Building ceramic reinforced with graded waste porcelain powder and preparation method thereof

Abstract

The application relates to the technical field of building ceramics, and discloses a kind of building ceramics enhanced by hierarchical waste porcelain powder and a preparation method thereof, raw materials of the building ceramics include base material raw materials and glaze; base material raw materials include body basic raw materials and waste porcelain powder; waste porcelain powder includes fine particle reaction material with a particle size of 0.05-0.15 mm and coarse particle decoration material with a particle size of 0.425-0.85 mm; by first wet ball milling, spray granulation of fine particle reaction material, coconut oil, sodium tripolyphosphate, body basic raw materials and polyvinyl alcohol to obtain body powder, then stirring and mixing the body powder with coarse particle decoration material, glycerol to obtain base material raw materials, followed by pressing forming, glaze application and firing to obtain building ceramics. The application improves dispersibility and interfacial bonding by functional classification and targeted process optimization of waste porcelain powder, and the fired ceramics not only has high strength, but also naturally presents spot or star point decorative texture.

Description

Technical Field

[0001] This invention belongs to the technical field of building ceramics, specifically relating to a building ceramic reinforced with graded waste ceramic powder and its preparation method. Background Technology

[0002] As a key material for modern building decoration and structure, the production of architectural ceramics has long relied heavily on natural mineral raw materials such as clay, feldspar, and quartz. However, with the continuous growth of market demand and the increasing depletion of high-quality mineral resources, the pressure on raw material supply is constantly increasing. At the same time, the ceramics industry itself generates a huge amount of solid waste, creating a dual dilemma of resource consumption and environmental pollution. Specifically, the ceramics industry consumes more than 200 million tons of natural mineral resources annually, while the total amount of waste generated each year exceeds 18 million tons. Currently, the treatment of these wastes is still mainly through landfill and stockpiling, which not only occupies land but also poses serious environmental risks—the lead content in the soil of some landfill areas has exceeded the standard by 300%, directly threatening groundwater resources. On the other hand, the recovery rate of valuable components such as silicon dioxide and alumina rich in waste ceramics is less than 15%, resulting in a huge waste of resources.

[0003] To promote the sustainable development of the industry, the resource utilization of ceramic waste (especially waste ceramics) has become an inevitable choice. Current technologies generally employ simple crushing methods to prepare waste ceramic aggregates, which are mainly used to produce low-value-added paving bricks or concrete products. However, this extensive utilization method has significant bottlenecks: firstly, the amount of waste ceramics added is usually limited to below 30%, resulting in limited resource substitution; secondly, due to unreasonable particle size distribution after crushing or poor bonding between the glaze on the surface of waste ceramic particles and the new interface, key mechanical properties such as flexural strength of recycled products often decline, making it difficult to meet the quality requirements of high-performance engineering.

[0004] Waste ceramics (especially those used in medium- and high-temperature applications) have a high alumina content, and the mullite phase formed during the initial sintering process can theoretically serve as a reinforcing phase, potentially improving the mechanical properties of building ceramics. Studies have shown that when the waste ceramic powder content reaches 10%, the flexural strength of the green body can be increased to over 35 MPa. However, the key to realizing this potential lies in solving the sintering compatibility problem between the waste ceramic powder and the matrix. Improper handling can lead to cracking and deformation due to mismatched sintering shrinkage, ultimately degrading the finished product's performance. Summary of the Invention

[0005] The main objective of this invention is to address the aforementioned problems by providing a building ceramic reinforced with graded waste porcelain powder and its preparation method. This method assigns different roles to the waste porcelain powder based on its particle size differences, enabling functional grading and utilization through "reaction / reinforcement." Targeted process optimization is then applied to each grade to improve dispersibility and interfacial bonding. The resulting product exhibits superior mechanical properties compared to products made with traditional formulas or simply mixed with waste porcelain powder, providing a practical and feasible technical path for achieving high-proportion resource utilization of waste porcelain powder. Simultaneously, the fired ceramic naturally displays speckled or star-shaped decorative textures, creating a unique aesthetic signature and enhancing added value and market competitiveness.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0007] One of the technical solutions of the present invention is a building ceramic reinforced with graded waste porcelain powder. The raw materials of the building ceramic include base material and glaze. The base material includes body base material, waste porcelain powder, coconut oil, sodium tripolyphosphate, polyvinyl alcohol, and glycerin. The body base material comprises, by mass percentage: clay 45-55%, porcelain stone 30-37%, feldspar 10-15%, and talc 0-5%. The waste porcelain powder includes fine particulate reactant comprising 20-50% of the body base material mass and 15% of the body base material mass. The ceramic material comprises ~35% coarse-grained decorative material, with fine-grained reactive material having a particle size of 0.05~0.15mm and coarse-grained decorative material having a particle size of 0.425~0.85mm; the glaze includes fine-grained reactive material and cashew phenol glycidyl ether; the building ceramic is produced by first wet ball milling and spray granulation of fine-grained reactive material, coconut oil, sodium tripolyphosphate, body base raw material and polyvinyl alcohol to obtain body powder, then mixing body powder with coarse-grained decorative material and glycerin to obtain base material, and then pressing, glazing and firing to obtain the finished product.

