Preparation method of honeycomb blue-gray and blue-brown foamed glaze and product prepared thereby

Abstract

This invention discloses a method for preparing honeycomb-shaped blue-gray and blue-brown foamed glazes and the resulting products. The base glaze is prepared using feldspar, quartz, kaolin, calcined talc, limestone, and zinc oxide. Silicon-oxygen-carbon (SiOC) and iron oxide serve as both foaming agents and colorants, with cobalt oxide, chromium oxide, and nickel oxide as auxiliary colorants. This invention enriches the preparation technology of foamed glazes, expands the types of foaming agents, and features a simple preparation process that is easy to industrialize, thus promoting the application and development of artistic glazes.

Description

Technical Field

[0001] This invention relates to the field of glaze technology, and in particular to a method for preparing a honeycomb-shaped foamed raw material colored glaze and the product obtained therefrom. Background Technology

[0002] Glaze is a glassy substance that adheres to the surface of ceramic bodies, imparting physical properties (mechanical strength, whiteness, etc.) and aesthetic appeal to ceramics. Foamed glaze is a special type of artistic glaze that gives ceramic surfaces effects such as antique finish, color change, relief, and texture, possessing high artistic value and being widely used in fields such as art porcelain.

[0003] Foamed glazes are typically composed of low-temperature flux (frit), feldspar, kaolin, quartz, talc, and foaming agents, and are prepared through processes such as ball milling, glazing, and firing. The foaming mechanism involves the foaming agent generating gas during the high-temperature melting process, which then foams within the glaze melt. Upon cooling, a large number of open or closed bubbles remain in the glaze layer, resulting in the foamed effect. Currently, foamed glazes mainly consist of closed pores, and the glaze surface effect is controlled by adjusting the size of the bubbles and the color of the glaze layer. Commonly used foaming agents include silicon carbide, carbonates, and sulfates, which utilize high-temperature oxidation and decomposition to generate gases (such as carbon dioxide and sulfur dioxide) that produce the foaming effect within the glaze layer. However, current technology still suffers from a limited variety of foamed glazes and foaming agents, hindering the application and development of artistic glazes. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a method for preparing honeycomb-shaped blue-gray and blue-brown foamed glazes. This method uses silicon-oxygen-carbon (SiOC) and iron oxide as both foaming agents and colorants, supplemented with cobalt oxide, chromium oxide, and nickel oxide as colorants to prepare honeycomb-shaped blue-gray and blue-brown foamed glazes. This enriches the preparation technology of foamed glazes, expands the types of foaming agents, and promotes the technical application and development of artistic glazes. Another objective of this invention is to provide products obtained using the above-described preparation method.

[0005] The objective of this invention is achieved through the following technical solution:

[0006] This invention provides a method for preparing honeycomb-shaped blue-gray and blue-brown foamed glazes. The raw materials for the foamed glazes consist of a base glaze, a foaming and coloring agent, and an auxiliary coloring agent. The base glaze consists of 25-35 wt% feldspar, 20-25 wt% quartz, 20-30 wt% kaolin, 10-15 wt% calcined talc, 2-6 wt% limestone, and 3-8 wt% zinc oxide. The foaming and coloring agent consists of silicon dioxide carbon and iron oxide, used in amounts of 0.3-2 wt% and 0.5-4 wt% of the base glaze, respectively. The auxiliary coloring agent consists of chromium oxide, cobalt oxide, and nickel oxide, used in amounts of 1.5-3 wt%, 4-8 wt%, and 0.3-0.6 wt% of the base glaze, respectively. The preparation method includes the following steps:

[0007] (1) After weighing the raw materials of the above foamed glaze, add sodium tripolyphosphate as a diluent and carboxymethyl cellulose as a binder, with the amounts being 0.2-0.3 wt% and 0.1-0.2 wt% of the base glaze, respectively. Add the glaze to a ball mill for ball milling for 30-60 min. After passing through a 250-mesh sieve, the glaze slurry is obtained.

