Lightweight domestic ceramic material and method for its production

Abstract

The application discloses a kind of light daily ceramic materials and preparation method thereof, it is related to ceramic material technical field.The application discloses a kind of preparation method of light daily ceramic materials, including the following steps: according to the blank body raw material proportion configuration raw material, crushing, ball milling, sieving, stale treatment, obtain green paste;Utilize green paste to make blank body, blank body drying, repair blank, biscuit, obtain blank body;Glaze is applied on the surface of blank body, is fired into shape, cooling, obtain light daily ceramic materials;Blank body includes the following weight parts of raw materials: 48-60 parts kaolin, 17-23 parts potassium feldspar, 20-26 parts quartz, 1-2 parts functional additives, 2-3 parts talc, 4-8 parts wollastonite, 6-9 parts calcium oxide, 15-25 parts barium carbonate.In blank body, the strength of blank body is effectively improved by adding functional additives, so that the blank body still maintains excellent flexural strength during thinning process.

Description

Technical Field

[0001] This invention relates to the field of ceramic materials technology, specifically to a lightweight daily-use ceramic material and its preparation method. Background Technology

[0002] Mutton fat porcelain, originating from Dehua, Fujian, known as the "Ceramic Capital of the World," is a highly representative category of Chinese white porcelain. Dehua mutton fat porcelain is characterized by its pure, lustrous white glaze, high gloss, warm and smooth color, seamless transparency, high density, and excellent light transmission. It stands out in terms of its body, glaze, and decoration. Traditionally, mutton fat porcelain is made primarily from kaolin, quartz, and feldspar. Through raw material processing, thin-walled forming, and high-temperature firing, it achieves the unique effect of being "as white as snow, as thin as paper, and as resonant as a chime." With the rapid development of the ceramics industry and the improvement of people's living standards, mutton fat porcelain has entered modern life. The demand for lightweight and portable mutton fat porcelain is gradually increasing. How to achieve lightweight improvements while maintaining the aesthetic characteristics of mutton fat porcelain has become a key direction for technological breakthroughs in the industry.

[0003] Currently, lightweight ceramic technology mainly revolves around two approaches: increasing the porosity of the body and thinning the body. Porosity control reduces material density by introducing porous structures, but this method has significant drawbacks: First, the porous structure disrupts the characteristic dense body of mutton fat jade porcelain, leading to decreased translucency and impaired surface smoothness, making it difficult to meet the visual texture requirements of high-end products; second, the porous structure significantly reduces the material's mechanical strength, lowering its flexural strength and making it prone to fracture due to external impact or thermal stress. In contrast, thinning the body, through optimized forming processes, reduces the body thickness from the traditional 2-3 mm to below 1 mm, achieving lightweighting while maintaining the porcelain's density and translucency, better meeting the aesthetic and functional needs of mutton fat jade porcelain. However, the core bottleneck of the thinning process is that as the body thickness decreases, the bending strength of the green body drops sharply during drying, firing and use. Under conventional formulas and processes, the bending strength of a 1mm thick green body is generally less than 30MPa, which makes it difficult to pass the drop test of the national standard GB / T 3299-2011 "Test Method for Impact Resistance of Daily-use Ceramic Ware", which seriously restricts its practical application. Summary of the Invention

[0004] The purpose of this invention is to provide a lightweight daily-use ceramic material and its preparation method, thereby solving the following technical problems:

[0005] To achieve lightweight modification, existing mutton fat jade porcelain requires thinning of the body. However, the flexural strength of the thinned body decreases sharply during drying, firing, and use, making it difficult to meet the impact resistance requirements of daily-use ceramics.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A method for preparing a lightweight daily-use ceramic material includes the following steps:

[0008] S1: Prepare raw materials according to the proportion of raw materials for the green body, crush, ball mill, sieve, and age to obtain green slurry;

[0009] S2: Use slurry to make the blank body, dry the blank body, trim the blank body, and bisque fire to obtain the bisque body;

[0010] S3: Glaze the surface of the unglazed ceramic body, fire it to form a shape, and cool it to obtain a lightweight daily-use ceramic material;

[0011] The green body comprises the following raw materials in parts by weight: 48-60 parts kaolin, 17-23 parts potassium feldspar, 20-26 parts quartz, 1-2 parts functional additives, 2-3 parts talc, 4-8 parts wollastonite, 6-9 parts calcium oxide, and 15-25 parts barium carbonate.

[0012] The preparation method of functional additives includes the following steps:

[0013] A1: γ-aminopropyltriethoxysilane, ethanol, and water were mixed and the pH was adjusted to 4.5-5.0. ZrO2@alumina was added to the reaction vessel and dispersed evenly. The temperature was controlled at 50-60℃ and the reaction was kept at this temperature for 6-12 hours. After centrifugation, washing, and drying, organic ZrO2@alumina was obtained.

