A high-temperature sea blue pigment and its preparation method and application

Abstract

The present invention provides a high-temperature blue pigment and its preparation method and application, which relates to the technical field of high-temperature pigments. The high-temperature blue pigment of the present invention is composed of Co2O3, (NH4)2Cr2O7, ZnO, Al2O3, Na6Al4Si6S4O 20 The pigment is prepared from raw materials such as Na2B4O7·10H2O through high-temperature calcination and ball milling. The raw material combination of the present invention can form a chromium-cobalt spinel phase, an aluminum-cobalt spinel phase, and blue ultramarine during the preparation process, thereby achieving composite coloration. This makes the high-temperature pigment of the present invention bright in color, highly chemically stable, and not prone to fading. It is particularly suitable for the preparation of high-temperature ceramics, especially Liling underglaze multicolored porcelain. Furthermore, the high-temperature pigment preparation process of the present invention is environmentally friendly and has low energy consumption, which is of great significance to the inheritance and innovation of high-temperature artistic porcelain, especially Liling underglaze multicolored porcelain.

Description

Technical Field

[0001] The present invention relates to the technical field of high-temperature pigments, in particular to a high-temperature blue pigment and a preparation method and application thereof. Background Art

[0002] High-temperature art porcelain is a type of ceramic artwork created through a high-temperature firing process, possessing unique artistic value and craftsmanship. High-temperature art porcelain not only possesses exceptional artistic value and is widely used in home decoration, art collections, and practical utensils, but is also highly valued for its environmental friendliness and durability, becoming a model for the fusion of traditional porcelain craftsmanship with modern art and design.

[0003] Liling underglaze multicolored porcelain, originating in the early 20th century, is a key branch of Liling porcelain. After nearly a century of inheritance and development, it has become a vital component of Chinese ceramic art, hailed as a "treasure of Oriental art." Unlike traditional overglaze painting, Liling underglaze multicolored porcelain is first painted on a semi-finished blank before being glazed and fired in a high-temperature kiln. Its unique characteristic is the blending of high-temperature pigments to create a variety of colors, employing the unique "double-outline Fenshui" technique of traditional Chinese painting, and then firing. The result is a delicate porcelain with a translucent, crystal-clear glaze, possessing exceptional aesthetic and artistic value. Underglaze multicolored porcelain features a rich palette of colors, including red, green, yellow, blue, and purple. The harmonious color combinations are rich in artistic flair, and the designs often feature flowers, birds, landscapes, and figures, with flowing lines and vivid imagery, possessing high artistic value.

[0004] Liling underglaze colorful pigments played a vital role in the emergence of Liling underglaze colorful porcelain. Without the invention of underglaze colorful pigments, there would be no underglaze colorful porcelain. Therefore, underglaze colorful high-temperature pigments are an important component of underglaze colorful porcelain.

[0005] There are as many as 9 types of underglaze blue pigment series, among which 1175 sea blue is the best in the blue series. The Liling underglaze multicolored porcelain designed with 1175 sea blue pigment has clear, bright, grand and colorful pictures, which are full of national characteristics and contemporary flavor. It is one of the most important pigments in Liling underglaze multicolored porcelain.

[0006] However, the preparation of traditional high-temperature ... Summary of the Invention

[0007] In light of this, the present invention provides a high-temperature, blue-colored pigment, its preparation method, and application. The pigment is produced through high-temperature calcination of raw materials, ball milling, and other processes to form a composite coloration of chromium-cobalt spinel, aluminum-cobalt spinel, and blue ultramarine. The pigment exhibits vibrant color, high chemical stability, and resistance to fading, meeting the requirements of the handmade Fenshui craft for pigments. Furthermore, the pigment preparation process provided by the present invention is environmentally friendly and energy-efficient, significantly contributing to the inheritance and innovation of high-temperature artistic porcelain, particularly Liling underglaze multicolored porcelain.

[0008] The high-temperature pigment of the present invention is prepared by mixing raw materials, calcining at high temperature, ball milling, drying, crushing, and screening. The raw materials include the following raw materials in the following mass percentages:

[0009] Co2O36~8%, (NH4)2Cr2O720~30%, ZnO 6~10%, Al2O325~35%, Na6Al4Si6S4O 20 25~35%, Na2B4O7·10H2O 1~2%.

[0010] Preferably, the sea blue high temperature pigment D 50 2~8μm.

