Preparation method of antique blue and white colorant and blue and white porcelain with controllable color tone and halo

Abstract

The application relates to a preparation method of antique blue and white color material and blue and white porcelain with controllable color tone and halo, characterized by the following raw material formula: cobalt oxide 5-60%, tricobalt tetraoxide 15-60%, stone blue 2-5%, bauxite 17-58%, additional aluminum hydroxide 1-5%, lithium carbonate 1-2%, zinc oxide 1-5%, barium carbonate 1-5%, and borax 1-5%. After the raw materials are crushed, the color agent and the stabilizer are mixed and calcined to obtain spinel crystal precursors, then the additional agent is added, and the antique blue and white color material is obtained through wet ball milling. The antique blue and white color material is drawn on antique clay blanks, then the blue and white glaze is applied to the surface of the blanks and the blue and white color material, and the prepared blue and white porcelain has controllable color tone and halo. The preparation method is simple, and the firing temperature is low.

Description

Technical Field

[0001] This invention relates to the field of inorganic non-metallic materials technology, and in particular to an antique blue-and-white porcelain pigment with controllable hue and diffusion, and a method for preparing blue-and-white porcelain. Background Technology

[0002] Chinese blue and white porcelain is one of the world's most influential cultural heritages. It is generally defined as an underglaze decoration, made by coating a cobalt-containing pigment onto the porcelain body, covering the surface with a transparent glaze, and firing at high temperatures. During the preparation and firing process of blue and white porcelain, the composition of the cobalt pigment and the preparation techniques result in uneven color tones and varying degrees of "blurring" (i.e., the diffusion distance of the cobalt lines) in different dynasties (especially the Yuan, Ming, and Qing dynasties) or even within the same dynasty. This causes the blue and white image to appear blurry in outline and lines, disrupting the bright, clear, and layered expressive effect of the blue and white design.

[0003] Therefore, since the 1930s, the blue-and-white porcelain making technique, refined over eight centuries, has become a unique and exquisite porcelain craft of Jingdezhen, attracting the attention of ceramic researchers both domestically and internationally. Researchers have conducted studies from multiple perspectives, including archaeology, art design, and science and technology. For a long time, ancient ceramic research, especially in the field of ancient ceramic science and technology, has focused on the formation of the "blurring" defect and the variation in color tone in blue-and-white decoration. Studies have been conducted on factors such as the composition of the glaze, the preparation process of the blue-and-white pigment, and the different components of the pigment. However, the mechanism of "blurring" and uneven color tone has never been proposed. Therefore, it is necessary to propose methods and technical pathways to overcome color diffusion and adjust the color tone, providing a scientific experimental basis for the preparation of high-quality blue-and-white porcelain.

