Formula and preparation process of ceramic glaze

Abstract

The invention relates to the technical field of ceramic glaze preparation, in particular to a formula of ceramic glaze, which comprises the following components in percentage by mass: 25-30% of modified zircon sand; 20 to 25% of spodumene; 15 to 20 percent of nano aluminum oxide; 10 to 15% of petalite; 8-12% of kaolin; 3-5% of a silver-loaded zeolite antibacterial agent; 5-8% of boron carbide-silicon nitride composite powder; 2-3% of zinc borate; and 10-15% of a composite frit. A three-dimensional grid structure (the Vickers hardness is greater than or equal to 1800 HV) is formed through boron carbide-silicon nitride composite powder, and the wear resistance is improved by 40% in combination with a potassium feldspar modification technology; the silver-loaded zeolite realizes slow release of Ag, the antibacterial rate is greater than 99.9%, a gradient sintering process enables a glaze layer to form a gradient density structure, the porosity of a surface layer is less than 0.5%, the porosity of a bottom layer is 3-5%, the oxidation defect of the copper red glaze is avoided through CO / N atmosphere control, and the color development uniformity delta E is less than or equal to 0.8; the firing temperature is reduced by 150 DEG C, and the energy consumption is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic glaze preparation, and in particular to a formula and preparation process of ceramic glaze. Background Art

[0002] Ceramic glaze, as a thin glassy layer covering the surface of ceramic products, plays a vital role in the performance and appearance of ceramics. Traditional ceramic glazes have certain limitations in terms of hardness, wear resistance, corrosion resistance, and bonding strength with the body. With the continuous improvement of the performance requirements of ceramic products in modern industry and life, the development of a new type of ceramic glaze that can significantly improve the comprehensive performance of ceramics is of great practical significance. For example, in the field of architectural ceramics, the glaze surface is required to have higher hardness and wear resistance to resist friction and scratches in daily use; in the field of sanitary ceramics, the glaze surface is required to have better corrosion resistance and antibacterial properties to ensure long-term hygiene and safety. However, the existing ceramic glaze formula and preparation process are difficult to meet these diverse high-performance requirements at the same time.

[0003] Therefore, those skilled in the art provide a formula and preparation process of a ceramic glaze to solve the problems raised in the above background technology. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a formula and preparation process of ceramic glaze. A ceramic glaze formula comprises the following components in percentage by mass: Modified zircon sand 25-30% (treated with silane coupling agent KH-570, treatment temperature is 60-80℃, surface contact angle ≤15°) Spodumene 20-25%; Nano-alumina 15-20%; Petalite 10-15%; Kaolin 8-12%; Functional additives: 3-5% silver-loaded zeolite antibacterial agent (prepared using metal-organic framework technology), silver ion loading ≥ 8wt%, zeolite pore size 0.5-2nm; Boron carbide-silicon nitride composite powder 5-8% (1:1 composite, particle size ≤ 500nm), and plasma activated to form a three-dimensional grid structure; Zinc borate 2-3%; Flux: Composite frit 10-15%, containing SiO2 50%, B2O3 15%, ZnO 10%, BaO 25%; The composite frit also contains 0.5-1.2% CeO2 to improve the color uniformity of the glaze.

[0005] Preparation process Step 1: Glaze Slurry Preparation ① Modified zircon sand, spodumene, nano-alumina, petalite, kaolin, composite frit and other basic glaze materials are mixed in proportion and ball-milled until the residue on a 400-mesh sieve is ≤0.5%, and 0.5 wt% of a polycarboxylic acid dispersant is added; ② Add functional additives step by step: first add boron carbide-silicon nitride composite powder and ball mill for 2-2.5 hours, then add silver-loaded zeolite and stir at a low speed of 200 r / min for 0.5-1 hour; ③ Adjust the glaze slurry density to 1.65-1.75g / cm³ and age for 24 hours.

[0006] Step 2: Gradient sintering process ① Green pretreatment: nitrogen purge technology is used, the flow rate is 12m / s, and the humidity is ≤5%RH; ② Glazing: Glazing method, glaze amount 80g / piece (300×600mm specification); ③ Three-stage sintering: Initial firing stage: room temperature → 850℃, heating rate 5℃ / min, holding temperature for 30min; Crystallization stage: 850→1150℃, heating rate 3℃ / min, introduction of CO2 / N2 mixed gas with a volume ratio of 1:4; Densification stage: 1150→1280℃, heating rate 2℃ / min, holding for 15min and then cooling to 600℃; Preferably, the rapid cooling stage adopts nitrogen curtain cooling technology, and the cooling rate is ≥50°C / s.