[0008] (2) Glaze the body by dipping, with a glaze thickness of 0.3-0.5 mm. After drying, fire it by heating at 5℃ / min to 800℃, then heating at 3℃ / min to the firing temperature of 1290-1310℃, holding for 30-60 min, and then cooling naturally to obtain honeycomb blue-gray and blue-brown foamed glaze.

[0009] In the above scheme, the method for preparing silicon-oxygen-carbon in the raw materials of the present invention is as follows:

[0010] (1) After mixing polyorganosiloxane, crosslinking agent and catalyst evenly, the mixture is injected into a mold and thermally crosslinked at 80-100℃ for 8-10 hours to obtain a crosslinked body. The obtained crosslinked body is crushed and sieved to obtain precursor powder. The mass ratio of polyorganosiloxane to crosslinking agent is 1-4:1, and the amount of catalyst is 0.3-0.5% of the total mass of polyorganosiloxane and crosslinking agent. The crosslinking agent is a cyclic siloxane or a vinyl siloxane, and the catalyst is a nickel complex or a platinum complex.

[0011] (2) The precursor powder is subjected to pyrolysis under inert gas protection, that is, the temperature is increased to the pyrolysis temperature of 1100~1300℃ at 5℃ / min, the holding time is 30~90min, and the temperature is reduced to room temperature at 3℃ / min after the holding time is completed to obtain black silicon oxide carbon powder.

[0012] Furthermore, the polyorganosiloxane of the present invention is a hydrogen-containing polymethylsiloxane, or a combination of a hydrogen-containing polymethylsiloxane and a polyphenylmethylsiloxane; the crosslinking agent is tetramethyltetravinylcyclotetrasiloxane, or a combination of tetramethyltetravinylcyclotetrasiloxane and a terminal vinyl polydimethylsiloxane; and the catalyst is a methylvinylsiloxane-coordinated Pt complex.

[0013] The products prepared using the above-mentioned method for honeycomb-shaped blue-gray and blue-brown foamed glazes have an uneven glaze surface, with air bubbles in the depressions ranging from 4.0 to 10.0 mm in size, and a colorimetric value of L. * =29.8~34.7, a=-1.4~-0.3, b=-9.2~-2.0; the chromaticity value at the convex point is L * =31.6~37.8, a=1.0~1.7, b=-0.9~0.3.

[0014] The present invention has the following beneficial effects:

[0015] (1) This invention uses feldspar, quartz, kaolin, calcined talc, limestone, and zinc oxide as raw materials to prepare the base glaze. Silicon oxide carbon (SiOC) and iron oxide serve as both foaming agents and colorants, with cobalt oxide, chromium oxide, and nickel oxide as auxiliary colorants to prepare honeycomb-shaped blue-gray and blue-brown foamed glazes. Silicon oxide carbon (SiOC) is prepared by a polymer precursor method. Because this material contains network carbon and free carbon (40-50%), it appears black. During high-temperature oxidation, SiOC produces carbon dioxide gas (see Equation 1) and forms a SiO2 coating layer on its surface, preventing further oxidation and forming a SiOC@SiO2 core-shell structure colorant. Furthermore, iron oxide is brownish-red and undergoes a decomposition reaction at high temperatures (see Equation 2) to produce black iron(III) oxide and oxygen.

[0016] SiOC+O2 → SiOC@SiO2+CO2↑ (1)

[0017] Fe2O3→Fe3O4+O2↑ (2)

[0018] (2) This invention utilizes silicon-oxygen-carbon (SiOC) and iron oxide to function as foaming agents and colorants, causing the glaze melt to foam and layer. Under the combined action of other colorants, the glaze melt exhibits a blue bottom layer and a gray or brown surface layer. After the glaze bubbles rupture, open pores are generated. After the sample cools, the glaze surface exhibits a honeycomb effect, that is, the concave areas are blue and the protruding areas are gray or brown, thus giving the product extremely high artistic value.

[0019] (3) This invention enriches the preparation technology of foamed glaze, expands the types of foaming agents, and has a simple preparation process that is easy to industrialize, which is conducive to promoting the application and development of artistic glaze.