[0008] This invention utilizes functional grading of waste ceramic powder. Fine-grained waste ceramic powder with a particle size of 0.05~0.15mm is used as the reactant. This portion of waste ceramic powder has a high specific surface area and high reactivity, aiming to fully react with the green body components during high-temperature sintering to form a liquid phase and promote green body densification. Coarse-grained waste ceramic powder with a particle size of 0.425~0.85mm is used as the reinforcing material. This portion of waste ceramic powder has high chemical inertness and basically does not participate in the reaction during green body sintering. It is dispersed in the ceramic matrix as an inert skeleton, achieving toughening and strengthening effects through crack deflection, bridging, and other mechanisms, and producing unique decorative textures.

[0009] However, high-dosage waste ceramic powder, due to its incompatibility with the basic green body, still leads to problems such as poor compatibility, low dosage, and performance degradation. Therefore, this invention improves the process through stepwise mixing, synergistic additives, and glaze layer matching to achieve high-value utilization of waste ceramic powder and synergistic improvement of product performance. Specifically, during wet ball milling, the combined addition of coconut oil and sodium tripolyphosphate forms a stable oil-in-water emulsion dispersion system. The fatty acid chains of coconut oil create steric hindrance, while sodium tripolyphosphate strengthens electrostatic repulsion through the electric layer, jointly inhibiting the agglomeration of fine particles. The addition of polyvinyl alcohol as a binder not only facilitates the subsequent spray granulation process but also allows polyvinyl alcohol to form hydrogen bonds with ammonium tripolyphosphate, strengthening the stable emulsion system and synergistically promoting the dispersion of fine particles in the green body's base raw materials.

[0010] The green body powder obtained after spray granulation is mixed with coarse-particle decorative material. After pre-wetting and modification with glycerol, the coarse-particle decorative material not only improves the dispersion of the coarse particles and reduces agglomeration, but also improves the dispersibility between the coarse particles and the green body powder, increasing the uniformity of the coarse particle distribution within the green body powder and preventing localized enrichment. Simultaneously, due to the large size of the coarse-particle decorative material, various protrusions form on the green body surface, making surface glazing more difficult. After sintering, the glaze surface is prone to incompleteness and cracking, which in turn affects the strength of the ceramic. By adding fine-particle reactants to the glaze, whose composition is consistent with the fine-particle reactants in the green body, it is beneficial to form a continuous phase during sintering, reducing the glaze-green body interfacial tension and preventing glaze layer detachment. Cashew phenol glycidyl ether is also added to the glaze. It adheres to the surface of the fine-particle reactant and is also dispersed among the other components of the glaze. During firing, the epoxy groups of cashew phenol glycidyl ether react and bond with the body, further enhancing interfacial bonding in conjunction with the fine-particle reactant in the glaze. The glycerol wetting modification of the coarse particles in the body also promotes their reaction and bonding with the cashew phenol glycidyl ether in the glaze, improving the density and integrity of the glaze layer at the raised areas. Moreover, the long alkyl chains contained in cashew phenol glycidyl ether can reduce the surface tension of the glaze, allowing the glaze to uniformly cover the coarse-particle raised areas, and preventing residual impurities from forming pores after firing, further ensuring flexural strength.

[0011] Finally, after firing, a high-strength ceramic product is obtained. The surface of the prepared building ceramic has a decorative effect of raised particles, spots, or stars. When the water absorption rate of the building ceramic is ≤0.5%, the flexural strength is ≥40MPa; when the water absorption rate is 0.5~3%, the flexural strength is ≥35MPa. Therefore, this invention effectively solves the compatibility problem between waste ceramic powder and the matrix, and achieves synergistic performance gains under high doping levels.

[0012] More preferably, the waste ceramic powder comprises the following chemical composition by mass percentage: SiO2 68~70%, Al2O3 19~23%, K2O+Na2O 4~7%, CaO+MgO 1~3%, and other metal oxides ≤3%; the other metal oxides include one or more of ZnO, BaO, Fe2O3, and TiO2.

[0013] More preferably, the amount of coconut oil added is 2-3% of the mass of the fine particulate reactant; the amount of sodium tripolyphosphate added is 0.7-1% of the mass of the fine particulate reactant; the amount of polyvinyl alcohol added is 2.5-3.5% of the mass of the base raw material of the green body; and the amount of glycerol added is 0.5-0.9% of the mass of the coarse particulate decorative material.

[0014] More preferably, the clay is one or more of kaolin, kaolinite, and ball clay; and the feldspar is one or more of potassium feldspar and sodium feldspar.

[0015] More preferably, the glaze comprises the following components by mass percentage: 38-42% potassium feldspar, 20-23% quartz powder, 11-15% kaolin, 10-13% dolomite, 9-10% fine-particle reactant, and 2-4% cashew phenol glycidyl ether; the thickness of the glaze layer is 0.3-0.5 mm.

[0016] The fine-particle reactants in the glaze have the same composition as those in the body, which is beneficial for the continuous phase during sintering, reduces the interfacial tension between the glaze and the body, and prevents the glaze layer from peeling off. Cashew phenol glycidyl ether in the glaze reacts with the hydroxyl groups on the surface of the body and in the glaze, such as kaolin and waste porcelain powder, promoting glaze densification and improving the glaze-body bonding strength, reducing glaze cracks, and thus improving the flexural strength of the ceramic. The ratio of fine-particle reactants to cashew phenol glycidyl ether also affects the glaze-body bonding strength and glaze strength, which in turn affects the flexural strength of the ceramic material.