[0014] A2: In a nitrogen atmosphere, bis[3-(triethoxysilyl)propyl]-disulfide (CAS: 56706-10-6), anhydrous toluene, and acetic acid were added to a reaction vessel and dispersed evenly. Organic ZrO2@alumina was then added. The temperature was controlled at 40-50℃ and the reaction was maintained at this temperature for 4-8 hours. The temperature was then raised to 70-80℃ and the reaction was maintained at this temperature for 2-4 hours. After centrifugation, washing, and drying, modified alumina was obtained.

[0015] A3: Carboxymethyl cellulose and deionized water are added to a reaction vessel and dispersed evenly. The pH is adjusted to 4.5-5.0. EDC (CAS: 25952-53-8) and NHS (CAS: 6066-82-6) are added and activated for 0.5-1 h. Modified alumina is added and the pH is adjusted to 7.0-7.5. The reaction is carried out at a temperature of 50-60℃ with stirring for 6-9 h. The mixture is then purified and dried to obtain the functional additive.

[0016] As a further embodiment of the present invention: the addition ratio of γ-aminopropyltriethoxysilane, ethanol, water and ZrO2@alumina in A1 is 1-1.5mL:80-95mL:5-20mL:10g.

[0017] As a further embodiment of the present invention: the addition ratio of bis[3-(triethoxysilyl)propyl]-disulfide, anhydrous toluene, acetic acid, and organic ZrO2@alumina in A2 is 1.5-3g: 25-50mL: 0.15-0.3g: 10g.

[0018] As a further embodiment of the present invention: the addition ratio of carboxymethyl cellulose, deionized water, EDC, NHS and modified alumina in A3 is 10g: 300-600mL: 0.05-0.1g: 0.035-0.07g: 1-1.5g.

[0019] As a further aspect of the present invention, the method for preparing ZrO2@alumina includes the following steps:

[0020] Nano-alumina and isopropanol were added to a reaction vessel and dispersed evenly. Water and zirconium isopropoxide were mixed and added to the reaction vessel. The temperature was controlled at 70-80℃ and the hydrolysis reaction was carried out for 4-8 hours. The mixture was then filtered, washed with water, dried, and calcined to obtain core-shell particles. The core-shell particles were dispersed in a 75 wt% hydrogen peroxide aqueous solution. The temperature was controlled at 70-80℃ and the mixture was ultrasonically treated for 2-4 hours. The mixture was then centrifuged, washed until neutral, and dried to obtain ZrO2@alumina.

[0021] As a further aspect of the present invention: the addition ratio of nano-alumina, isopropanol, water, and zirconium isopropoxide is 1g: 20mL-100mL: 0.075-0.3mL: 0.5mL-1mL.

[0022] As a further aspect of the present invention, the glaze comprises the following raw materials by weight percentage: 40-45 parts potassium feldspar, 13-18 parts shell powder, 18-24 parts quartz, 6-9 parts barium carbonate, 12-14 parts zirconium silicate, 1-2 parts zinc oxide, and 3-6 parts talc.

[0023] As a further aspect of the present invention: the process of making blanks from slurry in S2 is manual throwing or slip casting.

[0024] As a further aspect of the present invention, the specific process for drying the green body in S2 is as follows: controlling the ambient temperature at 20-35℃ and letting it stand for 5-8 hours.

[0025] As a further aspect of the present invention, the specific process of bisque firing in S2 is as follows: the trimmed body is placed in a kiln, and the bisque firing temperature is 800-900℃ for 2-4 hours. Bisque firing helps to remove organic matter from the body and enhances the strength of the body, facilitating subsequent glazing.

[0026] As a further aspect of the present invention: the ball milling process in S1 specifically involves adding the pulverized raw material into a ball mill, adding water equal to 70-80% of the total weight of the raw material, and performing wet ball milling.

[0027] As a further aspect of the present invention, the specific process for firing in S3 is as follows:

[0028] First stage of heating: Control the heating rate to 80-100℃ / h, heat to 400-500℃, and hold for 1-1.5h; heat slowly to avoid cracking;

[0029] Two-stage heating: control the heating rate at 150-200℃ / h, heat to 900-1100℃, and hold for 2-4 hours;

[0030] Three-stage heating: control the heating rate at 50-70℃ / h, heat to 1280-1320℃, and hold for 1-2 hours; promote vitrification and densification.

[0031] As a further aspect of the present invention: CO / CH4 gas with a volume ratio of 1:1 is introduced during the two-stage heating process to reduce Fe2O3 to FeO and eliminate the yellow tint.

