Application method of environment-friendly high-temperature copper-based glaze fired in multi-element atmosphere

Abstract

The application discloses an application method of an environment-friendly high-temperature copper glaze fired in a multi-element atmosphere, and comprises the following steps: S1, uniformly mixing raw materials according to the following weight percentage: 30-32% of nepheline syenite, 5-10% of talc, 4-9% of kaolin, 15-18% of calcite, 30-35.5% of quartz, 4-9% of barium carbonate, 0.8-2% of tin oxide and 0.2-1.4% of copper oxide to obtain powder; S2, performing mixed ball milling; S3, performing glaze pulp mesh screening and aging to obtain glaze material; and S4, applying the glaze material to the surface of a blank, drying, and firing in an oxidizing or reducing atmosphere to obtain an environment-friendly high-temperature copper glaze decoration product. The application provides an original solution for solving the contradiction between the atmosphere sensitivity and the environmental protection of the high-temperature copper glaze, and therefore has a good market prospect.

Description

Technical Field

[0001] This invention relates to the field of ceramic technology, and in particular to a method for applying an environmentally friendly high-temperature copper-based glaze fired in a multi-atmosphere environment. Background Technology

[0002] Copper-based glazes hold a significant place and technological legacy in the history of Chinese ceramics. For example, the high-temperature copper-red glaze pioneered by the Qiongyao kiln in the Tang Dynasty is hailed as "the first red in the world," and its high-temperature lead-free and underglaze painting techniques profoundly influenced later kilns such as Changsha Kiln and Jingdezhen underglaze red. However, the preparation of traditional copper-red glaze has long relied on empirical techniques, lacking systematic scientific research on the response mechanism to dynamic changes in firing atmosphere. This results in poor glaze color stability and low yield, severely restricting its artistic reproducibility and large-scale development. Looking at the current state of research both domestically and internationally, existing explorations of copper glazes largely focus on low-temperature glaze systems, while significant shortcomings remain in the color stability and environmental performance of copper-based glazes under high-temperature conditions. In particular, there is a lack of high-temperature lead-free copper glaze formulas capable of achieving stable color development in multi-element firing atmospheres. Although CN107382067A discloses a method for preparing copper rust glaze using nepheline syenite, it requires firing in an oxidizing atmosphere, and the resulting glaze color varies with the texture, without a clear understanding of the specific color development rules. CN113087393B prepared a copper-red glaze with uniform color distribution by combining a base glaze and a top glaze under a reducing atmosphere of low-temperature oxidation and high-temperature strong reduction, but the process is relatively complex and requires two glazing applications. CN113979636B produced a bluish-green copper-based glaze by firing in a reducing atmosphere of low-temperature oxidation and medium-temperature reduction, but did not address the glaze coloration under an oxidizing atmosphere. The glaze formulation involved in this technical solution breaks through the limitation of existing copper-based glazes that can only be fired in a single atmosphere. It can be fired in an oxidizing atmosphere throughout the process, or in a combination of low-temperature oxidation and high-temperature reduction atmospheres, and can exhibit a stable glaze color. This advancement not only broadens the firing process path of copper-based glazes, but also significantly enhances the consistency and controllability of glaze color, providing richer technical options for ceramic decoration processes.

[0003] Therefore, it is urgent to combine materials science with modern glaze design methods to deeply analyze the evolution of the valence state and color development mechanism of copper ions in different kiln atmospheres such as oxidation and reduction, and to develop new high-temperature copper-based glazes that have both excellent environmental protection characteristics and artistic expression, so as to break through the limitations of traditional processes and promote the green and scientific development of ceramic glaze technology. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for applying environmentally friendly high-temperature copper-based glazes that are low-cost, simple to process, and have excellent performance in a multi-atmosphere firing process.

[0005] This invention is achieved through the following technical solution:

[0006] A method for applying an environmentally friendly high-temperature copper-based glaze fired in a multi-atmosphere environment, characterized by:

[0007] Step 1: Mix the raw materials according to the following weight percentage formula: nepheline syenite 30-32%, talc 5-10%, kaolin 4-9%, calcite 15-18%, quartz 30-35.5%, barium carbonate 4-9%, with the addition of tin oxide 0.8-2% and copper oxide 0.2-1.4%, weigh them and mix them evenly to obtain the powder.