[0017] The second technical solution of the present invention: a method for preparing building ceramics reinforced with graded waste ceramic powder, comprising the following steps:

[0018] (1) The waste porcelain powder is divided into fine particles of reactant with a particle size of 0.05~0.15mm and coarse particles of decorative material with a particle size of 0.425~0.85mm;

[0019] (2) Wet ball mill the fine particulate reactant, coconut oil and sodium tripolyphosphate, then add the base raw material of the green body and polyvinyl alcohol and continue ball milling to obtain a slurry;

[0020] (3) The slurry is spray-granulated to obtain the green body powder;

[0021] (4) Mix the coarse-particle decorative material and glycerin, then add the blank powder and continue mixing to obtain the base material;

[0022] (5) After the base material is aged, pressed, dried, glazed and fired, the building ceramics can be obtained.

[0023] More preferably, in step (2), the ball-to-material ratio of the wet ball mill is 2~3:1, the water-to-material ratio is 0.6~0.8:1, the time is 2~4h, and the ball milling is continued to make the particle size of the obtained slurry ≤2% on a 325-mesh sieve.

[0024] More preferably, in step (3), the conditions for spray granulation are: inlet air temperature 300~350℃, outlet temperature 100~120℃; and the moisture content of the green body powder is 6~8%.

[0025] More preferably, in step (4), the stirring and mixing is carried out at 150~200r / min for 10~20min, and the mixing time is continued for 10~20min.

[0026] More preferably, in step (5), the aging time is 24 hours or more.

[0027] More preferably, in step (5), the drying is performed until the moisture content is 5-8%.

[0028] More preferably, in step (5), the firing temperature is 1190~1220℃ and the firing cycle is 45~60min.

[0029] Compared with the prior art, the present invention has the following advantages:

[0030] (1) The functional grading and utilization of waste porcelain powder through "reaction / enhancement" has broken through the technical bottleneck of high-value and high-dosage recycling of waste porcelain powder. This method does not simply treat waste porcelain powder as a homogeneous filler, but assigns different roles according to its particle size differences and performs targeted process optimization to improve dispersibility and interfacial bonding. Fine particles play a highly active role in the reaction, promoting sintering and densification of the green body, laying the foundation for material strength; coarse particles act as an inert skeleton to enhance and toughen the material. This fundamentally solves the industry problems of poor compatibility, low dosage, and performance degradation caused by the mismatch between the physicochemical properties of waste porcelain powder and the basic green body. The mechanical properties of the prepared products are superior to those of products with traditional formulas or simply mixed with waste porcelain powder, providing a practical and feasible technical path for achieving high-proportion resource utilization of waste porcelain powder.

[0031] (2) The inert skeleton formed by coarse-particle waste porcelain powder in the matrix naturally presents a speckled or star-shaped decorative texture after firing. The effect is natural and avoids the need for later decorative processes such as printing and inkjet printing, thus reducing costs. This texture can be designed according to the particle size and dosage of coarse particles to form a unique aesthetic mark of the product, thereby enhancing added value and market competitiveness. Attached Figure Description

[0032] Figure 1 This is a photograph of the ceramic obtained in Example 1;

[0033] Figure 2 The image shows the actual ceramic product obtained in Comparative Example 1.

[0034] Figure 3 The image shows the actual ceramic product obtained in Comparative Example 2.

[0035] Figure 4 The image shows the actual ceramic product obtained in Comparative Example 3.

[0036] Figure 5 The image shows the actual ceramic product obtained in Comparative Example 4.

[0037] Figure 6 This is a photograph of the ceramic produced in Comparative Example 5. Detailed Implementation

[0038] The following embodiments further illustrate the above-described content of the present invention in detail, but it should not be construed as limiting the scope of the present invention to the following embodiments. All technologies implemented based on the above-described content of the present invention fall within the scope of the present invention. The raw materials for the body and the glaze all adopt commonly used specifications and dimensions in the art.

[0039] Example 1

[0040] (1) The waste porcelain powder is sourced from medium-temperature daily-use porcelain fired at 1200℃. The waste porcelain powder, by mass percentage, includes the following chemical composition: SiO2 69%, Al2O3 19%, K2O+Na2O 7%, CaO+MgO 3%, and other metal oxides 2%. The waste porcelain powder is divided into fine-particle reactive materials with a particle size of 0.05~0.15mm and coarse-particle decorative materials with a particle size of 0.425~0.85mm. The basic raw materials for the body, by mass percentage, include the following components: kaolin 50%, porcelain stone 37%, potassium feldspar 10%, and talc 3%.

[0041] (2) The fine particulate reactant (30% of the mass of the base raw material), coconut oil (2.2% of the mass of the fine particulate reactant) and sodium tripolyphosphate (0.8% of the mass of the fine particulate reactant) were wet ball milled with a ball-to-material ratio of 2:1 and a water-to-material ratio of 0.6:1 for 2 hours. Then, the base raw material and polyvinyl alcohol 1788 (2.5% of the mass of the base raw material) were added and ball milled for another 8 hours to obtain a slurry with a particle size of 1.2% residue on a 325-mesh sieve.

[0042] (3) Spray granulation of the slurry with an inlet air temperature of 320°C and an outlet air temperature of 110°C to obtain a green body powder with a moisture content of 7%.

[0043] (4) Mix coarse granular decorative material (20% of the mass of the base raw material of the green body) and glycerin (0.6% of the mass of the coarse granular decorative material) at 180 r / min for 10 min, then add the green body powder and continue mixing for 15 min.