[0032] As a further aspect of the present invention: CO / CH4 gas with a volume ratio of 7:3 is introduced in a three-stage heating process to enhance the reduction reaction of Fe2O3 to FeO.

[0033] As a further aspect of the present invention: the three-stage heat preservation process uses CO / CH4 gas with a volume ratio of 6:4 to balance reduction and glaze leveling.

[0034] A lightweight daily-use ceramic material, prepared by any one of the above methods.

[0035] The beneficial effects of this invention are:

[0036] (1) This application first deposits a ZrO2 layer on the surface of nano-alumina using zirconium isopropoxide hydrolysis condensation to obtain a ZrO2@alumina core-shell composite oxide; then treats the ZrO2@alumina core-shell composite oxide with hydrogen peroxide aqueous solution to obtain ZrO2@alumina with a surface rich in hydroxyl groups; this application uses KH550 to organically treat ZrO2@alumina and then introduces bis[3-(triethoxysilyl)propyl]-disulfide to form a double bond of -Si-O-Zr- and -SS- to obtain modified alumina; finally, this application uses the amino groups on the surface of modified alumina to react with the carboxyl groups of activated carboxymethyl cellulose to obtain a functional additive. This application links ZrO2@alumina and carboxymethyl cellulose through covalent bonds to form a three-dimensional network, effectively achieving inorganic-organic synergistic effect, possessing both bonding and inorganic reinforcement functions, and avoiding the problem of uneven dispersion in traditional physical mixing.

[0037] The functional additives prepared in this application fill the micropores of the green body, improving the flexural strength of the material without affecting its light transmittance. Carboxymethyl cellulose in the functional additives acts as a temporary binder for the green body, improving its plasticity and effectively avoiding the risk of cracking during drying. This application also deposits a zirconium dioxide layer on the surface of nano-alumina. The zirconium dioxide layer has a phase transformation toughening effect, absorbing crack propagation energy; moreover, the thermal expansion coefficient of the zirconium dioxide layer matches that of the ceramic body, further reducing microcracks during firing. This application also modifies the ZrO2@alumina surface with KH550 and bis[3-(triethoxysilyl)propyl]-disulfide. The disulfide bonds grafted onto the ZrO2@alumina surface break during low-temperature firing, causing particle slippage and stress release. This inhibits cracking of the green body during thermal expansion, reducing the problem of easy cracking during material sintering.

[0038] (2) This application uses kaolin, quartz, potassium feldspar, functional additives, and a small amount of auxiliary materials as raw materials for the green body. Kaolin provides plasticity and skeletal support for the material, quartz enhances the strength of the green body and reduces firing shrinkage, and potassium feldspar melts at high temperature to form a glassy phase, promoting material densification. Auxiliary materials such as talc play a role in adjusting the coefficient of thermal expansion. In addition, during the firing and molding process of the ceramic material, CO / CH4 gas is introduced to reduce Fe2O3 in the effective raw materials to FeO, eliminating the yellow tint and improving the whiteness of the ceramic material. Detailed Implementation

[0039] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0040] Example 1: The preparation method of the functional additive includes the following steps:

[0041] A1: 10g of nano-alumina and 200mL of isopropanol were added to a reaction vessel and dispersed evenly. 0.75mL of water and 5mL of zirconium isopropoxide were mixed and added to the reaction vessel. The temperature was controlled at 70℃ and the hydrolysis reaction was carried out for 4 hours. After filtration, washing with water, drying, and calcination at 600℃ for 2 hours in air atmosphere, core-shell particles were obtained. The core-shell particles were dispersed in 75vt% hydrogen peroxide aqueous solution, and the temperature was controlled at 70℃ and ultrasonically treated for 2 hours. After centrifugation and washing until neutral, and drying, ZrO2@alumina was obtained.

[0042] A2: Mix 1 mL of γ-aminopropyltriethoxysilane, 80 mL of ethanol, and 20 mL of water, adjust the pH to 4.5, add 10 g of ZrO2@alumina to the reaction vessel and disperse evenly, control the temperature at 50℃ and keep the reaction at this temperature for 6 h, centrifuge, wash, and dry to obtain organic ZrO2@alumina;

[0043] A3: In a nitrogen atmosphere, 1.5 g of bis[3-(triethoxysilyl)propyl]-disulfide (CAS: 56706-10-6), 25 mL of anhydrous toluene, and 0.15 g of acetic acid were added to a reaction vessel and dispersed evenly. Then, 10 g of organic ZrO2@alumina was added. The temperature was controlled at 40℃ and the reaction was maintained at this temperature for 4 h. The temperature was then raised to 70℃ and the reaction was maintained at this temperature for 2 h. After centrifugation, washing, and drying, modified alumina was obtained.