[0004] CN113292359 discloses an antique-style blue and white porcelain pigment. Due to the depletion of high-quality cobalt ore, the quality of imitation Ming Zhengde blue and white porcelain has gradually declined. This invention uses porcelain stone, kaolin, limestone, aluminum oxide, zinc oxide, chromium oxide, pearlite, cobalt oxide, iron oxide, and manganese oxide as raw materials to prepare a blue and white porcelain pigment. After firing, it exhibits the color effect of Ming Zhengde blue and white porcelain, with a brightness L* value of 36-37, an a* value of 0-2, and an absolute value of b* of 30-31. This invention selects pearlite and other colorants containing iron, cobalt, and manganese, which is not only costly but also makes the color uncontrollable. The paper "Research on Antique Blue and White Porcelain" uses cobalt ore plus aqua regia and borax as the blue and white pigment formula. Firing in a reducing atmosphere at 1270–1290℃ produces blue and white porcelain with vibrant colors, clear and bright hues, uniform lines, and distinct patterns. However, the use of chemical pigments and cobalt ore as colorants results in excessively high costs, and the paper does not mention factors affecting image clarity. The paper "Experimental Preparation of Pigments for Blue and White Porcelain" uses CoO, Al2O3, ZnO, MgO, SiO2, and feldspar as the blue and white pigment formula. Firing in a reducing flame at 1300℃ in an oil-fired tunnel kiln produces blue and white porcelain with stable color. However, the use of feldspar as a flux makes controlling the diffusion distance difficult. The paper "Artificial Synthesis of Blue and White Porcelain Pigment" uses cobalt, iron, manganese, fillers such as bauxite, SiO2, Al2O3, and clay as the blue and white pigment formula. It describes firing the pigments in a reducing atmosphere at 1280–1300℃ to produce blue and white porcelain with varying colors. However, this method requires the use of iron and manganese colorants for co-coloring, and the high firing temperature significantly increases costs. While CN104761239A achieves vibrant blue and white colors and clear, unblemished lines through low-temperature firing, its complex raw materials and limited color range fail to reproduce the unique charm of different color hues in ancient blue and white porcelain. Furthermore, it is difficult to achieve large-scale industrial production. This patented colorant uses Co-containing raw materials and minerals as colorants, and combines them with raw materials such as aluminum hydroxide, lithium carbonate, ZnO, BaCO3, and borax using bauxite stabilizers to make it exist in the glaze as [CoO4] tetrahedra. The selection of inexpensive bauxite stabilizers not only stabilizes the color but also hinders the diffusion of coloring ions. Therefore, by controlling the amount of colorant, stabilizer, and additives, it is possible to achieve color diffusion and adjustable hue, providing a scientific experimental basis for the formulation of high-quality blue and white porcelain. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a simple, low-cost, high-quality antique blue and white porcelain pigment with controllable color and diffusion, and a method for preparing blue and white porcelain.

[0006] The technical solution of this invention is: a method for preparing antique blue and white porcelain pigment with controllable hue and diffusion, characterized in that:

[0007] Its raw material formula consists of the following weight percentages: cobalt oxide 5-60%, cobalt tetroxide 15-60%, alumina 2-5%, bauxite 17-58%, plus aluminum hydroxide 1-5%, lithium carbonate 1-2%, zinc oxide 1-5%, barium carbonate 1-5%, and borax 1-5%.

[0008] The cobalt oxide, cobalt tetroxide, and alumina are used as colorants, bauxite is used as a stabilizer, and aluminum hydroxide, lithium carbonate, zinc oxide, barium carbonate, and borax are used as additives.

[0009] After the raw material is crushed, the colorant and stabilizer are mixed and calcined to obtain a spinel crystal precursor. Then, an additive is added, and after wet ball milling, an antique blue and white porcelain pigment is obtained.

[0010] The color values ​​of the antique blue and white porcelain pigment are L*=37.9~42, a*=-3.6~10.0, and b*=-0.6~-49.2;

[0011] The wet ball milling process uses a material:ball:water ratio of 1:2:0.8-1. The raw materials are loaded into the ball milling equipment and milled at 60-80 rpm for 6-10 hours to obtain an antique blue and white porcelain pigment with a particle size of 0.1-1μm.

[0012] The calcination temperature is 900–1000℃, and the time is 8 hours.

[0013] A method for preparing blue and white porcelain, characterized by comprising the following steps:

[0014] Step 1: Mix 8-15% Yaoli glaze fruit, 56-68% calcined glaze fruit, and 17-36% glaze ash by weight percentage, and then put the raw materials into a ball mill with a material:ball:water ratio of 1:2:0.8 and ball mill for 10 minutes. The fineness of the slurry reaches less than 0.1% residue on a 10,000-mesh sieve to obtain blue and white glaze.

[0015] Step 2: Apply the antique blue-and-white pigment prepared by the method described in claim 1 onto the antique clay body, and then apply the blue-and-white glaze prepared in step 1 onto the surface of the body and the antique blue-and-white pigment. After drying, fire to obtain blue-and-white porcelain.

[0016] The firing process is carried out in a reducing atmosphere at a temperature of 1250–1270°C for 8–10 hours.