[0044] (5) The mixed powder is aged for 24 hours, then pressed and molded (pressure 22MPa, holding pressure for 4s), and dried.

[0045] (6) The glaze raw materials, by mass percentage, include the following components: 40% potassium feldspar, 23% quartz powder, 15% kaolin, 10% dolomite, 9% fine-particle reactant, and 3% cashew phenol glycidyl ether. Water is added, the mixture is stirred, wet-milled for 6 hours, and 0.05% residue is obtained after passing through a 325-mesh sieve, resulting in a glaze with a solid content of 60%. The glaze is then applied by spraying, with a glaze layer thickness of 0.4 ± 0.02 mm.

[0046] (7) Finally, the temperature is raised to 1200℃ for firing. The heating rate is 50℃ / h and the firing cycle is 50min to obtain building ceramics.

[0047] Example 2

[0048] (1) The waste porcelain powder is sourced from medium-temperature daily-use porcelain fired at 1180℃. The waste porcelain powder, by mass percentage, includes the following chemical composition: SiO2 68%, Al2O3 20%, K2O+Na2O 7%, CaO+MgO 3%, and other metal oxides 2%. The waste porcelain powder is divided into fine-particle reactive material with a particle size of 0.05~0.15mm and coarse-particle decorative material with a particle size of 0.425~0.85mm. The basic raw materials for the body, by mass percentage, include the following components: kaolin 55%, porcelain stone 33%, potassium feldspar 12%, and talc 0%.

[0049] (2) The fine particulate reactant (50% of the mass of the base raw material), coconut oil (3% of the mass of the fine particulate reactant), and sodium tripolyphosphate (1% of the mass of the fine particulate reactant) were wet ball milled with a ball-to-material ratio of 2:1 and a water-to-material ratio of 0.6:1 for 3 hours. Then, the base raw material and polyvinyl alcohol 1788 (3.5% of the mass of the base raw material) were added and ball milled for another 10 hours to obtain a slurry with a particle size of 1.0% residue on a 325-mesh sieve.

[0050] (3) Spray granulation of the slurry with an inlet air temperature of 350°C and an outlet temperature of 120°C to obtain a green body powder with a moisture content of 6%.

[0051] (4) Mix coarse granular decorative material (30% of the mass of the base raw material of the green body) and glycerin (0.6% of the mass of the coarse granular decorative material) at 200 r / min for 20 min, then add the green body powder and continue mixing for 15 min.

[0052] (5) The mixed powder is aged for 24 hours, then pressed and molded (pressure 25MPa, holding pressure for 5s), and dried.

[0053] (6) The glaze raw materials, by mass percentage, include the following components: 40% potassium feldspar, 20% quartz powder, 15% kaolin, 12% dolomite, 10% fine-particle reactant, and 3% cashew phenol glycidyl ether. Water is added, the mixture is stirred, wet-milled for 6 hours, and 0.05% residue is obtained after passing through a 325-mesh sieve, resulting in a glaze with a solid content of 60%. The glaze is then applied by spraying, with a glaze layer thickness of 0.4 ± 0.02 mm.

[0054] (7) Finally, the temperature is raised to 1190℃ for firing. The heating rate is 50℃ / h and the firing cycle is 60min to obtain building ceramics.

[0055] Example 3

[0056] (1) The waste porcelain powder is sourced from high-temperature daily-use porcelain fired at 1350℃. The waste porcelain powder comprises the following chemical composition by mass percentage: SiO2 70%, Al2O3 23%, K2O+Na2O 5%, CaO+MgO 1%, and other metal oxides 1%. The waste porcelain powder is divided into fine-particle reactive material with a particle size of 0.05~0.15mm and coarse-particle decorative material with a particle size of 0.425~0.85mm. The basic raw materials for the body comprise the following components by mass percentage: kaolin 45%, porcelain stone 35%, potassium feldspar 15%, and talc 5%.

[0057] (2) The fine particulate reactant (25% of the mass of the base raw material), coconut oil (2% of the mass of the fine particulate reactant) and sodium tripolyphosphate (0.7% of the mass of the fine particulate reactant) were wet ball milled with a ball-to-material ratio of 2:1 and a water-to-material ratio of 0.6:1 for 2 hours. Then, the base raw material and polyvinyl alcohol 1788 (3% of the mass of the base raw material) were added and ball milled for another 7 hours to obtain a slurry with a particle size of 1.5% residue on a 325-mesh sieve.

[0058] (3) Spray granulation of the slurry with an inlet air temperature of 300℃ and an outlet temperature of 100℃ to obtain a green body powder with a moisture content of 8%.

[0059] (4) Mix coarse granular decorative material (15% of the mass of the base raw material of the green body) and glycerin (0.5% of the mass of the coarse granular decorative material) at 150 r / min for 20 min, then add the green body powder and continue mixing for 10 min.

[0060] (5) The mixed powder is aged for 24 hours, then pressed and molded (pressure 20MPa, holding pressure for 3s), and dried.

[0061] (6) The glaze raw materials, by mass percentage, include the following components: 42% potassium feldspar, 23% quartz powder, 11% kaolin, 13% dolomite, 9% fine-particle reactant, and 2% cashew phenol glycidyl ether. Water is added, the mixture is stirred, wet-milled for 6 hours, and 0.05% residue is obtained after passing through a 325-mesh sieve, resulting in a glaze with a solid content of 60%. The glaze is then applied by spraying, with a glaze layer thickness of 0.4 ± 0.02 mm.