[0044] A4: Add 10g of carboxymethyl cellulose and 300mL of deionized water to a reaction vessel and disperse evenly. Adjust the pH to 4.5, add 0.05g of EDC (CAS: 25952-53-8) and 0.035g of NHS (CAS: 6066-82-6), activate for 0.5h, add 1.5g of modified alumina, adjust the pH to 7.0, keep the reaction at 50℃ with stirring for 6h, purify and dry to obtain the functional additive.

[0045] Example 2: The preparation method of the functional additive includes the following steps:

[0046] A1: 10g of nano-alumina and 500mL of isopropanol were added to a reaction vessel and dispersed evenly. 2mL of water and 7mL of zirconium isopropoxide were mixed and added to the reaction vessel. The temperature was controlled at 75℃ and the hydrolysis reaction was carried out for 6 hours. After filtration, washing with water, drying, and calcination at 600℃ for 2 hours in air atmosphere, core-shell particles were obtained. The core-shell particles were dispersed in 75vt% hydrogen peroxide aqueous solution, and the temperature was controlled at 75℃ and ultrasonic treatment was carried out for 3 hours. After centrifugation and washing until neutral, and drying, ZrO2@alumina was obtained.

[0047] A2: Mix 1.2 mL of γ-aminopropyltriethoxysilane, 95 mL of ethanol, and 5 mL of water, adjust the pH to 4.5, add 10 g of ZrO2@alumina to the reaction vessel and disperse evenly, control the temperature at 55℃ and keep the reaction at that temperature for 9 h, centrifuge, wash, and dry to obtain organic ZrO2@alumina;

[0048] A3: In a nitrogen atmosphere, 2.2 g of bis[3-(triethoxysilyl)propyl]-disulfide (CAS: 56706-10-6), 40 mL of anhydrous toluene, and 0.22 g of acetic acid were added to a reaction vessel and dispersed evenly. Then, 10 g of organic ZrO2@alumina was added. The temperature was controlled at 45℃ and the reaction was maintained at this temperature for 6 h. The temperature was then raised to 75℃ and the reaction was maintained at this temperature for 3 h. After centrifugation, washing, and drying, modified alumina was obtained.

[0049] A4: Add 10g of carboxymethyl cellulose and 450mL of deionized water to a reaction vessel and disperse evenly. Adjust the pH to 4.5, add 0.07g of EDC (CAS: 25952-53-8) and 0.05g of NHS (CAS: 6066-82-6), activate for 0.5h, add 1.5g of modified alumina, adjust the pH to 7.5, maintain the temperature at 55℃ and stir for 7.5h, purify and dry to obtain the functional additive.

[0050] Example 3: The preparation method of the functional additive includes the following steps:

[0051] A1: 10g of nano-alumina and 1000mL of isopropanol were added to a reaction vessel and dispersed evenly. 3mL of water and 10mL of zirconium isopropoxide were mixed and added to the reaction vessel. The temperature was controlled at 80℃ and the hydrolysis reaction was carried out for 8 hours. After filtration, washing with water, drying, and calcination at 600℃ for 2 hours in air atmosphere, core-shell particles were obtained. The core-shell particles were dispersed in a 75vt% hydrogen peroxide aqueous solution, and the temperature was controlled at 80℃ and ultrasonically treated for 4 hours. After centrifugation and washing until neutral, and drying, ZrO2@alumina was obtained.

[0052] A2: Mix 1.5 mL of γ-aminopropyltriethoxysilane, 90 mL of ethanol, and 10 mL of water, adjust the pH to 5.0, add 10 g of ZrO2@alumina to the reaction vessel and disperse evenly, control the temperature at 60℃ and keep the reaction at this temperature for 12 h, centrifuge, wash, and dry to obtain organic ZrO2@alumina;

[0053] A3: In a nitrogen atmosphere, 3g of bis[3-(triethoxysilyl)propyl]-disulfide (CAS: 56706-10-6), 50mL of anhydrous toluene, and 0.3g of acetic acid were added to a reaction vessel and dispersed evenly. 10g of organic ZrO2@alumina was added, and the temperature was controlled at 50℃ and the reaction was maintained at this temperature for 8h. The temperature was then raised to 80℃ and the reaction was maintained at this temperature for 4h. After centrifugation, washing, and drying, modified alumina was obtained.

[0054] A4: Add 10g of carboxymethyl cellulose and 600mL of deionized water to a reaction vessel and disperse evenly. Adjust the pH to 5.0, add 0.1g of EDC (CAS: 25952-53-8) and 0.07g of NHS (CAS: 6066-82-6), activate for 1h, add 1.5g of modified alumina, adjust the pH to 7.5, keep the reaction at 60℃ with stirring for 9h, purify and dry to obtain the functional additive.

