Composite flow line glaze ceramic and preparation method thereof

Abstract

The invention relates to the technical field of ceramics, in particular to composite flow-line glaze ceramic and a preparation method thereof.The composite flow-line glaze ceramic comprises a green body, bottom-layer glaze, middle-layer glaze and top-layer glaze, the bottom-layer glaze comprises basic glaze and bottom-layer flow-line particles, the middle-layer glaze comprises basic glaze and middle-layer flow-line particles, and the top-layer glaze comprises basic glaze and top-layer flow-line particles. According to the invention, through the design of viscosity difference between bottom-layer, middle-layer and top-layer flow-line particles and basic glaze, in combination with particle raw materials with Yishan stone, calcined botryolith and blue cone ore as cores, and in combination with differential glazing modes of each layer, a stable flow-line framework is constructed by virtue of the slow flow characteristic of the bottom-layer particles; and natural transition of hierarchical boundaries is achieved by means of the medium flow characteristic of the middle-layer particles, visual focuses are formed by means of the fast flow characteristic of the top-layer particles, and the flow line effect that blocky dark green lines, light yellow and green interlaced lines and slender indigo lines are well arranged and prominent in decoration feeling is achieved.

Description

Technical Field

[0001] This invention relates to the field of ceramic technology, specifically to composite flow-patterned glaze ceramics and their preparation methods. Background Technology

[0002] Traditional flow-pattern glaze products have significant shortcomings in decorative effect, color stability, and overall performance: In terms of decoration, they rely heavily on simple color combinations to achieve layered effects, lacking precise control over the viscosity difference between the flowing particles and the base glaze. This results in monotonous flow patterns with harsh boundaries, making it difficult to create a three-dimensional and orderly decorative effect. In terms of color, during high-temperature firing, metal ions within the flow particles are prone to reduction reactions due to improper atmosphere control, causing color fading and reduced saturation. Furthermore, there are significant color differences between different batches, indicating poor color stability. In terms of performance and quality, the design of the matching coefficients of thermal expansion between the body and glaze is crude, and the raw material pretreatment process is inadequate, easily leading to defects such as glaze cracking and pinholes. Simultaneously, the mechanical properties of the glaze layer, such as wear resistance and impact resistance, are weak, making it difficult to meet long-term usage requirements. In terms of process, traditional processes do not differentiate the glazing methods according to the functional requirements of different flow layers, and the firing atmosphere is not optimized for the key stages of flow pattern formation. This further leads to unstable flow patterns and inconsistent overall product quality, failing to meet the market's demand for high-quality flow-pattern glaze ceramics. Summary of the Invention

[0003] One object of the present invention is to solve at least the above-mentioned problems by means of composite flow-patterned glaze ceramics and their preparation methods.

[0004] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows: the composite flow-patterned glaze ceramic includes a body, a bottom glaze, a middle glaze and a top glaze. The bottom glaze includes a base glaze and bottom flow-patterned particles, the middle glaze includes a base glaze and middle flow-patterned particles, and the top glaze includes a base glaze and top flow-patterned particles.

[0005] Preferably, the base glaze comprises the following raw materials in parts by weight: 35-40 parts quartz, 20-25 parts potassium-sodium feldspar, 10-12 parts kaolin for glaze, 5-10 parts calcium carbonate, 3-5 parts lightly calcined magnesium oxide, 4-6 parts industrial-grade zinc oxide, 2-5 parts 3Y stabilized zirconium oxide, 0.3-0.6 parts sodium nitrate, and 0.5-0.8 parts organosilicon defoamer.

[0006] Preferably, the bottom layer of flow-textured particles comprises the following raw materials in parts by weight: 15-20 parts of vesuvianite, 20-25 parts of zinc borate, 3-5 parts of chromium oxide green, 20-30 parts of quartz, and 20-25 parts of potassium feldspar. The vesuvianite is melted at 1350℃ for 2 hours and then water-quenched, and its Fe2O3 content is ≤0.05wt%.