[0062] (7) Finally, the temperature is raised to 1220℃ for firing. The heating rate is 50℃ / h and the firing cycle is 55min to obtain building ceramics.

[0063] Example 4

[0064] (1) The waste porcelain powder is sourced from high-temperature daily-use porcelain fired at 1300℃. The waste porcelain powder, by mass percentage, includes the following chemical composition: SiO2 69%, Al2O3 23%, K2O+Na2O 4%, CaO+MgO 2%, and other metal oxides 2%. The waste porcelain powder is divided into fine-particle reactive material with a particle size of 0.05~0.15mm and coarse-particle decorative material with a particle size of 0.425~0.85mm. The basic raw materials for the body, by mass percentage, include the following components: kaolin 30%, ball clay 20%, porcelain stone 30%, potassium feldspar 15%, and talc 5%.

[0065] (2) The fine particulate reactant (20% of the mass of the base raw material), coconut oil (2% of the mass of the fine particulate reactant), and sodium tripolyphosphate (0.7% of the mass of the fine particulate reactant) were wet ball milled with a ball-to-material ratio of 2:1 and a water-to-material ratio of 0.6:1 for 2 hours. Then, the base raw material and polyvinyl alcohol 1788 (2.5% of the mass of the base raw material) were added and ball milled for another 6 hours to obtain a slurry with a particle size of 1.7% residue on a 325-mesh sieve.

[0066] (3) Spray granulation of the slurry with an inlet air temperature of 330°C and an outlet temperature of 115°C to obtain a green body powder with a moisture content of 7%.

[0067] (4) Mix coarse granular decorative material (35% of the mass of the base raw material of the green body) and glycerin (0.9% of the mass of the coarse granular decorative material) at 170 r / min for 10 min, then add the green body powder and continue mixing for 20 min.

[0068] (5) The mixed powder is aged for 24 hours, then pressed and molded (pressure 23MPa, holding pressure for 4s), and dried.

[0069] (6) The glaze raw materials, by mass percentage, include the following components: 38% potassium feldspar, 23% quartz powder, 15% kaolin, 10% dolomite, 10% fine-particle reactant, and 4% cashew phenol glycidyl ether. Water is added, the mixture is stirred, wet-milled for 6 hours, and 0.05% residue is obtained after passing through a 325-mesh sieve, resulting in a glaze with a solid content of 60%. The glaze is then applied by spraying, with a glaze layer thickness of 0.4 ± 0.02 mm.

[0070] (7) Finally, the temperature is raised to 1210℃ for firing. The heating rate is 50℃ / h and the firing cycle is 45min to obtain building ceramics.

[0071] Comparative Example 1

[0072] This comparative example uses the same steps as Example 1 to prepare building ceramics, except that coconut oil and sodium tripolyphosphate were not added.

[0073] (1) The waste porcelain powder is sourced from medium-temperature daily-use porcelain fired at 1200℃. The waste porcelain powder, by mass percentage, includes the following chemical composition: SiO2 69%, Al2O3 19%, K2O+Na2O 7%, CaO+MgO 3%, and other metal oxides 2%. The waste porcelain powder is divided into fine-particle reactive materials with a particle size of 0.05~0.15mm and coarse-particle decorative materials with a particle size of 0.425~0.85mm. The basic raw materials for the body, by mass percentage, include the following components: kaolin 50%, porcelain stone 37%, potassium feldspar 10%, and talc 3%.

[0074] (2) The fine particulate reactant (30% of the mass of the green body base raw material), the green body base raw material and polyvinyl alcohol 1788 (2.5% of the mass of the green body base raw material) were wet ball milled with a ball-to-material ratio of 2:1 and a water-to-material ratio of 0.6:1 for 10 hours to obtain a slurry with a particle size of 1.3% on a 325 mesh sieve.

[0075] (3) Spray granulation of the slurry with an inlet air temperature of 320°C and an outlet air temperature of 110°C to obtain a green body powder with a moisture content of 7%.

[0076] (4) Mix coarse granular decorative material (20% of the mass of the base raw material of the green body) and glycerin (0.6% of the mass of the coarse granular decorative material) at 180 r / min for 10 min, then add the green body powder and continue mixing for 15 min.

[0077] (5) The mixed powder is aged for 24 hours, then pressed and molded (pressure 22MPa, holding pressure for 4s), and dried.

[0078] (6) The glaze raw materials, by mass percentage, include the following components: 40% potassium feldspar, 23% quartz powder, 15% kaolin, 10% dolomite, 9% fine-particle reactant, and 3% cashew phenol glycidyl ether. Water is added, the mixture is stirred, wet-milled for 6 hours, and 0.05% residue is obtained after passing through a 325-mesh sieve, resulting in a glaze with a solid content of 60%. The glaze is then applied by spraying, with a glaze layer thickness of 0.4 ± 0.02 mm.

[0079] (7) Finally, the temperature is raised to 1200℃ for firing. The heating rate is 50℃ / h and the firing cycle is 50min to obtain building ceramics.

[0080] Comparative Example 2

[0081] This comparative example uses the same steps as Example 1 to prepare building ceramics, the only difference being that the amount of coconut oil added is too much compared to sodium tripolyphosphate.