[0008] Step 2: Add the powder prepared in Step 1, the alumina ball mill, and water to the ball mill jar according to the mass ratio of powder: alumina ball mill: water = 1: 1.5~1.8: 0.6~0.8, and mix and ball mill.

[0009] Step 3: After ball milling in Step 2, the glaze slurry is first passed through a 40-mesh sieve and then through a 200-mesh sieve, and then aged to obtain the glaze material;

[0010] Step 4: Apply the glaze obtained in Step 3 to the surface of the body, dry it, and then fire it in an oxidizing or reducing atmosphere to obtain an environmentally friendly high-temperature copper-based glaze decorative product.

[0011] The total firing time in step four under an oxidizing atmosphere is 12 hours, of which the holding time at the highest firing temperature of 1250~1280℃ is 1.5~3 hours.

[0012] Step four, the firing in a reducing atmosphere, employs a two-stage firing process, specifically:

[0013] First stage: Under an oxidizing atmosphere, the temperature inside the kiln is uniformly raised from room temperature to 1020℃. The firing time for this stage is 5 hours.

[0014] The second stage: switch to a reducing atmosphere and uniformly raise the temperature inside the kiln from 1020℃ to the maximum firing temperature of 1290~1310℃, wherein the holding time at the maximum firing temperature is 1.5~3 hours;

[0015] The total firing time for the first and second stages is 12 hours;

[0016] The product obtained by firing in an oxidizing atmosphere in step four exhibits a peacock blue color with the following chromaticity values: L*71.11~81.01, a* -13.88~-19.43, b* -0.05~-2.70;

[0017] The product obtained by firing in a reducing atmosphere in step four is dark red, with a color value of: L*19.71~24.85, a*17.86~28.53, b*4.75~8.69.

[0018] In step two, the ratio of alumina ball milling particles with diameters of 12mm, 6mm, and 2.5mm is 10%:80%:10%, and the milling time is 8–12 hours.

[0019] The residue after sieving in step three is 0.05-0.07%.

[0020] The aging process in step three takes 8 to 12 hours.

[0021] The present invention has the following beneficial effects:

[0022] (1) This invention successfully developed a high-temperature environmentally friendly copper-based glaze that can be fired in a multi-atmosphere environment. Its core breakthrough lies in utilizing the unique physicochemical properties of nepheline syenite, which fundamentally expands the performance boundaries of copper-based glazes. Compared with traditional copper glazes, existing technologies generally rely on the simple physical dissolution and volatilization diffusion of copper ions in high-temperature melts, resulting in unstable and uneven color development. This product achieves significant improvements in three key performance aspects: First, this patent uses nepheline syenite as its core, whose unique "hyperalkaline" and low viscosity characteristics enable it to form a dense and flexible glass phase network before a large amount of copper ions volatilize. This network not only effectively locks in copper ions, significantly reducing their volatilization loss (>30%), but more importantly, it provides a uniform and stable chemical coordination environment for copper ions, transforming them from easily volatile and migratable free states into stable color-producing centers chemically bound by the glass network. Secondly, it achieves a breakthrough in color uniformity. The rapid melting of nepheline syenite generates a unique "instantaneous high-temperature" effect, causing a sharp decrease in system viscosity at key temperature points and an increase in component diffusion rate by approximately 50%. This ensures that copper ions achieve a molecular-level uniform distribution in the glaze, completely solving the common process problems of color spots and color differences in traditional copper glazes, presenting a full and uniform ideal color effect. Thirdly, traditional technologies have extremely stringent requirements for the firing atmosphere (oxidation or reduction), requiring a single, strictly controlled atmosphere to obtain the desired color. This patent achieves significant progress in atmosphere adaptability, thanks to the flexible glass network structure formed by the moderate silica-alumina ratio of nepheline syenite. While maintaining necessary stability, the glaze provides an ideal space for the controllable conversion of copper ions between different valence states. This innovative structure successfully creates a tolerant and stable color-producing environment, effectively buffering the impact of ±5% oxygen concentration fluctuations and simultaneously stabilizing the color-producing behavior of multiple copper valence states. In an oxidizing atmosphere, the system stably exhibits a bright and uniform peacock blue by regulating the valence state and coordination of copper; in a reducing atmosphere, the system rapidly adapts to changes in oxygen partial pressure, causing copper to precipitate uniformly in elemental or cuprous ion states, resulting in a deep and pure crimson red. The ability to achieve stable and sophisticated polychromatic colors under two completely different firing atmospheres with the same formula is a technical effect that traditional copper glazes have never revealed and cannot achieve.