[0007] Preferably, the intermediate flow-textured particles comprise the following raw materials in parts by weight: 15-20 parts prehnite, 5-8 parts lithium carbonate, 3-5 parts zirconium silicate, 18-25 parts quartz, and 22-28 parts potassium feldspar. The prehnite is calcined under vacuum at 600-650℃ for 2.5 hours, and the removal rate of crystal water is ≥98%.

[0008] Preferably, the top layer of flow-textured particles comprises the following raw materials in parts by weight: 8-12 parts beniote, 3-5 parts potassium fluorosilicate, 1-2 parts nano TiO2, 22-26 parts quartz, and 18-22 parts potassium feldspar.

[0009] Preferably, the green body comprises the following raw materials in parts by weight: 30-35 parts Suzhou kaolin, 28-35 parts quartz sand, 20-25 parts potassium feldspar, 6-8 parts calcium-based montmorillonite, 4-8 parts talc, 2-5 parts barium carbonate, and 0.2-0.3 parts carboxymethyl cellulose.

[0010] The preparation method of composite flow-patterned glaze ceramics includes the following steps:

[0011] Step a: After forming the green body, bisque fire at a temperature of 980-1000℃ for 1.5-2 hours with a heating rate of 100℃ / h.

[0012] Step b: Prepare the bottom layer glaze, middle layer glaze, and top layer glaze;

[0013] Step c: Apply the bottom layer glaze, the middle layer glaze, and the top layer glaze to the body in sequence;

[0014] Step d: Place the glazed body into the kiln for glaze firing.

[0015] Preferably, in step b, the preparation method of the bottom layer flow pattern particles, the middle layer flow pattern particles and the top layer flow pattern particles is as follows: the raw material components are successively mixed, melted and rapidly cooled, and then crushed and graded to the target particle size. In step c, the bottom layer glaze is applied by dipping, the middle layer glaze is applied by pouring, and the top layer glaze is applied by spraying. The glaze thickness ratio of the bottom layer glaze, the middle layer glaze and the top layer glaze is 3-3.5:2-2.5:1.

[0016] Preferably, in step d, the firing curve is:

[0017] Low-temperature dehumidification: room temperature -300℃, heating rate 100℃ / h;

[0018] Oxidative decomposition: 300-900℃, heating rate 150℃ / h;

[0019] Glaze melting: 900-1200℃, heating rate 180℃ / h;

[0020] Flow pattern formation: 1200-1300℃, heating rate 100℃ / h;

[0021] High temperature insulation: Insulate at 1300℃ for 30 minutes;

[0022] Cooling and shaping: 1300-800℃, cooling rate 70℃ / h;

[0023] Slow cooling: 800°C to room temperature, cooling rate 30°C / h.

[0024] Preferably, in step d, during the flow pattern formation stage, in addition to controlling the oxygen content to be ≥8%, ozone gas with a kiln volume fraction of 0.6-0.8% is also introduced. The ozone is introduced in a pulsed manner with a pulse frequency of 30s / time, and the amount introduced in a single pulse is 0.1% of the kiln volume.

[0025] As described above, the composite flow-patterned glaze ceramic and its preparation method provided by this invention have the following beneficial effects: This invention, through the viscosity difference design between the bottom, middle, and top layers of flow-patterned particles and the base glaze, combined with granular raw materials with vesuvianite, calcined prehnite, and beniote as the core, and with differentiated glazing methods for each layer, utilizes the slow-flowing characteristics of the bottom layer particles to construct a stable flow-pattern framework, utilizes the moderate-flowing characteristics of the middle layer particles to achieve a natural transition of layer boundaries, and utilizes the fast-flowing characteristics of the top layer particles to form a visual focus, creating a flow pattern with distinct layers and a prominent decorative effect, consisting of "blocky dark green patterns - light yellow-green interwoven patterns - slender indigo patterns". The effects are significant; by using specific components in the base glaze to enhance the wear resistance and impact resistance of the glaze surface, combined with the precise matching of the thermal expansion coefficients of the body and glaze and the raw material pretreatment process, the problems of ceramic thermal shock cracking and glaze pinholes are effectively avoided; at the same time, during the glaze firing flow pattern formation stage, the reduction reaction of metal ions at high temperatures is suppressed by controlling the oxygen content and synergistic atmosphere regulation through pulsed introduction of strong oxidizing gas, which significantly enhances the color saturation and batch color consistency of dark green and indigo patterns, ultimately achieving a comprehensive and synergistic improvement in the decorative layering, color stability, mechanical properties and glaze quality of ceramic products, which is significantly superior to traditional flow pattern glaze products. Detailed Implementation

[0026] The present invention will be further described below through specific embodiments.