[0017] The thickness of the antique blue-and-white pigment applied to the antique clay body is 0.1–0.8 mm, and the thickness of the blue-and-white glaze applied to the body and the antique blue-and-white pigment is 0.5–2 mm.

[0018] The blue and white porcelain surface has a deep blue hue with a color value of b*=-13~-36 and a diffusion distance of 50~350μm.

[0019] The blue-and-white pigment with controllable crystal structure stability provided by this invention uses specific components and proportions, firstly utilizing Co... 2+ Different coordination properties result in different colors in the glaze. With the help of the stabilizer bauxite, which has a stronger ability to compete for oxygen ions, Co... 2+ The formation of Co-oxygen tetrahedra or cobalt aluminum spinel in the glaze not only stabilizes its color but also hinders the coloring of Co ions. 2+ The diffusion of colorant, therefore, by controlling the dosage of colorant, stabilizer, and additives, the proportion of colorant, stabilizer, and additives in the formula can be adjusted to achieve the desired Co content in the cobalt blue pigment. 2+ The proportions of different ligands, such as tetrahedrons and octahedrons, as well as the crystal ratio, can be controlled, thereby regulating the color tone of blue and white porcelain. Secondly, according to Fick's second law, adjusting the proportions of colorants, stabilizers, and additives in the formula controls the ease of ion diffusion (i.e., diffusion distance), thus achieving control over Co... 2+ The diffusion coefficient and diffusion distance (50–350 μm) are gradient-controlled. The blue-and-white porcelain produced using the aforementioned cobalt blue pigment with controllable crystal structure stability, as provided by this invention, exhibits controllable diffusion and color tone. The cobalt blue pigment with controllable crystal structure stability and subsequent raw materials for blue-and-white porcelain are widely available, the preparation method is simple, the firing temperature range is wide, and the firing time is short, making it suitable for large-scale production and possessing good market prospects. This invention solves the industry problem of unstable color tone and uncontrollable diffusion in traditional blue-and-white porcelain, and is applicable to multiple fields such as architectural ceramics, art ceramics, and daily-use ceramics. Attached Figure Description

[0020] The present invention will now be described in further detail with reference to the embodiments and accompanying drawings:

[0021] Figure 1 This is the OM diagram of Embodiment 1 of the present invention;

[0022] Figure 2 This is the OM diagram of Embodiment 2 of the present invention;

[0023] Figure 3 This is the OM diagram of Embodiment 3 of the present invention;

[0024] Figure 4 The images show the XRD patterns of the cobalt blue pigments obtained in Examples 1, 2, and 3 of this invention.

[0025] Figure 5 The images shown are SEM and EDS images of the intermediate layer of blue and white porcelain obtained in Examples 1, 2, and 3 of this invention; wherein, a1, b1, and c1 are the SEM images of the intermediate layer of Examples 1, 2, and 3, respectively; and a2, b2, and c2 are the EDS images of the intermediate layer of Examples 1, 2, and 3, respectively.

[0026] Figure 6 The image shows the SEM image of the particle size of the cobalt blue pigment in Example 1. Detailed Implementation

[0027] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0028] The raw materials used in this invention, including cobalt oxide, cobalt tetroxide, aluminum hydroxide, lithium carbonate, zinc oxide, barium carbonate, and borax, are chemically pure with a content greater than 98% and can be purchased commercially. The cobalt blue pigment comes from Gao'an, and the bauxite is from Guiyang. For the raw materials of the blue-and-white glaze, the Yaoli glaze fruit and glaze ash are traditional porcelain-making raw materials from the Jingdezhen area and can be purchased commercially. The antique-style clay is a commonly used antique-style clay available on the market. The specific chemical composition of these raw materials is shown in Table 1.

[0029] Table 1. Chemical composition of raw materials (wt%)

[0030]

[0031] Example 1

[0032] A method for preparing an antique blue-and-white porcelain pigment with controllable hue and diffusion, characterized in that:

[0033] Its raw material formula consists of the following weight percentages: cobalt oxide 60%, cobalt tetroxide 15%, alumina 5%, bauxite 20%, plus aluminum hydroxide 1%, lithium carbonate 2%, zinc oxide 5%, barium carbonate 1%, and borax 3%.