[0007] Preferably, the CO2 partial pressure in the CO2 / N2 mixed gas is 0.02-0.05 MPa, and the gas flow rate is 8-12 L / min.

[0008] The technical effects and advantages of the present invention are as follows: Boron carbide-silicon nitride composite powder forms a three-dimensional grid structure (Vickers hardness ≥ 1800HV), and combined with potassium feldspar modification technology, wear resistance is improved by 40%; Silver-loaded zeolite achieves sustained release of Ag⁺, with an antibacterial rate of >99.9% The gradient sintering process creates a gradient density structure in the glaze layer, with a surface porosity of <0.5% and a bottom porosity of 3-5%. CO2 / N2 atmosphere control avoids oxidation defects in the copper red glaze, and a color uniformity of ΔE ≤ 0.8. The firing temperature is lowered by 150℃, which reduces energy consumption. DETAILED DESCRIPTION

[0009] The present invention will be described in further detail below with reference to specific embodiments. The embodiments of the present invention are provided for purposes of illustration and description and are not intended to be exhaustive or to limit the invention to the disclosed forms. Many modifications and variations will be apparent to those skilled in the art. The embodiments are chosen and described to better illustrate the principles and practical applications of the present invention and to enable those skilled in the art to understand the present invention and design various embodiments with various modifications suitable for specific applications. Example

[0010] In this embodiment, a ceramic glaze formula and preparation process are provided. A ceramic glaze formula comprises the following components in percentage by mass: Modified zircon sand 25-30% (treated with silane coupling agent KH-570, treatment temperature is 60-80℃, surface contact angle ≤15°) Spodumene 20-25%; Nano-alumina 15-20%; Petalite 10-15%; Kaolin 8-12%; Functional additives: 3-5% silver-loaded zeolite antibacterial agent (prepared using metal-organic framework technology), silver ion loading ≥ 8wt%, zeolite pore size 0.5-2nm; Boron carbide-silicon nitride composite powder 5-8% (1:1 composite, particle size ≤ 500nm), and plasma activated to form a three-dimensional grid structure; Zinc borate 2-3%; Flux: Composite frit 10-15%, containing SiO2 50%, B2O3 15%, ZnO 10%, BaO 25%; The composite frit also contains 0.5-1.2% CeO2 to improve the color uniformity of the glaze.

[0011] Preparation process Step 1: Glaze Slurry Preparation ① Modified zircon sand, spodumene, nano-alumina, petalite, kaolin, composite frit and other basic glaze materials are mixed in proportion and ball-milled until the residue on a 400-mesh sieve is ≤0.5%, and 0.5 wt% of a polycarboxylic acid dispersant is added; ② Add functional additives step by step: first add boron carbide-silicon nitride composite powder and ball mill for 2-2.5 hours, then add silver-loaded zeolite and stir at a low speed of 200 r / min for 0.5-1 hour; ③ Adjust the glaze slurry density to 1.65-1.75g / cm³ and age for 24 hours.

[0012] Step 2: Gradient sintering process ① Green pretreatment: nitrogen purge technology is used, the flow rate is 12m / s, and the humidity is ≤5%RH; ② Glazing: Glazing method, glaze amount 80g / piece (300×600mm specification); ③ Three-stage sintering: Initial firing stage: room temperature → 850℃, heating rate 5℃ / min, holding temperature for 30min; Crystallization stage: 850→1150℃, heating rate 3℃ / min, introduction of CO2 / N2 mixed gas with a volume ratio of 1:4; Densification stage: 1150→1280℃, heating rate 2℃ / min, holding for 15min and then cooling to 600℃; The rapid cooling stage adopts nitrogen curtain cooling technology, and the cooling rate is ≥50°C / s. Example

[0013] The selected formula is: modified zircon sand 28%, spodumene 22%, nano alumina 18%, petalite 12%, kaolin 10%, silver-loaded zeolite 4%, boron carbide-silicon nitride 6%, zinc borate 2.5%, and composite frit 13.5%.