[0055] Example 4: A method for preparing a lightweight daily-use ceramic material, comprising the following steps:

[0056] S1: 540g kaolin, 210g potassium feldspar, 200g quartz, 15g functional additives prepared in Example 1, 20g talc, 50g wollastonite, 60g calcium oxide, and 170g barium carbonate were pulverized and mixed together, then added to a ball mill with 950mL of water for wet ball milling and sieve through a 400-mesh sieve. The mixture was then aged for 48 hours after being mixed with water to obtain a slurry.

[0057] S2: The slurry is poured and molded to obtain the green body. The green body is dried at 30℃ for 8 hours and then trimmed. The trimmed green body is placed in a kiln and bisque-fired at 800℃ for 3 hours to obtain the bisque body.

[0058] S3: 420g potassium feldspar, 140g seashell powder, 210g quartz, 70g barium carbonate, 130g zirconium silicate, 1.20g zinc oxide, and 3.30g talc are pulverized, ball-milled, and passed through a 400-mesh sieve. Water is added to prepare a glaze with a density of 1.3g / cm³. 3 Glaze;

[0059] S4: Apply glaze to the surface of the unglazed body (glaze amount: 90g / m²) 2 The glazed blanks are placed in a kiln (10m). 3 In the process, the heating rate was controlled at 80℃ / h, the temperature was raised to 440℃, and held for 1.2h; a CO / CH4 (volume ratio 1:1) mixed gas was introduced at a flow rate of 1.1m³. 3 The heating rate was controlled at 170℃ / h, reaching 1100℃ and holding for 2.2h; a CO / CH4 (volume ratio 7:3) mixed gas was introduced at a flow rate of 1.1m³. 3 The heating rate is controlled at 50℃ / h, and the temperature is increased to 1320℃. At 1320℃, a CO / CH4 (volume ratio of 6:4) mixed gas is introduced at a flow rate of 1.1m³. 3 / h, heat preservation for 1.6h, and natural cooling to room temperature to obtain lightweight daily-use ceramic material.

[0060] Example 5: A method for preparing a lightweight daily-use ceramic material, comprising the following steps:

[0061] S1: 540g kaolin, 210g potassium feldspar, 200g quartz, 15g functional additives prepared in Example 2, 20g talc, 50g wollastonite, 60g calcium oxide, and 170g barium carbonate were pulverized and mixed together, then added to a ball mill with 950mL of water for wet ball milling and sieve through a 400-mesh sieve. The mixture was then aged for 48 hours after being mixed with water to obtain a slurry.

[0062] S2: The slurry is poured and molded to obtain the green body. The green body is dried at 30℃ for 8 hours and then trimmed. The trimmed green body is placed in a kiln and bisque-fired at 800℃ for 3 hours to obtain the bisque body.

[0063] S3: 420g potassium feldspar, 140g seashell powder, 210g quartz, 70g barium carbonate, 130g zirconium silicate, 1.20g zinc oxide, and 3.30g talc are pulverized, ball-milled, and passed through a 400-mesh sieve. Water is added to prepare a glaze with a density of 1.3g / cm³. 3 Glaze;

[0064] S4: Apply glaze to the surface of the unglazed body (glaze amount: 90g / m²) 2 The glazed blanks are placed in a kiln (10m). 3 In the process, the heating rate was controlled at 80℃ / h, the temperature was raised to 440℃, and held for 1.2h; a CO / CH4 (volume ratio 1:1) mixed gas was introduced at a flow rate of 1.1m³. 3 The heating rate was controlled at 170℃ / h, reaching 1100℃ and holding for 2.2h; a CO / CH4 (volume ratio 7:3) mixed gas was introduced at a flow rate of 1.1m³. 3 The heating rate is controlled at 50℃ / h, and the temperature is increased to 1320℃. At 1320℃, a CO / CH4 (volume ratio of 6:4) mixed gas is introduced at a flow rate of 1.1m³. 3 / h, heat preservation for 1.6h, and natural cooling to room temperature to obtain lightweight daily-use ceramic material.

[0065] Example 6: A method for preparing a lightweight daily-use ceramic material, comprising the following steps:

[0066] S1: 540g kaolin, 210g potassium feldspar, 200g quartz, 15g functional additives prepared in Example 3, 20g talc, 50g wollastonite, 60g calcium oxide, and 170g barium carbonate were pulverized and mixed together, then added to a ball mill with 950mL of water for wet ball milling and sieve through a 400-mesh sieve. The mixture was then aged for 48 hours after being mixed with water to obtain a slurry.

[0067] S2: The slurry is poured and molded to obtain the green body. The green body is dried at 30℃ for 8 hours and then trimmed. The trimmed green body is placed in a kiln and bisque-fired at 800℃ for 3 hours to obtain the bisque body.