[0027] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below in conjunction with specific embodiments.

[0028] The composite flow-patterned glaze ceramic of this invention comprises a body, a bottom glaze, a middle glaze, and a top glaze. The bottom glaze comprises a base glaze and bottom flow-patterned particles, the middle glaze comprises a base glaze and middle flow-patterned particles, and the top glaze comprises a base glaze and top flow-patterned particles. The viscosity of the bottom flow-patterned particles is 1.0 × 10⁻⁶ higher than that of the base glaze. 4 -1.5×10 4At 1280℃, the flow rate is slower than that of the base glaze (Pa·s), creating a lag trajectory. The base glaze carries the particles slowly, and due to their higher viscosity and density, the particles have short and coarse trajectories, exhibiting "blocky dark green streaks," anchoring the underlying framework of the entire flow pattern. The viscosity of the particles in the middle layer of the flow pattern is 0.2 × 10⁻⁶ higher than that of the base glaze. 4 -0.4×10 4 At 1280℃, the flow rate (Pa·s) is close to that of the base glaze, forming an interwoven trajectory. As the particles flow with the base glaze, they also diffuse slightly. The light yellow-green veins partially overlap with the dark green veins of the underlying layer, eliminating the harshness of the layer boundaries. The viscosity of the top layer of flow particles is 0.2 × 10⁻⁶ lower than that of the base glaze. 4 -0.4×10 4 Pa·s (at 1280℃), the flow rate is faster than that of the base glaze, forming an advanced trajectory. The base glaze serves as a carrier, and the particles quickly shuttle through it. Because the particles are fine and light, the trajectory is long and thin, presenting a slender indigo pattern that covers the middle layer and forms a visual focal point.

[0029] The base glaze comprises the following raw materials in parts by weight: 35-40 parts quartz, 20-25 parts potassium-sodium feldspar, 10-12 parts kaolin for glaze, 5-10 parts calcium carbonate, 3-5 parts lightly calcined magnesium oxide, 4-6 parts industrial-grade zinc oxide, 2-5 parts 3Y stabilized zirconium oxide, 0.3-0.6 parts sodium nitrate, and 0.5-0.8 parts organosilicon defoamer. In the basic glaze composition, quartz serves as the glaze network framework, enhancing the glaze's hardness and acid / alkali resistance. Potassium-sodium feldspar contains 8-10 wt% K₂O, 3-5 wt% Na₂O, and ≤0.2 wt% Fe₂O₃. This potassium-sodium feldspar acts as a flux, regulating the glaze's melting temperature; the initial melting temperature is 850℃, and the complete melting temperature is 1250℃. Kaolin enhances the glaze slurry's suspension and improves surface smoothness. Calcium carbonate acts as a flux, reducing glaze viscosity and enhancing gloss. Lightly calcined magnesium oxide inhibits glaze crystallization, preventing devitrification and adjusting the coefficient of thermal expansion to match the body. Industrial-grade zinc oxide improves glaze elasticity, preventing thermal shock cracking and reducing pinholes. 3Y stabilized zirconium oxide enhances glaze wear resistance and impact resistance. Sodium nitrate acts as an auxiliary flux, lowering the glaze's initial melting temperature and preventing flow lines from becoming stuck. Organosilicon defoamer eliminates bubbles generated during ball milling and mixing.

