raw materials of the green body further comprise 0.2 wt% of a water reducing agent.

[0115] The chemical composition of the green body is shown in Table 3, and the specific preparation steps of the green body are as follows:

[0116] (1) The raw materials are weighed and wet ball-milled (material: ball stone: water = 1:2:1.2) to obtain a slurry; the particle size of the slurry is controlled to have a residue of 0.5% or less on a 250-mesh sieve;

[0117] (2) The slurry is spray granulated to form a powder having a water content of 6-7 wt%;

[0118] (3) The powder is dry-pressed after standing for 24 h at room temperature to obtain a green body;

[0119] (4) The green body is placed in a kiln, and a low-temperature fast-fired porcelain tile product is obtained after firing at a calcining temperature of 1125°C for 70 min.

[0120] Table 3: Chemical composition of the green body of each example (%)

[0121]

[0122] (1) The performance parameters of the fired products of each green body of Examples 1-6 are shown in Table 4.

[0123] Table 4: Performance indicators of the porcelain tile products of each example

[0124]

[0125]

[0126] The water absorption can reflect the sintering degree of the body, and the bending strength can reflect the practicability of the body, when the water absorption is less than or equal to 0.5% and the bending strength is greater than or equal to 35MPa, the body can meet the requirements of the national standard of sintered brick. It can be seen from Table 4 that the low-temperature fast-fired porcelain tile prepared by each of the above examples has excellent mechanical properties, and the performance of the low-temperature fast-fired porcelain tile is not much different from that of the porcelain tile fired by the traditional method, and the present application breaks through the traditional firing temperature, and realizes the complete sintering of the body at a low temperature of 1100-1125℃, and under the reasonable optimization of the formula, the performance of the porcelain tile can be obviously better than that of the ordinary ceramic product.

[0127] Further analysis of examples 1 and 2, the main difference between example 1 and example 2 is that example 1 does not contain F. Fluoride as an effective flux can reduce the activation energy of the sintering system, and can significantly reduce the sintering temperature. Fluoride ions react with various metal oxides to form low-melting fluoride glass phases, which can form liquid phases at lower temperatures. The liquid phase formed by fluoride is distributed at the grain boundary, which not only can enhance the bonding strength between adjacent grains, but also can optimize the grain boundary structure and improve the overall mechanical properties of the material. Therefore, under the same low temperature conditions, the example 2 doped with fluorine-rich waste can obtain better strength.

[0128] Further analysis of examples 2 and 3 can find that the chemical composition of the sintered products of examples 2 and 3 is almost the same, the main difference is that the silicon-rich waste is used to replace the quartz in example 2. However, the data comparison shows that example 3 is significantly better than example 2. It is speculated that the reason may be that the silicon-rich waste can activate sufficient surface diffusion and chemical reaction process at a lower temperature, and the silicon-rich waste contains various alkali metal oxide components, which can better form a low-eutectic liquid phase, promote the particle rearrangement and densification process, so that the silicon-rich waste can replace the quartz to obtain a product with better sintering performance under low temperature environment.

[0129] (2) Scanning electron microscope image comparison

[0130] Figure 1 The scanning electron microscope image of the low-temperature fast-fired porcelain tile of example 1 is shown, which shows that the body sintered at low temperature by Li2O-Na2O-K2O-CaO-MgO multi-component flux has a high degree of surface densification. Figure 2 、 Figure 3 The scanning electron microscope images of the low-temperature fast-fired porcelain tile of examples 3 and 5 are shown, respectively, which shows that after the introduction of fluorine-rich waste and silicon-rich waste, the number of pores on the surface of the body is further reduced, the pore size is less than 10μm, and the body has a higher degree of densification.

[0131] The raw materials and equipment used in the present application are conventional raw materials and equipment in the art unless otherwise specified; the methods used in the present application are conventional methods in the art unless otherwise specified.

[0132] The above merely describes preferred embodiments of the present application, and is not intended to limit the present application. Any simple modification, change, and equivalent transformation of the above embodiments according to the technical essence of the present application are still within the protection scope of the technical scheme of the present application.