[0011] Preferably, the high-temperature sea-blue pigment is 1175 high-temperature sea-blue pigment.

[0012] The present invention provides a method for preparing a high-temperature blue pigment, which specifically comprises the following steps:

[0013] The raw materials are weighed in proportion, mixed evenly and sieved, the mixed raw materials are calcined at high temperature, and the calcined raw materials are ball-milled, dried, crushed and sieved to obtain a high-temperature pigment of sea blue.

[0014] Preferably, the heating rate of the high-temperature calcination is 3°C / min to 6°C / min, the calcination temperature is 1360°C to 1380°C, and the holding time is 0.5 to 2 hours.

[0015] Preferably, the ball milling medium is alcohol, the concentration of the alcohol is 95%, and the mass ratio of the alcohol to the calcined raw material is (0.5-0.8):1.

[0016] Preferably, the ball-to-material ratio of the ball mill is (1.5-2.5):1, the rotation speed is 150-250 rpm, and the ball milling time is 60-80 h.

[0017] The present invention also provides a use of a high-temperature sea-blue pigment in the preparation of ceramic products. The high-temperature sea-blue pigment is the high-temperature sea-blue pigment described in the above technical solution.

[0018] Preferably, the ceramic is high-temperature art porcelain. More preferably, the ceramic is Liling underglaze multicolored porcelain.

[0019] Preferably, the high temperature pigment is used for manual water painting.

[0020] The high-temperature pigments of the present invention are mainly made of inorganic raw materials, which conforms to the concept of green manufacturing and meets the environmental protection needs of the ceramic industry. The present invention optimizes the raw material ratio and high-temperature calcination process to make the high-temperature pigments stable in color, bright in color, and high in artistic level. They are not easy to fade or discolor and meet the requirements of the manual Fenshui process for pigments, while reducing energy consumption and calcination time, and improving production efficiency. The present invention uses processes such as ball milling and crushing to make the high-temperature pigment particles produced have good uniformity, which helps to evenly distribute the pigment in the ceramic glaze or body, and improve the coloring effect and smoothness. The high-temperature pigments of the present invention are suitable for high-temperature art porcelain, especially Liling underglaze multicolored porcelain, showing high artistic value and practicality. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The present invention will be further described below with reference to the accompanying drawings.

[0022] Figure 1 This is a photo of a teacup made of high-temperature pigment according to Example 1 of the present invention;

[0023] Figure 2 This is a photo of a teacup made of high-temperature pigment in Comparative Example 1 of the present invention;

[0024] Figure 3 This is a real picture of the high-temperature pigment of the present invention being used in blue crabapple edge flower tableware. DETAILED DESCRIPTION

[0025] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0026] The high-temperature pigment of the present invention is prepared by mixing raw materials, calcining at high temperature, ball milling, drying, crushing, and screening. The raw materials include the following raw materials in the following mass percentages:

[0027] Co2O36~8%, (NH4)2Cr2O720~30%, ZnO 6~10%, Al2O325~35%, Na6Al4Si6S4O 20 25~35%, Na2B4O7·10H2O 1~2%.

[0028] In the high-temperature pigment of the present invention, (NH4)2Cr2O7 decomposes into Cr2O3, N2, and H2O at a temperature above 190°C. During the subsequent calcination process, in a high-temperature reducing flame atmosphere at 1360°C to 1380°C, Cr2O3 and Co2O3 react to form a cyan chromium-cobalt spinel phase CoO·Cr2O3. N2 cooperates with the reducing atmosphere to a certain extent to protect the metal from oxidation; ZnO, Al2O3, and Co2O3 react to form a sea-blue aluminum-cobalt spinel Zn·Al2O3(Co) phase; Na6Al4Si6S4O 20 This vibrant blue powder is transparent, has weak hiding power, and high brightness, serving as a color enhancer. Na₂B₄O₇·10H₂O melts at high temperatures into a glassy substance that dissolves the aforementioned spinel phase, promoting stable color development in the finished product. This invention, through extensive experimental verification and combining raw material selection, controlled component ratios, high-temperature reducing flame calcination, and ball milling dispersion, has successfully combined a cyan chromium-cobalt spinel phase, a cyan aluminum-cobalt spinel phase, and a blue ultramarine to produce a cyan color.