[0030] The bottom layer of flowing particles comprises the following raw materials in parts by weight: 15-20 parts vesuvianite, 20-25 parts zinc borate, 3-5 parts chromium oxide green, 20-30 parts quartz, and 20-25 parts potassium feldspar. The vesuvianite is melted at 1350℃ for 2 hours and then water-quenched, with an Fe2O3 content ≤0.05wt%. Vesuvianite provides a dark green hue and a wear-resistant framework, zinc borate can offset the high viscosity of the glaze caused by the high aluminum content in the raw materials, and chromium oxide green enhances the green saturation. The bottom layer of flowing particles flows slowly in the base glaze, and after firing, they present as blocky dark green veins.

[0031] The intermediate flow-pattern particles consist of the following raw materials in parts by weight: 15-20 parts prehnite, 5-8 parts lithium carbonate, 3-5 parts zirconium silicate, 18-25 parts quartz, and 22-28 parts potassium feldspar. The prehnite is calcined at 600-650℃ under vacuum for 2.5 hours, achieving a crystal water removal rate of ≥98%. Calcination of the prehnite ensures a crystal water removal rate of ≥98%, preventing pinholes in the glaze due to moisture evaporation during firing. Lithium carbonate regulates the reactivity between the prehnite and the glaze, while zirconium silicate enhances the glaze gloss. The intermediate flow-pattern particles exhibit a moderate flow rate in the base glaze, ultimately resulting in a light yellow-green flow pattern after firing.

[0032] The top layer of flow-patterned particles comprises the following raw materials in parts by weight: 8-12 parts benitoite, 3-5 parts potassium fluorosilicate, 1-2 parts nano-TiO2, 22-26 parts quartz, and 18-22 parts potassium feldspar. Benitoite exhibits a unique indigo blue color, while nano-TiO2 enhances the intensity of electron transitions within the particles, making the indigo blue brighter. The top layer of flow-patterned particles flows relatively quickly in the base glaze, ultimately resulting in slender indigo blue flow patterns after firing.

[0033] The green body comprises the following raw materials by weight: 30-35 parts Suzhou kaolin, 28-35 parts quartz sand, 20-25 parts potassium feldspar, 6-8 parts calcium-based montmorillonite, 4-8 parts talc, 2-5 parts barium carbonate, and 0.2-0.3 parts carboxymethyl cellulose. The coefficient of thermal expansion of the green body is 6.5-7.5 × 10⁻⁶. -6 / ℃ (20-600℃).

[0034] The preparation method of composite flow-patterned glaze ceramics includes the following steps:

[0035] Step a: After forming the green body, bisque fire at a temperature of 980-1000℃ for 1.5-2 hours with a heating rate of 100℃ / h.

[0036] Step b: Prepare the bottom layer glaze, middle layer glaze, and top layer glaze;

[0037] Step c: Apply the bottom layer glaze, the middle layer glaze, and the top layer glaze to the body in sequence;

[0038] Step d: Place the glazed body into the kiln for glaze firing.

[0039] In step b, the preparation methods for the bottom layer, middle layer, and top layer flow pattern particles are as follows: the raw material components are sequentially mixed, melted, and rapidly cooled, then crushed and graded to the target particle size. In step c, the bottom layer glaze is applied by dipping, the middle layer glaze by pouring, and the top layer glaze by spraying. The glaze thickness ratio of the bottom layer, middle layer, and top layer glaze is 3-3.5:2-2.5:1. The bottom layer is thicker to ensure the stability of the flow pattern framework; the top layer is thinner to avoid covering the middle layer texture.

[0040] In step d, the firing curve is as follows:

[0041] Low-temperature dehumidification: room temperature -300℃, heating rate 100℃ / h; slowly remove residual moisture from the body and glaze to avoid cracking of the body or glaze due to rapid heating.

[0042] Oxidative decomposition: 300-900℃, heating rate 150℃ / h; burn off organic matter and decompose carbonates in the green body;

[0043] Glaze melting: 900-1200℃, heating rate 180℃ / h; the base glaze begins to melt, and the flow grains gradually soften.

[0044] Flow pattern formation: 1200-1300℃, heating rate 100℃ / h; this stage is the core stage of firing, with oxygen content ≥8%, and flow patterns are formed in the three layers of particles due to viscosity difference, with the bottom layer flowing slowly and the top layer flowing quickly.