[0023] (2) The environmental advantages and technological innovation of this invention are particularly prominent. Through the scientific application of nepheline syenite, not only has the toxic components such as lead and cadmium in traditional formulas been completely replaced, but it is also worth noting that by introducing appropriate amounts of calcite, talc, and other components for system optimization, the adverse effects of alkaline glazes on copper-red coloration have been successfully overcome, establishing a new glaze system that can maintain the low-temperature advantages of nepheline syenite while stably presenting rich copper-based colors. This technical route fully complies with the requirements of the national green manufacturing policy, providing the ceramic industry with an innovative path that combines excellent artistic expression with significant environmental benefits, and therefore has good market prospects. Attached Figure Description

[0024] Figure 1 This is a photograph of the environmentally friendly high-temperature copper-based glaze decorative product obtained in Embodiment 1 of the present invention;

[0025] Figure 2 This is a photograph of the environmentally friendly high-temperature copper-based glaze decorative product obtained in Embodiment 2 of the present invention;

[0026] Figure 3 These are L*a*b* instrument photographs of the samples from Examples 1-3 prepared under an oxidizing atmosphere;

[0027] Figure 4 These are L*a*b* instrument photographs of the samples from Examples 4-5 prepared under an oxidizing atmosphere;

[0028] Figure 5 These are L*a*b* instrument test photographs of the samples from Examples 1-3 prepared under a reducing atmosphere;

[0029] Figure 6 These are L*a*b* instrument test photographs of the samples from Examples 4-5 prepared under a reducing atmosphere. Detailed Implementation

[0030] To further illustrate the present invention, the technical means and effects adopted to achieve the intended purpose of the invention, the present invention will be described in detail below with reference to preferred embodiments.

[0031] Example 1:

[0032] A method for applying an environmentally friendly high-temperature copper-based glaze fired in a multi-atmosphere environment.

[0033] Step 1: Mix the following raw materials by weight percentage according to the formula: nepheline syenite 30%, talc 10%, kaolin 9%, calcite 15%, quartz 30%, barium carbonate 6%, plus tin oxide 0.8% and copper oxide 0.2%, weigh them and mix them evenly to obtain powder.

[0034] Step 2: Add the powder prepared in Step 1, the alumina ball mill, and water to the ball mill jar according to the mass ratio of powder: alumina ball mill: water = 1: 1.8: 0.7, and mix and ball mill.

[0035] Step 3: After ball milling in Step 2, the glaze slurry is first passed through a 40-mesh sieve and then through a 200-mesh sieve, and then aged to obtain the glaze material;

[0036] Step 4: Apply the glaze obtained in Step 3 to the surface of the body, dry it, and then fire it in an oxidizing or reducing atmosphere to obtain an environmentally friendly high-temperature copper-based glaze decorative product.

[0037] In step two, the ratio of alumina ball milling particles with diameters of 12mm, 6mm, and 2.5mm is 10%:80%:10%, and the milling time is 9 hours.

[0038] The residue after sieving in step three is 0.06%.

[0039] The aging process in step three takes 12 hours.

[0040] The total firing time in step four under an oxidizing atmosphere is 12 hours, of which the holding time at the highest firing temperature of 1250℃ is 3 hours.

[0041] The product obtained by firing in an oxidizing atmosphere in step four is peacock blue, with a color value of L*74.42, a*-13.88, b*-0.05.

[0042] Step four, the firing in a reducing atmosphere, employs a two-stage firing process, specifically:

[0043] First stage: Under an oxidizing atmosphere, the temperature inside the kiln is uniformly raised from room temperature to 1020℃. The firing time for this stage is 5 hours.