[0020] The present invention will now be described in further detail with reference to embodiments. Detailed Implementation

[0021] This invention discloses a method for preparing honeycomb-shaped blue-gray and blue-brown foamed glazes. The raw materials for the foamed glaze consist of a base glaze, a foaming and coloring agent, and an auxiliary coloring agent. The base glaze consists of 25-35 wt% feldspar, 20-25 wt% quartz, 20-30 wt% kaolin, 10-15 wt% calcined talc, 2-6 wt% limestone, and 3-8 wt% zinc oxide.

[0022] The foaming and coloring agents are silicon-oxygen-carbon (SiOC) and iron oxide, with dosages of 0.3–2 wt% and 0.5–4 wt% of the base glaze, respectively; the auxiliary coloring agents are chromium oxide, cobalt oxide, and nickel oxide, with dosages of 1.5–3 wt%, 4–8 wt%, and 0.3–0.6 wt% of the base glaze, respectively. The raw material formulations of each embodiment are shown in Table 1.

[0023] The preparation method of honeycomb-shaped blue-gray and blue-brown foamed glazes includes the following steps:

[0024] (1) After weighing the raw materials of foamed glaze, add sodium tripolyphosphate as a diluent and carboxymethyl cellulose as a binder, with the amounts being 0.2-0.3 wt% and 0.1-0.2 wt% of the base glaze, respectively. Add the mixture to a ball mill for ball milling (according to the mass ratio of material:ball:water = 1:1.5-2.0:0.5-0.8), and the ball milling time is 30-60 min. After passing through a 250-mesh sieve, the glaze slurry is obtained.

[0025] (2) Glaze the body by dipping, with a glaze thickness of 0.3-0.5 mm. After drying at 80°C for 2 hours in an oven, fire it by raising the temperature to 800°C at 5°C / min and then raising it to the firing temperature of 1290-1310°C at 3°C / min. Hold the temperature for 30-60 minutes and then let it cool naturally after holding the temperature to obtain honeycomb-shaped blue-gray and blue-brown foamed glaze.

[0026] The process parameters for the preparation methods of each embodiment are shown in Table 2.

[0027] The preparation method of silicon-oxygen carbon (SiOC) in the raw materials is as follows:

[0028] (1) After the polyorganosiloxane, crosslinking agent and catalyst are mixed evenly, they are injected into the mold and thermally crosslinked at 100°C for 10 hours to obtain the crosslinked body. The obtained crosslinked body is crushed and passed through a 200-mesh sieve to obtain the precursor powder. The mass ratio of polyorganosiloxane to crosslinking agent is 2:1, and the amount of catalyst is 0.3wt% of the total mass of polyorganosiloxane and crosslinking agent. The polyorganosiloxane is a hydrogen-containing polysiloxane, the crosslinking agent is tetramethyltetravinylcyclotetrasiloxane, and the catalyst is a methylvinylsiloxane-coordinated Pt complex.

[0029] (2) The above precursor powder was subjected to pyrolysis under the protection of an inert gas (argon), that is, the temperature was increased to the pyrolysis temperature of 1200℃ at 5℃ / min, the holding time was 60min, and the temperature was reduced to room temperature at 3℃ / min after the holding time was completed to obtain black silicon oxide carbon powder (SiOC).

[0030] Table 1. Raw material formulation composition (wt%) of various embodiments of the present invention

[0031]

[0032] Note: The amounts of foaming agents, colorants, and auxiliary colorants are relative to the base glaze.

[0033] Table 2. Process parameters of the preparation methods in various embodiments of the present invention

[0034]

[0035] Note: The amounts of sodium tripolyphosphate and carboxymethyl cellulose are relative to the base glaze.

[0036] Performance testing characteristics:

[0037] 1. Describe the color of the concave and convex areas of the glaze using the observation method;

[0038] 2. Use vernier calipers to measure the size of the opening (pit) in the glaze. Since the pit is close to a circle, take the average value (mm) of the perpendicular cross measurements.