[0045] High-temperature heat preservation: heat preservation at 1300℃ for 30 minutes; promotes the reaction between the body and glaze and eliminates bubbles on the glaze surface;

[0046] Cooling and shaping: 1300-800℃, cooling rate 70℃ / h; rapid cooling fixes the flow pattern and avoids secondary flow.

[0047] Slow cooling: 800°C to room temperature, cooling rate 30°C / h. This reduces thermal stress on the body and glaze, preventing cracking.

[0048] In step d, during the flow pattern formation stage, in addition to controlling the oxygen content to ≥8%, ozone gas with a kiln volume fraction of 0.6-0.8% is introduced. The ozone is introduced in a pulsed manner, with a pulse frequency of 30 seconds per pulse, and the amount introduced in a single pulse is 0.1% of the kiln volume. During the flow pattern formation stage, the flow pattern particles are in a semi-molten state with high surface metal ion activity. Ozone reacts with the metal oxides on the surface of the flow pattern particles to form a stable high-valence metal oxide film. Pulsed introduction avoids excessive oxidation and devitrification of the glaze caused by continuous high concentrations of ozone. Simultaneously, the strong oxidizing properties of ozone enhance the color stability of the flow pattern particles, solving the problem of Cr deterioration caused by high temperatures under traditional oxidizing atmospheres. 3+ →Cr 2+ Ti 4+ →Ti 3+ The problem was solved by increasing the color saturation of dark green and indigo patterns by ≥15%, and reducing the batch color difference ΔE to ≤1.5.

[0049] As described above, the composite flow-patterned glaze ceramic and its preparation method provided by this invention have the following beneficial effects: This invention, through the viscosity difference design between the bottom, middle, and top layers of flow-patterned particles and the base glaze, combined with granular raw materials with vesuvianite, calcined prehnite, and beniote as the core, and with differentiated glazing methods for each layer, utilizes the slow-flowing characteristics of the bottom layer particles to construct a stable flow-pattern framework, utilizes the moderate-flowing characteristics of the middle layer particles to achieve a natural transition of layer boundaries, and utilizes the fast-flowing characteristics of the top layer particles to form a visual focus, creating a flow pattern with distinct layers and a prominent decorative effect, consisting of "blocky dark green patterns - light yellow-green interwoven patterns - slender indigo patterns". The effects are significant; by using specific components in the base glaze to enhance the wear resistance and impact resistance of the glaze surface, combined with the precise matching of the thermal expansion coefficients of the body and glaze and the raw material pretreatment process, the problems of ceramic thermal shock cracking and glaze pinholes are effectively avoided; at the same time, during the glaze firing flow pattern formation stage, the reduction reaction of metal ions at high temperatures is suppressed by controlling the oxygen content and synergistic atmosphere regulation through pulsed introduction of strong oxidizing gas, which significantly enhances the color saturation and batch color consistency of dark green and indigo patterns, ultimately achieving a comprehensive and synergistic improvement in the decorative layering, color stability, mechanical properties and glaze quality of ceramic products, which is significantly superior to traditional flow pattern glaze products.

[0050] The above are merely some specific embodiments of the present invention, but the design concept of the present invention is not limited thereto. Any non-substantial modifications made to the present invention using this concept shall be considered as infringing upon the protection scope of the present invention.

Claims

1. Composite flow-patterned glaze ceramic, characterized in that: It includes a body, a bottom glaze, a middle glaze, and a top glaze. The bottom glaze includes a base glaze and bottom flow pattern particles. The middle glaze includes a base glaze and middle flow pattern particles. The top glaze includes a base glaze and top flow pattern particles.

2. The composite flow-patterned glaze ceramic according to claim 1, characterized in that: The base glaze comprises the following raw materials in parts by weight: 35-40 parts quartz, 20-25 parts potassium-sodium feldspar, 10-12 parts kaolin for glaze, 5-10 parts calcium carbonate, 3-5 parts lightly calcined magnesium oxide, 4-6 parts industrial-grade zinc oxide, 2-5 parts 3Y stabilized zirconium oxide, 0.3-0.6 parts sodium nitrate, and 0.5-0.8 parts organosilicon defoamer.