[0082] (1) The waste porcelain powder is sourced from medium-temperature daily-use porcelain fired at 1200℃. The waste porcelain powder, by mass percentage, includes the following chemical composition: SiO2 69%, Al2O3 19%, K2O+Na2O 7%, CaO+MgO 3%, and other metal oxides 2%. The waste porcelain powder is divided into fine-particle reactive materials with a particle size of 0.05~0.15mm and coarse-particle decorative materials with a particle size of 0.425~0.85mm. The basic raw materials for the body, by mass percentage, include the following components: kaolin 50%, porcelain stone 37%, potassium feldspar 10%, and talc 3%.

[0083] (2) The fine particulate reactant (30% of the mass of the base raw material), coconut oil (4% of the mass of the fine particulate reactant) and sodium tripolyphosphate (0.8% of the mass of the fine particulate reactant) were wet ball milled with a ball-to-material ratio of 2:1 and a water-to-material ratio of 0.6:1 for 2 hours. Then, the base raw material and polyvinyl alcohol 1788 (2.5% of the mass of the base raw material) were added and ball milled for another 8 hours to obtain a slurry with a particle size of 1.2% residue on a 325 mesh sieve.

[0084] (3) Spray granulation of the slurry with an inlet air temperature of 320°C and an outlet air temperature of 110°C to obtain a green body powder with a moisture content of 7%.

[0085] (4) Mix coarse granular decorative material (20% of the mass of the base raw material of the green body) and glycerin (0.6% of the mass of the coarse granular decorative material) at 180 r / min for 10 min, then add the green body powder and continue mixing for 15 min.

[0086] (5) The mixed powder is aged for 24 hours, then pressed and molded (pressure 22MPa, holding pressure for 4s), and dried.

[0087] (6) The glaze raw materials, by mass percentage, include the following components: 40% potassium feldspar, 23% quartz powder, 15% kaolin, 10% dolomite, 9% fine-particle reactant, and 3% cashew phenol glycidyl ether. Water is added, the mixture is stirred, wet-milled for 6 hours, and 0.05% residue is obtained after passing through a 325-mesh sieve, resulting in a glaze with a solid content of 60%. The glaze is then applied by spraying, with a glaze layer thickness of 0.4 ± 0.02 mm.

[0088] (7) Finally, the temperature is raised to 1200℃ for firing. The heating rate is 50℃ / h and the firing cycle is 50min to obtain building ceramics.

[0089] Comparative Example 3

[0090] This comparative example uses the same steps as Example 1 to prepare building ceramics, the only difference being that glycerol is used instead of coconut oil.

[0091] (1) The waste porcelain powder is sourced from medium-temperature daily-use porcelain fired at 1200℃. The waste porcelain powder, by mass percentage, includes the following chemical composition: SiO2 69%, Al2O3 19%, K2O+Na2O 7%, CaO+MgO 3%, and other metal oxides 2%. The waste porcelain powder is divided into fine-particle reactive materials with a particle size of 0.05~0.15mm and coarse-particle decorative materials with a particle size of 0.425~0.85mm. The basic raw materials for the body, by mass percentage, include the following components: kaolin 50%, porcelain stone 37%, potassium feldspar 10%, and talc 3%.

[0092] (2) The fine particulate reactant (30% of the mass of the base raw material), glycerol (2.2% of the mass of the fine particulate reactant) and sodium tripolyphosphate (0.8% of the mass of the fine particulate reactant) were wet ball milled with a ball-to-material ratio of 2:1 and a water-to-material ratio of 0.6:1 for 2 hours. Then, the base raw material of the green body and polyvinyl alcohol 1788 (2.5% of the mass of the base raw material of the green body) were added and ball milled for another 8 hours to obtain a slurry with a particle size of 1.2% residue on a 325 mesh sieve.

[0093] (3) Spray granulation of the slurry with an inlet air temperature of 320°C and an outlet air temperature of 110°C to obtain a green body powder with a moisture content of 7%.

[0094] (4) Mix coarse granular decorative material (20% of the mass of the base raw material of the green body) and glycerin (0.6% of the mass of the coarse granular decorative material) at 180 r / min for 10 min, then add the green body powder and continue mixing for 15 min.

[0095] (5) The mixed powder is aged for 24 hours, then pressed and molded (pressure 22MPa, holding pressure for 4s), and dried.

[0096] (6) The glaze raw materials, by mass percentage, include the following components: 40% potassium feldspar, 23% quartz powder, 15% kaolin, 10% dolomite, 9% fine-particle reactant, and 3% cashew phenol glycidyl ether. Water is added, the mixture is stirred, wet-milled for 6 hours, and 0.05% residue is obtained after passing through a 325-mesh sieve, resulting in a glaze with a solid content of 60%. The glaze is then applied by spraying, with a glaze layer thickness of 0.4 ± 0.02 mm.

[0097] (7) Finally, the temperature is raised to 1200℃ for firing. The heating rate is 50℃ / h and the firing cycle is 50min to obtain building ceramics.

[0098] Comparative Example 4

[0099] This comparative example uses the same steps as Example 1 to prepare building ceramics, the only difference being that glycerol was not added.