[0039] 3. Use a colorimeter to measure the colorimetric values ​​at the openings (pits) and edges (convexities) of the glaze surface. These values ​​are used to characterize the colorimetric values ​​at different locations on the sample, and are denoted as L*, a, and b. The L* value represents the brightness of the sample color; the smaller the value, the darker the color. The a value represents the red and green values; a positive value represents a reddish tint, and a negative value represents a greenish tint. The b value represents the yellow and blue values; a positive value represents a yellowish tint, and a negative value represents a bluish tint. The sample color is a combination of the L*, a, and b values.

[0040] The test results are shown in Table 3.

[0041] Table 3 Performance parameters of honeycomb blue-gray and blue-brown foamed glazes in various embodiments of the present invention

[0042]

Claims

1. A method for preparing honeycomb-shaped blue-gray and blue-brown foamed glazes, characterized in that: The foamed glaze is composed of a base glaze, a foaming and coloring agent, and an auxiliary coloring agent. The base glaze consists of 25-35 wt% feldspar, 20-25 wt% quartz, 20-30 wt% kaolin, 10-15 wt% calcined talc, 2-6 wt% limestone, and 3-8 wt% zinc oxide. The foaming and coloring agent is silicon dioxide carbon and iron oxide, used at amounts of 0.3-2 wt% and 0.5-4 wt% of the base glaze, respectively. The auxiliary coloring agent is chromium oxide, cobalt oxide, and nickel oxide, used at amounts of 1.5-3 wt%, 4-8 wt%, and 0.3-0.6 wt% of the base glaze, respectively. The preparation method includes the following steps: (1) After weighing the raw materials of the above foamed glaze, add sodium tripolyphosphate as a diluent and carboxymethyl cellulose as a binder, with the amounts being 0.2-0.3 wt% and 0.1-0.2 wt% of the base glaze, respectively. Add the glaze to a ball mill for ball milling for 30-60 min. After passing through a 250-mesh sieve, the glaze slurry is obtained. (2) The body is glazed by dipping, with a glaze thickness of 0.3–0.5 mm. After drying, it is fired by raising the temperature to 800℃ at 5℃ / min, then raising it to the firing temperature of 1290–1310℃ at 3℃ / min, holding it at that temperature for 30–60 min, and then allowing it to cool naturally. This results in a foamed glaze with a honeycomb-like texture, where the concave areas are bluish-gray and the convex areas are bluish-brown. The bubble size in the concave areas is 4.0–10.0 mm, and its color value is L. * =29.8~34.7, a=-1.4~-0.3, b=-9.2~-2.0; the chromaticity value at the convex point is L * =31.6~37.8, a=1.0~1.7, b=-0.9~0.3; The method for preparing the silicon-oxygen carbon is as follows: (1) After mixing polyorganosiloxane, crosslinking agent and catalyst evenly, the mixture is injected into a mold and thermally crosslinked at 80-100℃ for 8-10 hours to obtain a crosslinked body. The obtained crosslinked body is crushed and sieved to obtain precursor powder. The mass ratio of polyorganosiloxane to crosslinking agent is 1-4:1, and the amount of catalyst is 0.3-0.5% of the total mass of polyorganosiloxane and crosslinking agent. The crosslinking agent is a cyclic siloxane or a vinyl siloxane, and the catalyst is a nickel complex or a platinum complex. (2) The precursor powder is subjected to pyrolysis under inert gas protection, that is, the temperature is increased to the pyrolysis temperature of 1100~1300℃ at 5℃ / min, the holding time is 30~90min, and the temperature is reduced to room temperature at 3℃ / min after the holding time is completed, thus obtaining black silicon oxide carbon powder.

2. The method for preparing honeycomb-shaped blue-gray and blue-brown foamed glazes according to claim 1, characterized in that: The polyorganosiloxane is a hydrogen-containing polymethylsiloxane, or a combination of a hydrogen-containing polymethylsiloxane and a polyphenylmethylsiloxane; the crosslinking agent is tetramethyltetravinylcyclotetrasiloxane, or a combination of tetramethyltetravinylcyclotetrasiloxane and a terminal vinyl polydimethylsiloxane; the catalyst is a methylvinylsiloxane-coordinated Pt complex.

3. The product obtained by the preparation method of honeycomb blue-gray and blue-brown foamed glaze as described in claim 1 or 2.

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