3. The composite flow-patterned glaze ceramic according to claim 1, characterized in that: The bottom layer of flow-textured particles comprises the following raw materials in parts by weight: 15-20 parts of vesuvianite, 20-25 parts of zinc borate, 3-5 parts of chromium oxide green, 20-30 parts of quartz, and 20-25 parts of potassium feldspar. The vesuvianite is melted at 1350℃ for 2 hours and then water-quenched, and its Fe2O3 content is ≤0.05wt%.

4. The composite flow-patterned glaze ceramic according to claim 1, characterized in that: The intermediate flow-textured particles comprise the following raw materials in parts by weight: 15-20 parts prehnite, 5-8 parts lithium carbonate, 3-5 parts zirconium silicate, 18-25 parts quartz, and 22-28 parts potassium feldspar. The prehnite is calcined under vacuum at 600-650℃ for 2.5 hours, and the removal rate of crystal water is ≥98%.

5. The composite flow-patterned glaze ceramic according to claim 1, characterized in that: The top layer flow grains comprise the following raw materials in parts by weight: 8-12 parts beniote, 3-5 parts potassium fluorosilicate, 1-2 parts nano TiO2, 22-26 parts quartz, and 18-22 parts potassium feldspar.

6. The composite flow-patterned glaze ceramic according to claim 1, characterized in that: The green body comprises the following raw materials in parts by weight: 30-35 parts Suzhou kaolin, 28-35 parts quartz sand, 20-25 parts potassium feldspar, 6-8 parts calcium-based montmorillonite, 4-8 parts talc, 2-5 parts barium carbonate, and 0.2-0.3 parts carboxymethyl cellulose.

7. The method for preparing composite flow-patterned glaze ceramics according to any one of claims 1-6, characterized in that, Includes the following steps: Step a: After forming the green body, bisque fire at a temperature of 980-1000℃ for 1.5-2 hours with a heating rate of 100℃ / h. Step b: Prepare the bottom layer glaze, middle layer glaze, and top layer glaze; Step c: Apply the bottom layer glaze, the middle layer glaze, and the top layer glaze to the body in sequence; Step d: Place the glazed body into the kiln for glaze firing.

8. The method for preparing composite flow-patterned glaze ceramic according to claim 7, characterized in that: In step b, the preparation method of the bottom layer flow pattern particles, the middle layer flow pattern particles and the top layer flow pattern particles is as follows: the raw material components are mixed, melted and rapidly cooled in sequence, and then crushed and graded to the target particle size. In step c, the bottom layer glaze is applied by dipping, the middle layer glaze is applied by pouring, and the top layer glaze is applied by spraying. The glaze thickness ratio of the bottom layer glaze, the middle layer glaze and the top layer glaze is 3-3.5:2-2.5:

1.

9. The method for preparing composite flow-patterned glaze ceramic according to claim 7, characterized in that, In step d, the firing curve is as follows: Low-temperature dehumidification: room temperature -300℃, heating rate 100℃ / h; Oxidative decomposition: 300-900℃, heating rate 150℃ / h; Glaze melting: 900-1200℃, heating rate 180℃ / h; Flow pattern formation: 1200-1300℃, heating rate 100℃ / h; High temperature insulation: Insulate at 1300℃ for 30 minutes; Cooling and shaping: 1300-800℃, cooling rate 70℃ / h; Slow cooling: 800°C to room temperature, cooling rate 30°C / h.

10. The method for preparing composite flow-patterned glaze ceramic according to claim 7, characterized in that: In step d, during the flow pattern formation stage, in addition to controlling the oxygen content to be ≥8%, ozone gas with a kiln volume fraction of 0.6-0.8% is also introduced. The ozone is introduced in a pulsed manner with a pulse frequency of 30s / time, and the amount introduced in a single pulse is 0.1% of the kiln volume.