[0068] S3: 420g potassium feldspar, 140g seashell powder, 210g quartz, 70g barium carbonate, 130g zirconium silicate, 1.20g zinc oxide, and 3.30g talc are pulverized, ball-milled, and passed through a 400-mesh sieve. Water is added to prepare a glaze with a density of 1.3g / cm³. 3 Glaze;

[0069] S4: Apply glaze to the surface of the unglazed body (glaze amount: 90g / m²) 2 The glazed blanks are placed in a kiln (10m). 3In the process, the heating rate was controlled at 80℃ / h, the temperature was raised to 440℃, and held for 1.2h; a CO / CH4 (volume ratio 1:1) mixed gas was introduced at a flow rate of 1.1m³. 3 The heating rate was controlled at 170℃ / h, reaching 1100℃ and holding for 2.2h; a CO / CH4 (volume ratio 7:3) mixed gas was introduced at a flow rate of 1.1m³. 3 The heating rate is controlled at 50℃ / h, and the temperature is increased to 1320℃. At 1320℃, a CO / CH4 (volume ratio of 6:4) mixed gas is introduced at a flow rate of 1.1m³. 3 / h, heat preservation for 1.6h, and natural cooling to room temperature to obtain lightweight daily-use ceramic material.

[0070] Comparative Example 1: The preparation method of the functional additive includes the following steps:

[0071] A1: Mix 1.2 mL of γ-aminopropyltriethoxysilane, 95 mL of ethanol, and 5 mL of water, adjust the pH to 4.5, add 10 g of alumina to the reaction vessel and disperse evenly, control the temperature at 55℃ and keep the reaction at that temperature for 9 h, centrifuge, wash, and dry to obtain organic alumina;

[0072] A2: In a nitrogen atmosphere, 2.2 g of bis[3-(triethoxysilyl)propyl]-disulfide (CAS: 56706-10-6), 40 mL of anhydrous toluene, and 0.22 g of acetic acid were added to a reaction vessel and dispersed evenly. Then, 10 g of organo-modified alumina was added. The temperature was controlled at 45℃ and the reaction was maintained at this temperature for 6 h. The temperature was then raised to 75℃ and the reaction was maintained at this temperature for 3 h. After centrifugation, washing, and drying, modified alumina was obtained.

[0073] A3: 10g of carboxymethyl cellulose and 450mL of deionized water were added to a reaction vessel and dispersed evenly. The pH was adjusted to 4.5. 0.07g of EDC (CAS: 25952-53-8) and 0.05g of NHS (CAS: 6066-82-6) were added and activated for 0.5h. 1.5g of modified alumina was added and the pH was adjusted to 7.5. The reaction was carried out at 55℃ with stirring for 7.5h. The mixture was then purified and dried to obtain the functional additive.

[0074] Comparative Example 2: The preparation method of the functional additive includes the following steps:

[0075] A1: 10g of nano-alumina and 500mL of isopropanol were added to a reaction vessel and dispersed evenly. 2mL of water and 7mL of zirconium isopropoxide were mixed and added to the reaction vessel. The temperature was controlled at 75℃ and the hydrolysis reaction was carried out for 6 hours. After filtration, washing with water, drying, and calcination at 600℃ for 2 hours in air atmosphere, core-shell particles were obtained. The core-shell particles were dispersed in 75vt% hydrogen peroxide aqueous solution, and the temperature was controlled at 75℃ and ultrasonic treatment was carried out for 3 hours. After centrifugation and washing until neutral, and drying, ZrO2@alumina was obtained.

[0076] A2: Mix 1.2 mL of γ-aminopropyltriethoxysilane, 95 mL of ethanol, and 5 mL of water, adjust the pH to 4.5, add 10 g of ZrO2@alumina to the reaction vessel and disperse evenly, control the temperature at 55℃ and keep the reaction at that temperature for 9 h, centrifuge, wash, and dry to obtain organic ZrO2@alumina;

[0077] A3: 10g of carboxymethyl cellulose and 450mL of deionized water were added to a reaction vessel and dispersed evenly. The pH was adjusted to 4.5. 0.07g of EDC (CAS: 25952-53-8) and 0.05g of NHS (CAS: 6066-82-6) were added and activated for 0.5h. 1.5g of organic ZrO2@alumina was added and the pH was adjusted to 7.5. The reaction was carried out at 55℃ with stirring for 7.5h. The mixture was then purified and dried to obtain the functional additive.