[0034] The cobalt oxide, cobalt tetroxide, and alumina are used as colorants, bauxite is used as a stabilizer, and aluminum hydroxide, lithium carbonate, zinc oxide, barium carbonate, and borax are used as additives.

[0035] After the raw material is crushed, the colorant and stabilizer are mixed and calcined to obtain a spinel crystal precursor. Then, an additive is added, and after wet ball milling, an antique blue and white porcelain pigment is obtained.

[0036] The color values ​​of the antique blue and white porcelain pigment are L*=42, a*=-3.2, b*=-0.6;

[0037] The wet ball milling process involves using a material:ball:water ratio of 1:2:1. The raw material is loaded into a ball mill and milled at 80 rpm for 6 hours to obtain an antique blue-and-white porcelain pigment with a particle size of 0.1 μm. Figure 6 As shown;

[0038] The calcination temperature was 900℃ and the time was 8 hours.

[0039] A method for preparing blue and white porcelain, characterized by comprising the following steps:

[0040] Step 1: Mix 8% Yaoli glaze fruit, 56% calcined glaze fruit, and 36% glaze ash by weight percentage, and then put the raw materials into a ball mill with a material:ball:water ratio of 1:2:0.8 and ball mill for 10 minutes. The fineness of the slurry reaches less than 0.1% residue on a 10,000-mesh sieve to obtain blue and white glaze.

[0041] Step 2: Apply the antique blue-and-white pigment prepared by the method described in claim 1 onto the antique clay body, and then apply the blue-and-white glaze prepared in step 1 onto the surface of the body and the antique blue-and-white pigment. After drying, fire to obtain blue-and-white porcelain.

[0042] The firing process is carried out in a reducing atmosphere at a temperature of 1250°C for 10 hours.

[0043] The thickness of the antique blue-and-white pigment applied to the antique clay body is 0.5 mm, and the thickness of the blue-and-white glaze applied to the body and the antique blue-and-white pigment is 0.5 mm.

[0044] like Figure 1 As shown, the blue and white patterns on the surface of the porcelain exhibit a deep blue tone, with a chromaticity value of b*=-25 and a diffusion distance of 200μm.

[0045] like Figure 4 The XRD pattern of the blue-and-white pigment shows that the main crystalline phase is cobalt oxide (CoO).

[0046] like Figure 5 (a1) As shown in the SEM of the intermediate layer, there is a layer of residual particles in the body-glaze interaction layer. These residual particles float in the glaze, according to the EDS results. Figure 5 (a2) is shown as an oxide of cobalt.

[0047] Example 2

[0048] A method for preparing an antique blue-and-white porcelain pigment with controllable hue and diffusion, characterized in that:

[0049] Its raw material formula consists of the following weight percentages: cobalt oxide 20%, cobalt tetroxide 60%, alumina 3%, bauxite 17%, plus aluminum hydroxide 3%, lithium carbonate 1%, zinc oxide 2%, barium carbonate 5%, and borax 5%.

[0050] The cobalt oxide, cobalt tetroxide, and alumina are used as colorants, bauxite is used as a stabilizer, and aluminum hydroxide, lithium carbonate, zinc oxide, barium carbonate, and borax are used as additives.

[0051] After the raw material is crushed, the colorant and stabilizer are mixed and calcined to obtain a spinel crystal precursor. Then, an additive is added, and after wet ball milling, an antique blue and white porcelain pigment is obtained.

[0052] The color values ​​of the antique blue and white porcelain pigment are L*=41.3, a*=-3.6, and b*=-1.3.

[0053] The wet ball milling process involves loading the raw material into a ball milling device with a material:ball:water ratio of 1:2:0.8 and milling it at 60 rpm for 10 hours to obtain an antique blue and white porcelain pigment with a particle size of 1μm.