Claims

1. A low-temperature fast-firing porcelain tile, characterized in that: It is made from the following mineral raw materials in the indicated mass percentages: clay 10-30%, barren raw materials 5-10%, potassium feldspar 30-40%, sodium feldspar 20-30%, wollastonite 0.5-5%, calcined talc 0.5-5%, lithium porcelain stone 0.5-10%, and fluorine-rich waste 0.5-17%. The barren raw materials are quartz and / or silicon-rich waste; Fluorine-rich waste and silicon-rich waste are waste generated after lithium extraction from lepidolite ore; among them, fluorine-rich waste contains 10-15 wt% F; silicon-rich waste contains 85-90% SiO2. The mass percentages of each chemical component in low-temperature fast-fired porcelain bricks are as follows: SiO2 56~78%, Al2O3 13~19%, Fe2O3 0.3~0.4%, CaO 1~4%, MgO 1~2%, K2O 3~4%, Na2O 2~3%, TiO2 0.1~0.3%, P2O5 0.1~0.3%, Li2O 0.05~0.15%, F 0.05~2.5%, Cl 0~0.05%; and the total amount of Li2O-Na2O-K2O-CaO-MgO-F accounts for 7-14wt%, with Li2O:F:CaO = 1:3~15:20~50.

2. The low-temperature fast-firing porcelain brick according to claim 1, characterized in that: It is made from the following mineral raw materials in the following mass percentages: clay 18-22%, barren raw materials 5-10%, potassium feldspar 30-35%, sodium feldspar 20-25%, wollastonite 0.5-5%, calcined talc 3-5%, lithium porcelain stone 3-9%, and fluorine-rich waste 0.5-10%.

3. The low-temperature fast-firing porcelain brick according to claim 1 or 2, characterized in that: The mass percentages of each chemical component in the fluorine-rich waste are as follows: SiO2 0.5~10%, Al2O3 30~50%, Fe2O3 0.3~0.5%, CaO 18~20%, MgO 1~3%, K2O 0~0.1%, TiO2 0~0.1%, P2O5 1~3%, F 10~15%, Cl ≤0.5%.

4. The low-temperature fast-firing porcelain brick according to claim 1 or 2, characterized in that: The mass percentages of each chemical component in the silicon-rich waste are as follows: SiO2 85~90%, Al2O3 2~10%, Fe2O3 0.1~0.3%, CaO 0.1~0.3%, MgO 0~0.1%, K2O 0.2~0.4%, Na2O 1~2%, TiO2 0~0.1%, P2O5 0.2~0.4%.

5. The low-temperature fast-firing porcelain tile according to claim 1, characterized in that: The mass percentages of each chemical component in low-temperature fast-fired porcelain bricks are as follows: SiO2 69.56%, Al2O3 18.51%, Fe2O3 0.31%, CaO 2.64%, MgO 1.81%, K2O 3.56%, Na2O 2.71%, TiO2 0.2%, P2O5 0.16%, Li2O 0.10%, and F 0.44%.

6. The low-temperature fast-firing porcelain brick according to claim 1, characterized in that: The mass percentages of each chemical component in low-temperature fast-fired porcelain bricks are as follows: SiO2 69.47%, Al2O3 18.21%, Fe2O3 0.32%, CaO 2.68%, MgO 1.81%, K2O 3.56%, Na2O 2.71%, TiO2 0.2%, P2O5 0.16%, Li2O 0.08%, and F 0.8%.

7. A method for preparing low-temperature rapid-fired porcelain tiles according to any one of claims 1-6, characterized in that... Includes the following steps: (1) Weigh out clay, quartz, potassium feldspar, sodium feldspar, wollastonite, calcined talc, lithium porcelain stone, fluorine-rich waste, and silicon-rich waste, and mix them evenly; (2) The above mineral raw materials are subjected to wet ball milling to obtain a slurry; (3) Spray granulation of the slurry to produce powder; (4) The aged powder is dry-pressed to obtain a green body; (5) The green body is fired at 1100~1125℃ for 40~75 min to obtain low-temperature fast-fired porcelain bricks.

8. The preparation method according to claim 7, characterized in that: In step (2), the mass ratio of mineral raw materials, balls and water in the wet ball mill is 1:1.8~2.2:0.6~1.

2.

9. The preparation method according to claim 7, characterized in that: In step (2), the particle size of the slurry is controlled to be within 0.5% of the residue on a 250-mesh sieve.

10. The preparation method according to claim 7, characterized in that: In step (3), the moisture content of the powder is 6-7 wt%.

11. The preparation method according to claim 7, characterized in that: In step (4), aging is to let the powder stand at room temperature for more than 24 hours.

Images