[0078] Comparative Example 3: The preparation method of the functional additive includes the following steps:

[0079] A1: 10g of nano-alumina and 500mL of isopropanol were added to a reaction vessel and dispersed evenly. 2mL of water and 7mL of zirconium isopropoxide were mixed and added to the reaction vessel. The temperature was controlled at 75℃ and the hydrolysis reaction was carried out for 6 hours. After filtration, washing with water, drying, and calcination at 600℃ for 2 hours in air atmosphere, core-shell particles were obtained. The core-shell particles were dispersed in 75vt% hydrogen peroxide aqueous solution, and the temperature was controlled at 75℃ and ultrasonic treatment was carried out for 3 hours. After centrifugation and washing until neutral, and drying, ZrO2@alumina was obtained.

[0080] A2: Mix 1.2 mL of γ-aminopropyltriethoxysilane, 95 mL of ethanol, and 5 mL of water, adjust the pH to 4.5, add 10 g of ZrO2@alumina to the reaction vessel and disperse evenly, control the temperature at 55℃ and keep the reaction at that temperature for 9 h, centrifuge, wash, and dry to obtain organic ZrO2@alumina;

[0081] A3: In a nitrogen atmosphere, 2.2g of bis[3-(triethoxysilyl)propyl]-disulfide (CAS: 56706-10-6), 40mL of anhydrous toluene, and 0.22g of acetic acid were added to a reaction vessel and dispersed evenly. 10g of organic ZrO2@alumina was added, and the temperature was controlled at 45℃ and the reaction was maintained for 6h. The temperature was then raised to 75℃ and the reaction was maintained for 3h. After centrifugation, washing, and drying, the functional additive was obtained.

[0082] Compared with Example 5, Comparative Example 4 only replaced the functional additives prepared in Example 2 with the functional additives prepared in Comparative Example 1 in equal amounts. The remaining components and preparation methods were completely the same as those in Example 5.

[0083] Compared with Example 5, Comparative Example 5 only replaced the functional additives prepared in Example 2 with the functional additives prepared in Comparative Example 2 in equal amounts. The remaining components and preparation methods were completely the same as those in Example 5.

[0084] Comparative Example 6 is the same as Example 5 except that the functional additives prepared in Example 2 are replaced in equal amounts with the functional additives prepared in Comparative Example 3. The other components and preparation methods are completely the same as those in Example 5.

[0085] Performance testing

[0086] (1) Flexural strength: The test was conducted according to GB / T 4741-1999 "Test method for flexural strength of ceramic materials". The number of cracking cycles of the ceramic material under rapid cooling treatment of 300℃→25℃ was tested. The test results are shown in Table 1.

[0087] (2) Thermal shock resistance: The test was conducted according to GB / T 3298-2022 "Test Method for Thermal Shock Resistance of Daily-use Ceramic Ware". The test results are shown in Table 1.

[0088] Table 1: Statistical Table of Mechanical Property Test Data of Ceramic Materials in Examples 4-6 and Comparative Examples 4-6

[0089]

[0090] As shown in Table 1, the functional additives prepared in this application, when added to the green body, greatly improve the flexural strength and thermal shock resistance of the ceramic material.

[0091] (3) Transmittance: The transmittance was tested according to GB / T 3296-2021 "Method for Determination of Transmittance of Daily-use Porcelain", and the test results are shown in Table 2;

[0092] (4) Water absorption rate: The test was conducted according to GB / T 3299-2011 "Method for Determination of Water Absorption Rate of Daily-use Ceramic Ware". The test results are shown in Table 2.

[0093] (5) Whiteness: The whiteness of building materials and non-metallic mineral products was measured according to GB / T 5950 "Measurement Method of Whiteness of Building Materials and Non-metallic Mineral Products". The CIE Lab* value was measured using a D65 standard light source and a 10° observation angle. The test results are shown in Table 2.

[0094] Table 2: Statistical Table of Ceramic Material Performance Test Data for Examples 4-6 and Comparative Examples 4-6

[0095]

[0096] As shown in Table 2, the transmittance and whiteness of the ceramic materials prepared by adding functional additives to the blanks in this application were not affected.

[0097] The foregoing has provided a detailed description of one embodiment of the present invention, but this description is merely a preferred embodiment and should not be construed as limiting the scope of the invention. All equivalent variations and modifications made within the scope of the claims of this invention should still fall within the patent coverage of this invention.

Claims

1. A method for preparing a lightweight daily-use ceramic material, characterized in that, Includes the following steps: S1: Prepare raw materials according to the proportion of raw materials for the green body, crush, ball mill, sieve, and age to obtain green slurry; S2: Using slurry to make the blank body, drying the blank body, trimming the blank body, and bisque firing to obtain the bisque body; S3: Glaze the surface of the unglazed ceramic body, fire it to form a shape, and cool it to obtain a lightweight daily-use ceramic material; The green body comprises the following raw materials in parts by weight: 48-60 parts kaolin, 17-23 parts potassium feldspar, 20-26 parts quartz, 1-2 parts functional additives, 2-3 parts talc, 4-8 parts wollastonite, 6-9 parts calcium oxide, and 15-25 parts barium carbonate. The preparation method of the functional additive includes the following steps: A1: γ-aminopropyltriethoxysilane, ethanol, and water were mixed and the pH was adjusted to 4.5-5.