[0044] The second stage: switch to a reducing atmosphere and uniformly raise the temperature inside the kiln from 1020℃ to the maximum firing temperature of 1290℃, wherein the holding time at the maximum firing temperature is 3 hours.

[0045] The total firing time for the first and second stages is 12 hours;

[0046] The product obtained by firing in a reducing atmosphere in step four is dark red, with a color value of L*22.52, a*27.68, b*7.51.

[0047] Example 2:

[0048] A method for applying an environmentally friendly high-temperature copper-based glaze fired in a multi-atmosphere environment.

[0049] Step 1: Mix the following raw materials by weight percentage according to the formula: nepheline syenite 32%, talc 7%, kaolin 7%, calcite 18%, quartz 32%, barium carbonate 4%, plus tin oxide 2% and copper oxide 0.2%, weigh them and mix them evenly to obtain the powder.

[0050] Step 2: Add the powder prepared in Step 1, the alumina ball mill, and water to the ball mill jar according to the mass ratio of powder: alumina ball mill: water = 1: 1.5: 0.6, and mix and ball mill.

[0051] Step 3: After ball milling in Step 2, the glaze slurry is first passed through a 40-mesh sieve and then through a 200-mesh sieve, and then aged to obtain the glaze material;

[0052] Step 4: Apply the glaze obtained in Step 3 to the surface of the body, dry it, and then fire it in an oxidizing or reducing atmosphere to obtain an environmentally friendly high-temperature copper-based glaze decorative product.

[0053] In step two, the ratio of alumina ball milling particles with diameters of 12mm, 6mm, and 2.5mm is 10%:80%:10%, and the milling time is 10 hours.

[0054] The residue on the sieve after sieving in step two is 0.05%.

[0055] The aging process in step three takes 8 hours.

[0056] The total firing time in step four under an oxidizing atmosphere is 12 hours, of which the holding time at the highest firing temperature of 1270℃ is 2 hours.

[0057] The product obtained by firing in an oxidizing atmosphere in step four is peacock blue, with a color value of L*78.55, a*-17.03, b*-2.70.

[0058] Step four, the firing in a reducing atmosphere, employs a two-stage firing process, specifically:

[0059] First stage: Under an oxidizing atmosphere, the temperature inside the kiln is uniformly raised from room temperature to 1020℃. The firing time for this stage is 5 hours.

[0060] The second stage: switch to a reducing atmosphere and uniformly raise the temperature inside the kiln from 1020℃ to the maximum firing temperature of 1310℃, wherein the holding time at the maximum firing temperature is 2 hours.

[0061] The total firing time for the first and second stages is 12 hours;

[0062] The product obtained by firing in a reducing atmosphere in step four is dark red, with a color value of L*20.69, a*21.04, b*5.07.

[0063] Example 3:

[0064] A method for applying an environmentally friendly high-temperature copper-based glaze fired in a multi-atmosphere environment.

[0065] Step 1: Mix the following raw materials by weight percentage according to the formula: nepheline syenite 32%, talc 5%, kaolin 4%, calcite 18%, quartz 32%, barium carbonate 9%, plus tin oxide 1% and copper oxide 1.4%, weigh them and mix them evenly to obtain the powder.

[0066] Step 2: Add the powder prepared in Step 1, the alumina ball mill, and water to the ball mill jar according to the mass ratio of powder: alumina ball mill: water = 1: 1.6: 0.75, and mix and ball mill.

[0067] Step 3: After ball milling in Step 2, the glaze slurry is first passed through a 40-mesh sieve and then through a 200-mesh sieve, and then aged to obtain the glaze material;

[0068] Step 4: Apply the glaze obtained in Step 3 to the surface of the body, dry it, and then fire it in an oxidizing or reducing atmosphere to obtain an environmentally friendly high-temperature copper-based glaze decorative product.

[0069] In step two, the ratio of alumina ball milling particles with diameters of 12mm, 6mm, and 2.5mm is 10%:80%:10%, and the milling time is 9 hours.

[0070] The residue on the sieve after sieving in step two is 0.06%.