[0014] Step 1: Glaze Slurry Preparation First, basic glaze materials such as modified zircon sand, spodumene, nano-alumina, petalite, kaolin, and composite frit are mixed in proportion and then ball-milled until the residue on a 400-mesh sieve is ≤0.5%, and then 0.5 wt% of a polycarboxylic acid dispersant is added; Then add boron carbide-silicon nitride composite powder and ball mill for 2-2.5h; Then add silver-loaded zeolite and stir at a low speed of 200 r / min for 0.5-1 h; Adjust the glaze slurry density to 1.65-1.75g / cm³ and age for 24 hours; Step 2: Gradient sintering process ① Green pretreatment: nitrogen purge technology is used, the flow rate is 12m / s, and the humidity is ≤5%RH; ② Glazing: Glazing method, glaze amount 80g / piece (300×600mm specification); ③ Three-stage sintering: Initial firing stage: room temperature → 850℃, heating rate 5℃ / min, holding temperature for 30min; Crystallization stage: 850→1150℃, heating rate 3℃ / min, introduction of CO2 / N2 mixed gas with a volume ratio of 1:4; Densification stage: 1150→1280℃, heating rate 2℃ / min, holding for 15min and then rapidly cooling to 600℃. Nitrogen curtain cooling technology is used in the rapid cooling stage, and the cooling rate is ≥50℃ / s.

[0015] Test after gradient sintering: Wear resistance: According to GB / T3810.7 test, the wear amount is only 32mg / 100r Antibacterial property: 99.96% inhibition rate against Escherichia coli within 24 hours (GB21551.2-2010) Lead and cadmium dissolution: 50% lower than the GB4806.4-2016 standard limit.

[0016] Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field and related fields without making creative efforts should fall within the scope of protection of the present invention. Structures, devices, and operating methods not specifically described and explained in the present invention shall be implemented in accordance with conventional means in the field unless otherwise specified or limited.

Claims

1. A ceramic glaze formula, characterized in that: Contains the following components in percentage by mass: Modified zircon sand 25-30%; Spodumene 20-25%; Nano-alumina 15-20%; Petalite 10-15%; Kaolin 8-12%; Silver-loaded zeolite antibacterial agent 3-5%; Boron carbide-silicon nitride composite powder 5-8%; Zinc borate 2-3%; The composite frit comprises 10-15% SiO2 50%, B2O3 15%, ZnO 10%, and BaO 25%.

2. The ceramic glaze formulation according to claim 1, characterized in that: The silver-loaded zeolite antibacterial agent is prepared by adopting metal organic framework technology, the silver ion loading amount is ≥8wt%, and the zeolite pore diameter is 0.5-2nm.

3. The ceramic glaze formulation according to claim 1, characterized in that: The mass ratio of the boron carbide-silicon nitride composite powder is 1:1, the particle size is ≤500nm, and a three-dimensional grid structure is formed after plasma activation treatment.

4. The ceramic glaze formulation according to claim 1, characterized in that: The modified zircon sand is treated with a silane coupling agent KH-570 at a temperature of 60-80° C., and a surface contact angle of ≤15°.

5. The ceramic glaze formulation according to claim 1, characterized in that: The composite frit further contains 0.5-1.2% of CeO2.

6. A process for preparing a ceramic glaze according to any one of claims 1 to 5, characterized in that: The following steps are involved: Step 1: Glaze Slurry Preparation ① Modified zircon sand, spodumene, nano-alumina, petalite, kaolin, and composite frit base glaze are mixed in proportion and ball-milled until the residue on a 400-mesh sieve is ≤0.5%, and 0.5 wt% of a polycarboxylic acid dispersant is added; ② Add functional additives step by step: first add boron carbide-silicon nitride composite powder and ball mill, then add silver-loaded zeolite and stir at a low speed of 200r / min; ③ Adjust the glaze slurry density to 1.65-1.75g / cm³ and age for 24 hours; Step 2: Gradient sintering process ① Green pretreatment: nitrogen purge technology is used, the flow rate is 12m / s, and the humidity is ≤5%RH; ② Glazing: Glazing method, glaze amount 80g / piece (300×600mm specification); ③ Three-stage sintering: Initial firing stage: room temperature → 850℃, heating rate 5℃ / min, holding temperature for 30min; Crystallization stage: 850→1150℃, heating rate 3℃ / min, introduction of CO2 / N2 mixed gas with a volume ratio of 1:4; Densification stage: 1150→1280℃, heating rate 2℃ / min, holding for 15min and then rapidly cooling to 600℃.

7. The process for preparing a ceramic glaze according to claim 6, characterized in that: The CO2 partial pressure in the CO2 / N2 mixed gas is 0.02-0.05 MPa, and the gas flow rate is 8-12 L / min.

8. The process for preparing a ceramic glaze according to claim 6, characterized in that: The rapid cooling stage adopts nitrogen curtain cooling technology, and the cooling rate is ≥50°C / s.

9. The process for preparing a ceramic glaze according to claim 6, characterized in that: During the glaze slurry preparation process, when the functional additives are added step by step, the ball milling time of the boron carbide-silicon nitride composite powder is 2-2.5 hours, and the low-speed stirring time of the silver-loaded zeolite is 0.5-1 hour.