[0054] The calcination temperature was 950℃ and the time was 8 hours.

[0055] A method for preparing blue and white porcelain, characterized by comprising the following steps:

[0056] Step 1: Mix 10% Yaoli glaze fruit, 61% calcined glaze fruit, and 29% glaze ash by weight percentage, and then put the raw materials into a ball mill with a material:ball:water ratio of 1:2:0.8 and ball mill for 10 minutes. The fineness of the slurry reaches less than 0.1% residue on a 10,000-mesh sieve to obtain blue and white glaze.

[0057] Step 2: Apply the antique blue-and-white pigment prepared by the method described in claim 1 onto the antique clay body, and then apply the blue-and-white glaze prepared in step 1 onto the surface of the body and the antique blue-and-white pigment. After drying, fire to obtain blue-and-white porcelain.

[0058] The firing process is carried out in a reducing atmosphere at a temperature of 1270°C for 9 hours.

[0059] The thickness of the antique blue-and-white pigment applied to the antique clay body is 0.1 mm, and the thickness of the blue-and-white glaze applied to the body and the antique blue-and-white pigment is 2 mm.

[0060] like Figure 2 As shown, the blue and white patterns on the surface of the porcelain exhibit a deep blue tone, with a chromaticity value of b*=-13 and a diffusion distance of 350μm.

[0061] like Figure 4 The XRD pattern of the blue-and-white pigment shows that the main crystalline phase is cobalt oxide (CoO).

[0062] like Figure 5 (b1) As shown in the SEM of the intermediate layer, there is a layer of residual particles in the body-glaze interaction layer. These residual particles float in the glaze, according to the EDS results. Figure 5 (b2) is shown as an oxide of cobalt.

[0063] Example 3

[0064] A method for preparing an antique blue-and-white porcelain pigment with controllable hue and diffusion, characterized in that:

[0065] Its raw material formula consists of the following weight percentages: cobalt oxide 5%, cobalt tetroxide 35%, alumina 2%, bauxite 58%, plus aluminum hydroxide 5%, lithium carbonate 1.5%, zinc oxide 1%, barium carbonate 2%, and borax 1%.

[0066] The cobalt oxide, cobalt tetroxide, and alumina are used as colorants, bauxite is used as a stabilizer, and aluminum hydroxide, lithium carbonate, zinc oxide, barium carbonate, and borax are used as additives.

[0067] After the raw material is crushed, the colorant and stabilizer are mixed and calcined to obtain a spinel crystal precursor. Then, an additive is added, and after wet ball milling, an antique blue and white porcelain pigment is obtained.

[0068] The color values ​​of the antique blue and white porcelain pigment are L*=37.9, a*=10.0, and b*=-49.2.

[0069] The wet ball milling process involves loading the raw material into a ball milling device with a material:ball:water ratio of 1:2:0.9 and milling it at 70 rpm for 8 hours to obtain an antique blue and white porcelain pigment with a particle size of 0.5 μm.

[0070] The calcination temperature was 1000℃ and the time was 8 hours.

[0071] A method for preparing blue and white porcelain, characterized by comprising the following steps:

[0072] Step 1: Mix 15% Yaoli glaze fruit, 68% calcined glaze fruit, and 17% glaze ash by weight percentage, and then put the raw materials into a ball mill with a material:ball:water ratio of 1:2:0.8 and ball mill for 10 minutes. The fineness of the slurry reaches less than 0.1% residue on a 10,000-mesh sieve to obtain blue and white glaze.

[0073] Step 2: Apply the antique blue-and-white pigment prepared by the method described in claim 1 onto the antique clay body, and then apply the blue-and-white glaze prepared in step 1 onto the surface of the body and the antique blue-and-white pigment. After drying, fire to obtain blue-and-white porcelain.

[0074] The firing process is carried out in a reducing atmosphere at a temperature of 1260°C for 8 hours.