[0071] The aging process in step three takes 10 hours.

[0072] The total firing time in step four under an oxidizing atmosphere is 12 hours, of which the holding time at the highest firing temperature of 1280°C is 1.5 hours.

[0073] The product obtained by firing in an oxidizing atmosphere in step four is peacock blue, with a color value of L*80.00, a*-15.14, b*-1.83.

[0074] Step four, the firing in a reducing atmosphere, employs a two-stage firing process, specifically:

[0075] First stage: Under an oxidizing atmosphere, the temperature inside the kiln is uniformly raised from room temperature to 1020℃. The firing time for this stage is 5 hours.

[0076] The second stage: switch to a reducing atmosphere and uniformly raise the temperature inside the kiln from 1020℃ to the maximum firing temperature of 1300℃, wherein the holding time at the maximum firing temperature is 1.5 hours.

[0077] The total firing time for the first and second stages is 12 hours;

[0078] The product obtained by firing in a reducing atmosphere in step four is dark red, with a color value of L*24.31, a*28.53, b*8.69.

[0079] Example 4:

[0080] A method for applying an environmentally friendly high-temperature copper-based glaze fired in a multi-atmosphere environment.

[0081] Step 1: Mix the following raw materials by weight percentage: nepheline syenite 31.5%, talc 5.5%, kaolin 5%, calcite 16%, quartz 35%, barium carbonate 7%, plus tin oxide 2% and copper oxide 1%, weigh them and mix them evenly to obtain powder.

[0082] Step 2: Add the powder prepared in Step 1, the alumina ball mill, and water to the ball mill jar according to the mass ratio of powder: alumina ball mill: water = 1: 1.7: 0.65, and mix and ball mill.

[0083] Step 3: After ball milling in Step 2, the glaze slurry is first passed through a 40-mesh sieve and then through a 200-mesh sieve, and then aged to obtain the glaze material;

[0084] Step 4: Apply the glaze obtained in Step 3 to the surface of the body, dry it, and then fire it in an oxidizing or reducing atmosphere to obtain an environmentally friendly high-temperature copper-based glaze decorative product.

[0085] In step two, the ratio of alumina ball milling particles with diameters of 12mm, 6mm, and 2.5mm is 10%:80%:10%, and the milling time is 8 hours.

[0086] The residue after sieving in step two is 0.07%.

[0087] The aging process in step three takes 12 hours.

[0088] The total firing time in step four under an oxidizing atmosphere is 12 hours, of which the holding time at the highest firing temperature of 1260℃ is 2 hours.

[0089] The product obtained by firing in an oxidizing atmosphere in step four is peacock blue, with a color value of L*81.01, a* -14.97, b* -1.77.

[0090] Step four, the firing in a reducing atmosphere, employs a two-stage firing process, specifically:

[0091] First stage: Under an oxidizing atmosphere, the temperature inside the kiln is uniformly raised from room temperature to 1020℃. The firing time for this stage is 5 hours.

[0092] The second stage: switch to a reducing atmosphere and uniformly raise the temperature inside the kiln from 1020℃ to the maximum firing temperature of 1310℃, wherein the holding time at the maximum firing temperature is 2 hours.

[0093] The total firing time for the first and second stages is 12 hours;

[0094] The product obtained by firing in a reducing atmosphere in step four is dark red, with a color value of L*24.85, a*24.95, b*6.89.

[0095] Example 5:

[0096] A method for applying an environmentally friendly high-temperature copper-based glaze fired in a multi-atmosphere environment.

[0097] Step 1: Mix the raw materials according to the following weight percentage formula: nepheline syenite 31.5%, talc 5.5%, kaolin 4.5%, calcite 16.5%, quartz 35.5%, barium carbonate 6.5%, plus tin oxide 1.5% and copper oxide 0.4%, weigh them and mix them evenly to obtain powder.

[0098] Step 2: Add the powder prepared in Step 1, the alumina ball mill, and water to the ball mill jar according to the mass ratio of powder: alumina ball mill: water = 1: 1.6: 0.8, and mix and ball mill.