[0100] (1) The waste porcelain powder is sourced from medium-temperature daily-use porcelain fired at 1200℃. The waste porcelain powder, by mass percentage, includes the following chemical composition: SiO2 69%, Al2O3 19%, K2O+Na2O 7%, CaO+MgO 3%, and other metal oxides 2%. The waste porcelain powder is divided into fine-particle reactive material with a particle size of 0.05~0.15mm and coarse-particle decorative material with a particle size of 0.425~0.85mm. The basic raw materials for the body include the following components by mass percentage: kaolin 50%, porcelain stone 37%, potassium feldspar 10%, and talc 3%.

[0101] (2) The fine particulate reactant (30% of the mass of the base raw material), coconut oil (2.2% of the mass of the fine particulate reactant) and sodium tripolyphosphate (0.8% of the mass of the fine particulate reactant) were wet ball milled with a ball-to-material ratio of 2:1 and a water-to-material ratio of 0.6:1 for 2 hours. Then, the base raw material and polyvinyl alcohol 1788 (2.5% of the mass of the base raw material) were added and ball milled for another 8 hours to obtain a slurry with a particle size of 1.2% residue on a 325-mesh sieve.

[0102] (3) Spray granulation of the slurry with an inlet air temperature of 320°C and an outlet air temperature of 110°C to obtain a green body powder with a moisture content of 7%.

[0103] (4) Mix the coarse-particle decorative material (20% of the mass of the base raw material) and the green body powder at 180 r / min for 30 min.

[0104] (5) The mixed powder is aged for 24 hours, then pressed and molded (pressure 22MPa, holding pressure for 4s), and dried.

[0105] (6) The glaze raw materials, by mass percentage, include the following components: 40% potassium feldspar, 23% quartz powder, 15% kaolin, 10% dolomite, 9% fine-particle reactant, and 3% cashew phenol glycidyl ether. Water is added, the mixture is stirred, wet-milled for 6 hours, and 0.05% residue is obtained after passing through a 325-mesh sieve, resulting in a glaze with a solid content of 60%. The glaze is then applied by spraying, with a glaze layer thickness of 0.4 ± 0.02 mm.

[0106] (7) Finally, the temperature is raised to 1200℃ for firing. The heating rate is 50℃ / h and the firing cycle is 50min to obtain building ceramics.

[0107] Comparative Example 5

[0108] This comparative example uses the same steps as Example 1 to prepare building ceramics, the only difference being that butyl glycidyl ether is added to the glaze instead of cashew phenol glycidyl ether.

[0109] (1) The waste porcelain powder is sourced from medium-temperature daily-use porcelain fired at 1200℃. The waste porcelain powder, by mass percentage, includes the following chemical composition: SiO2 69%, Al2O3 19%, K2O+Na2O 7%, CaO+MgO 3%, and other metal oxides 2%. The waste porcelain powder is divided into fine-particle reactive material with a particle size of 0.05~0.15mm and coarse-particle decorative material with a particle size of 0.425~0.85mm. The basic raw materials for the body include the following components by mass percentage: kaolin 50%, porcelain stone 37%, potassium feldspar 10%, and talc 3%.

[0110] (2) The fine particulate reactant (30% of the mass of the base raw material), coconut oil (2.2% of the mass of the fine particulate reactant) and sodium tripolyphosphate (0.8% of the mass of the fine particulate reactant) were wet ball milled with a ball-to-material ratio of 2:1 and a water-to-material ratio of 0.6:1 for 2 hours. Then, the base raw material and polyvinyl alcohol 1788 (2.5% of the mass of the base raw material) were added and ball milled for another 8 hours to obtain a slurry with a particle size of 1.2% residue on a 325-mesh sieve.

[0111] (3) Spray granulation of the slurry with an inlet air temperature of 320°C and an outlet air temperature of 110°C to obtain a green body powder with a moisture content of 7%.

[0112] (4) Mix coarse granular decorative material (20% of the mass of the base raw material of the green body) and glycerin (0.6% of the mass of the coarse granular decorative material) at 180 r / min for 10 min, then add the green body powder and continue mixing for 15 min.

[0113] (5) The mixed powder is aged for 24 hours, then pressed and molded (pressure 22MPa, holding pressure for 4s), and dried.

[0114] (6) The glaze raw materials, by mass percentage, include the following components: 40% potassium feldspar, 23% quartz powder, 15% kaolin, 10% dolomite, 9% fine-particle reactant, and 3% butyl glycidyl ether. Water is added, the mixture is stirred, wet-milled for 6 hours, and 0.05% residue is obtained after passing through a 325-mesh sieve, resulting in a glaze with a solid content of 60%. The glaze is then applied by spraying, with a glaze layer thickness of 0.4 ± 0.02 mm.

[0115] (7) Finally, the temperature is raised to 1200℃ for firing. The heating rate is 50℃ / h and the firing cycle is 50min to obtain building ceramics.