0. ZrO2@alumina was added to the reaction vessel and dispersed evenly. The temperature was controlled at 50-60℃ and the reaction was kept at this temperature for 6-12 hours. After centrifugation, washing, and drying, organic ZrO2@alumina was obtained. A2: In a nitrogen atmosphere, bis[3-(triethoxysilyl)propyl]-disulfide, anhydrous toluene, and acetic acid were added to a reaction vessel and dispersed evenly. Organic ZrO2@alumina was then added. The temperature was controlled at 40-50℃ and the reaction was maintained at this temperature for 4-8 hours. The temperature was then raised to 70-80℃ and the reaction was maintained at this temperature for 2-4 hours. After centrifugation, washing, and drying, modified alumina was obtained. A3: Carboxymethyl cellulose and deionized water are added to a reaction vessel and dispersed evenly. The pH is adjusted to 4.5-5.

0. EDC and NHS are added and activated for 0.5-1 h. Modified alumina is added and the pH is adjusted to 7.0-7.

5. The reaction is carried out at a temperature of 50-60℃ with stirring for 6-9 h. The mixture is then purified and dried to obtain the functional additive.

2. The method for preparing a lightweight daily-use ceramic material according to claim 1, characterized in that, The addition ratio of γ-aminopropyltriethoxysilane, ethanol, water, and ZrO2@alumina in A1 is 1-1.5 mL: 80-95 mL: 5-20 mL: 10 g.

3. The method for preparing a lightweight daily-use ceramic material according to claim 1, characterized in that, The addition ratio of bis[3-(triethoxysilyl)propyl]-disulfide, anhydrous toluene, acetic acid, and organic ZrO2@alumina in A2 is 1.5-3g: 25-50mL: 0.15-0.3g: 10g.

4. The method for preparing a lightweight daily-use ceramic material according to claim 1, characterized in that, The addition ratio of carboxymethyl cellulose, deionized water, EDC, NHS, and modified alumina in A3 is 10g: 300-600mL: 0.05-0.1g: 0.035-0.07g: 1-1.5g.

5. The method for preparing a lightweight daily-use ceramic material according to claim 1, characterized in that, The preparation method of ZrO2@alumina includes the following steps: Nano-alumina and isopropanol were added to a reaction vessel and dispersed evenly. Water and zirconium isopropoxide were mixed and added to the reaction vessel. The temperature was controlled at 70-80℃ and the hydrolysis reaction was carried out for 4-8 hours. The mixture was then filtered, washed with water, dried, and calcined to obtain core-shell particles. The core-shell particles were dispersed in an aqueous hydrogen peroxide solution and ultrasonically treated at 70-80℃ for 2-4 hours. After centrifugation and washing until neutral, the mixture was dried to obtain ZrO2@alumina.

6. The method for preparing a lightweight daily-use ceramic material according to claim 5, characterized in that, The addition ratio of nano-alumina, isopropanol, water, and zirconium isopropoxide is 1g: 20mL-100mL: 0.075-0.3mL: 0.5mL-1mL.

7. The method for preparing a lightweight daily-use ceramic material according to claim 1, characterized in that, The glaze comprises the following raw materials by weight percentage: 40-45 parts potassium feldspar, 13-18 parts shell powder, 18-24 parts quartz, 6-9 parts barium carbonate, 12-14 parts zirconium silicate, 1-2 parts zinc oxide, and 3-6 parts talc.

8. The method for preparing a lightweight daily-use ceramic material according to claim 1, characterized in that, The ball milling process in S1 is as follows: the pulverized raw material is added to the ball mill, and water is added at 70-80% of the total weight of the raw material for wet ball milling.

9. The method for preparing a lightweight daily-use ceramic material according to claim 8, characterized in that, The specific firing process in S3 is as follows: First stage of heating: control the heating rate at 80-100℃ / h, heat to 400-500℃, and hold for 1-1.5h; Two-stage heating: control the heating rate at 150-200℃ / h, heat to 900-1100℃, and hold for 2-4 hours; Three-stage heating: control the heating rate at 50-70℃ / h, heat to 1280-1320℃, and hold for 1-2 hours.

10. A lightweight daily-use ceramic material, characterized in that, It is prepared by the method described in any one of claims 1-9.

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