[0099] Step 3: After ball milling in Step 2, the glaze slurry is first passed through a 40-mesh sieve and then through a 200-mesh sieve, and then aged to obtain the glaze material;

[0100] Step 4: Apply the glaze obtained in Step 3 to the surface of the body, dry it, and then fire it in an oxidizing or reducing atmosphere to obtain an environmentally friendly high-temperature copper-based glaze decorative product.

[0101] In step two, the ratio of alumina ball milling particles with diameters of 12mm, 6mm, and 2.5mm is 10%:80%:10%, and the milling time is 12 hours.

[0102] The residue on the sieve after sieving in step two is 0.05%.

[0103] The aging process in step three takes 10 hours.

[0104] The total firing time in step four under an oxidizing atmosphere is 12 hours, of which the holding time at the highest firing temperature of 1270°C is 1.5 hours.

[0105] The product obtained by firing in an oxidizing atmosphere in step four is peacock blue, with a color value of L*71.11, a*-19.43, b*-2.04.

[0106] Step four, the firing in a reducing atmosphere, employs a two-stage firing process, specifically:

[0107] First stage: Under an oxidizing atmosphere, the temperature inside the kiln is uniformly raised from room temperature to 1020℃. The firing time for this stage is 5 hours.

[0108] The second stage: switch to a reducing atmosphere and uniformly raise the temperature inside the kiln from 1020℃ to the maximum firing temperature of 1290℃, wherein the holding time at the maximum firing temperature is 1.5 hours.

[0109] The total firing time for the first and second stages is 12 hours;

[0110] The product obtained by firing in a reducing atmosphere in step four is dark red, with a color value of L*19.71, a*17.86, b*4.75.

[0111] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the principles and spirit of the present invention are included within the protection scope of the present invention.

Claims

1. A method for applying an environmentally friendly high-temperature copper-based glaze fired in a multi-component atmosphere, characterized in that: Step 1: a powder is prepared by weighing and uniformly mixing the following raw materials according to the following weight percentage: nepheline syenite 30-32%, talc 5-10%, kaolin 4-9%, calcite 15-18%, quartz 30-35.5%, barium carbonate 4-9%, and additionally 0.8-2% tin oxide and 0.2-1.4% copper oxide; Step 2: the powder prepared in Step 1, alumina milling balls, and water are added to a ball mill in a mass ratio of 1:1.5-1.8:0.6-0.8, respectively, and mixed and milled; Step 3: the glaze slurry after milling in Step 2 is first passed through a 40-mesh sieve and then a 200-mesh sieve, and then aged to obtain a glaze; Step 4: the glaze prepared in Step 3 is applied to the surface of a body, dried, and fired in an oxidizing or reducing atmosphere to obtain an environmentally friendly high-temperature copper-based glaze decorative product; the total firing time in the oxidizing atmosphere in Step 4 is 12 hours, including a holding time of 1.5-3 hours at the maximum firing temperature of 1250-1280°C; the firing in the reducing atmosphere in Step 4 uses a two-stage firing schedule, specifically: First stage: the temperature in the kiln is uniformly raised from room temperature to 1020°C in an oxidizing atmosphere, and the firing time for this stage is 5 hours; Second stage: the temperature in the kiln is uniformly raised from 1020°C to the maximum firing temperature of 1290-1310°C in a reducing atmosphere, and the holding time at the maximum firing temperature is 1.5-3 hours; the total firing time for the first and second stages is 12 hours; the product obtained by firing in the oxidizing atmosphere in Step 4 exhibits a peacock blue color with a color value of L*71.11-81.01, a*-13.88--19.43, and b*-0.05--2.70; the product obtained by firing in the reducing atmosphere in Step 4 exhibits a deep red color with a color value of L*19.71-24.85, a*17.86-28.53, and b*4.75-8.69; the particle size ratio of the alumina milling balls in Step 2 is 10%:80%:10% for 12 mm, 6 mm, and 2.5 mm, respectively, and the milling time is 8-12 hours; the sieve residue after sieving in Step 3 is 0.05-0.07%; the aging time in Step 3 is 8-12 hours. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ 2. The use according to claim 1, characterized in that: ​ 3. The method of use of claim 1, wherein: ​ 4. The use according to claim 1, characterized in that: ​

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