[0116] Table 1 Performance test results and surface decorative effects of architectural ceramics

[0117]

[0118] As shown in Table 1, the waste porcelain powder content is the total amount of fine-particle reactant and coarse-particle decorative material relative to the mass content of the basic raw materials of the green body. This invention can achieve high strength under high waste porcelain powder content conditions, while also... Figure 1 As shown, ceramics can naturally exhibit speckled or star-like decorative textures, forming a unique aesthetic identity for the product and enhancing its added value and market competitiveness. And as... Figure 2 As shown, Comparative Example 1, due to the absence of coconut oil and sodium tripolyphosphate, exhibited poor dispersibility of fine-particle waste ceramic powder, significantly impacting ceramic strength. This also affected the subsequent dispersion of coarse particles, leading to agglomeration and consequently, crack formation at the bonding interface during sintering, further reducing ceramic strength. Figure 3As shown, the relatively large amount of coconut oil added in Comparative Example 2 will disrupt the emulsification system, affecting the dispersion effect. Excessive coconut oil will also hinder the co-sintering of fine particles and raw materials, affecting interfacial bonding and thus impacting the ceramic strength. Figure 4 As shown, Comparative Example 3 uses glycerin instead of coconut oil. Glycerin can wet coarse particles, but when used for fine particle dispersion, the synergistic effect between glycerin, sodium tripolyphosphate, and polyvinyl alcohol is poor, resulting in poor dispersion of fine particles, poor densification of the body, and internal porosity and stress leading to pinholes and microcracks in the glaze. Figure 5 and Figure 6 As shown in Comparative Examples 4 and 5, glycerol is beneficial for improving the uniformity of coarse particle distribution, and cashew phenol glycidyl ether can also promote glaze spreading. The glaze can evenly cover the raised areas of coarse particles. Furthermore, the reaction and combination of glycerol and cashew phenol glycidyl ether in the glaze can effectively enhance the interfacial effect (while the addition of short alkyl chain glycidyl ether to the glaze will result in insufficient improvement in the glaze-body bonding strength). Therefore, both are indispensable for ceramic materials to obtain good surface decoration effects.

[0119] Unless otherwise specified, the raw materials and equipment used in this invention are all commonly used in the field; unless otherwise specified, the methods used in this invention are all conventional methods in the field.

[0120] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, alterations, and equivalent transformations made to the above embodiments based on the technical essence of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A type of building ceramic reinforced with graded waste ceramic powder, characterized in that, The raw materials for the architectural ceramics include base materials and glazes. The base materials include body base materials, waste porcelain powder, coconut oil, sodium tripolyphosphate, polyvinyl alcohol, and glycerin. The body base materials, by mass percentage, include the following components: clay 45-55%, porcelain stone 30-37%, feldspar 10-15%, and talc 0-5%. The waste porcelain powder includes fine-particle reactant accounting for 20-50% of the mass of the body base materials and coarse-particle decorative material accounting for 15-35% of the mass of the body base materials. The particle size of the fine-particle reactant is 0.05-0.15 mm, and the particle size of the coarse-particle decorative material is 0.425-0.85 mm. The amount of coconut oil added is 2-3% of the mass of the fine-particle reactant in the waste porcelain powder. The amount of sodium tripolyphosphate added is 0.7-1% of the mass of the fine-particle reactant in the waste porcelain powder. The glaze includes fine-particle reactant and cashew phenol glycidyl ether.

2. The building ceramic reinforced with graded waste porcelain powder as described in claim 1, characterized in that, The waste ceramic powder comprises the following chemical composition by mass percentage: SiO2 68~70%, Al2O3 19~23%, K2O+Na2O 4~7%, CaO+MgO 1~3%, and other metal oxides ≤3%; the other metal oxides include one or more of ZnO, BaO, Fe2O3, and TiO2.

3. The building ceramic reinforced with graded waste porcelain powder as described in claim 1, characterized in that, The amount of polyvinyl alcohol added is 2.5-3.5% of the mass of the base raw material of the green body; the amount of glycerol added is 0.5-0.9% of the mass of the coarse-particle decorative material.

4. The building ceramic reinforced with graded waste porcelain powder as described in claim 1, characterized in that, The clay is one or more of kaolin, kaolinite, and ball clay; the feldspar is one or more of potassium feldspar and sodium feldspar.

5. The building ceramic reinforced with graded waste porcelain powder as described in claim 1, characterized in that, The glaze comprises the following components by mass percentage: 38-42% potassium feldspar, 20-23% quartz powder, 11-15% kaolin, 10-13% dolomite, 9-10% fine-particle reactant, and 2-4% cashew phenol glycidyl ether.

6. A method for preparing building ceramics reinforced with graded waste ceramic powder as described in any one of claims 1-5, characterized in that, Includes the following steps: (1) The waste porcelain powder is divided into fine particulate reactive material with a particle size of 0.05~0.15mm and coarse particulate decorative material with a particle size of 0.425~0.85mm; (2) Wet ball mill the fine particulate reactant, coconut oil and sodium tripolyphosphate, then add the base raw material of the green body and polyvinyl alcohol and continue ball milling to obtain a slurry; (3) Spray granulation of the slurry to obtain green body powder; (4) Mix the coarse-particle decorative material and glycerin, then add the blank powder and continue mixing to obtain the base material; (5) After the base material is aged, pressed, dried, glazed and fired, the building ceramics can be obtained.

7. The preparation method according to claim 6, characterized in that, In step (2), the ball milling is continued until the particle size of the resulting slurry is ≤2% on a 325-mesh sieve.

8. The preparation method according to claim 6, characterized in that, In step (3), the conditions for spray granulation are: inlet air temperature 300~350℃, outlet temperature 100~120℃; and the moisture content of the green body powder is 6~8%.

9. The preparation method according to claim 6, characterized in that, In step (4), the stirring and mixing is carried out at 150~200r / min for 10~20min, and the mixing time is continued for 10~20min.

10. The preparation method according to claim 6, characterized in that, In step (5), the firing temperature is 1190~1220℃ and the firing cycle is 45~60min.

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