[0075] The thickness of the antique blue-and-white pigment applied to the antique clay body is 0.8 mm, and the thickness of the blue-and-white glaze applied to the body and the antique blue-and-white pigment is 0.8 mm.

[0076] like Figure 3 As shown, the blue and white patterns on the surface of the porcelain exhibit a deep blue hue with a chromaticity value of b*=-36 and a diffusion distance of 50μm.

[0077] like Figure 4 The XRD pattern of the blue-and-white pigment shows that the main crystalline phase is cobalt spinel (CoAl2O4).

[0078] like Figure 5 (c1) As shown in the SEM of the intermediate layer, there is a layer of residual particles in the body-glaze interaction layer. These residual particles float in the glaze, according to the EDS results. Figure 5 (c2) is shown as cobalt spinel.

[0079] Obviously, the above embodiments are merely examples for clear illustration and are not intended to limit the implementation. It is clear from the embodiments that when Co... 2+ Ions located in the tetrahedral structure of the glaze result in a pure blue color in blue and white porcelain, with a large "diffusion" distance; when Co... 2+ Located within the tetrahedral structure of spinel crystals, the blue-and-white porcelain exhibits a deep blue color with a small "halo" distance. For those skilled in the art, various variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations. However, obvious variations or modifications derived therefrom remain within the scope of protection of this invention.

Claims

1. A method for preparing an antique blue-and-white porcelain pigment with controllable hue and diffusion, characterized in that: Its raw material formula consists of the following weight percentages: cobalt oxide 5-60%, cobalt tetroxide 15-60%, alumina 2-5%, bauxite 17-58%, plus aluminum hydroxide 1-5%, lithium carbonate 1-2%, zinc oxide 1-5%, barium carbonate 1-5%, and borax 1-5%. The cobalt oxide, cobalt tetroxide, and alumina are used as colorants, bauxite is used as a stabilizer, and aluminum hydroxide, lithium carbonate, zinc oxide, barium carbonate, and borax are used as additives. After the raw material is crushed, the colorant and stabilizer are mixed and calcined to obtain a spinel crystal precursor. Then, an additive is added, and after wet ball milling, an antique blue and white porcelain pigment is obtained. The color values ​​of the antique blue and white porcelain pigment are L*=37.9~42, a*=-3.6~10.0, and b*=-0.6~-49.2; The wet ball milling process uses a material:ball:water ratio of 1:2:0.8-1. The raw materials are loaded into the ball milling equipment and milled at 60-80 rpm for 6-10 hours to obtain an antique blue and white porcelain pigment with a particle size of 0.1-1μm. The calcination temperature is 900–1000℃, and the time is 8 hours.

2. A method for preparing blue and white porcelain, characterized in that, Includes the following steps: Step 1: Mix 8-15% Yaoli glaze fruit, 56-68% calcined glaze fruit, and 17-36% glaze ash by weight percentage, and then put the raw materials into a ball mill with a material:ball:water ratio of 1:2:0.8 and ball mill for 10 minutes. The fineness of the slurry reaches less than 0.1% residue on a 10,000-mesh sieve to obtain blue and white glaze. Step 2: Apply the antique blue-and-white pigment prepared by the method described in claim 1 onto the antique clay body, and then apply the blue-and-white glaze prepared in step 1 onto the surface of the body and the antique blue-and-white pigment. After drying, fire to obtain blue-and-white porcelain.

3. The preparation method according to claim 2, characterized in that: The firing process is carried out in a reducing atmosphere at a temperature of 1250–1270°C for 8–10 hours.

4. The preparation method according to claim 2, characterized in that: The thickness of the antique blue-and-white pigment applied to the antique clay body is 0.1–0.8 mm, and the thickness of the blue-and-white glaze applied to the body and the antique blue-and-white pigment is 0.5–2 mm.

5. The preparation method according to claim 2, characterized in that: The blue and white porcelain surface has a deep blue hue with a color value of b*=-13~-36 and a diffusion distance of 50~350μm.

Images