[0029] In some preferred embodiments of the present invention, the Co2O3, (NH4)2Cr2O7, ZnO, and Al2O3 are chemically pure, and Na6Al4Si6S4O 20 , Na2B4O7·10H2O is industrial grade.

[0030] In some specific embodiments of the present invention, the D of the sea blue high temperature pigment is 50 2~8μm.

[0031] The present invention also provides a method for preparing a high-temperature blue pigment, which specifically comprises the following steps:

[0032] S1. Weigh the raw materials in proportion and dry mix them. After mixing, sieve the mixed powder;

[0033] S2, calcining the sieved mixed powder at high temperature in a reducing flame atmosphere;

[0034] S3. The powder after high-temperature calcination is ball-milled, dried, crushed, and sieved to obtain a sea-blue high-temperature pigment.

[0035] In some specific embodiments of the present invention, the S1 mixed powder is sieved through a 300-mesh sieve.

[0036] In some specific embodiments of the present invention, the heating rate during the high-temperature calcination of S2 is 3°C / min to 6°C / min, the calcination temperature is 1360°C to 1380°C, and the holding time is 0.5 to 2 hours. In some preferred embodiments of the present invention, the holding time is 1 hour.

[0037] The present invention adopts a relatively slow heating rate to provide enough time for the reaction, so that the (NH4)2Cr2O7 in the raw material is completely decomposed into Cr2O3, while ensuring that the decomposition of other components such as Co2O3 and ZnO is carried out synchronously with the reaction. However, too fast heating may cause incomplete reaction or local overheating of some parts, thereby affecting the quality and color stability of the generated spinel phase (such as chromium cobalt spinel and aluminum cobalt spinel). In addition, the heating rate helps to reduce the unevenness of temperature distribution and reduce the thermal stress of the material during the heating process, prevent the phenomenon of uneven sintering of particles or crusting on the surface of the material due to rapid heating, avoid cracks or structural defects caused by too fast heating, and ensure the uniformity and hue consistency of the final pigment particles. The specific holding time can ensure that the chromium cobalt spinel phase and aluminum cobalt spinel phase in the raw material are fully generated, while Na6Al4Si6S4O 20 and Na2B4O7·10H2O can fully melt and promote the uniform distribution of the spinel phase. Shortening the holding time will lead to incomplete reaction, affecting the hue and stability of the pigment, while extending the holding time will increase energy consumption and have limited effect. Therefore, the present invention defines an appropriate holding time to ensure the full development of spinel crystals, reduce internal defects in the crystals, and improve the color vividness and stability of the pigment. This not only satisfies the requirements of reaction sufficiency and product quality consistency, but also takes into account the cost-effectiveness and operability of the process.

[0038] In some specific embodiments of the present invention, in S3, the milling medium is alcohol, the concentration of the alcohol is 95%, the mass ratio of the alcohol to the raw material after calcination is (0.5-0.8):1, the milling speed is 150-250 rpm, the ball-to-material ratio is (1.5-2.5):1, and the milling time is 60-80 h; the drying temperature is 150 ° C, and the drying time is 24 h. In some preferred embodiments of the present invention, the concentration of the alcohol is 95%, the mass ratio of the alcohol to the raw material after calcination is 0.6:1, the milling speed is 200 rpm, the ball-to-material ratio is 2:1, and the milling time is 72 h; the drying temperature is 150 ° C, and the drying time is 24 h.

[0039] In some specific embodiments of the present invention, the D of the sea blue high temperature pigment is 50 In the present invention, D 50 The particle size range of 2 to 8 μm can prevent Fenshui painting from being too thick, causing the blank surface to flip or warp, or cracking after sintering. At the same time, pigment particles with a moderate particle size can fully expose their surface area, improve the coloring ability, and make the ceramic products obtain a uniform and bright sea blue color. Finally, D 50The particle size range of 2 to 8 μm is suitable for processes such as ball milling and spraying, is easy to mix with ceramic raw materials, is not easily affected by environmental factors such as deliquescence or moisture absorption, maintains the stability and usability of the pigment powder, does not leave obvious granularity on the surface, helps to form a smooth ceramic surface, and at the same time maintains the gloss and delicate feeling of the glaze layer. In a large number of experiments of the present invention, it was found that when the D 50 When the particle size is within the range of 2 to 8 μm, the prepared high-temperature ceramics have the best color brightness, surface smoothness and process adaptability, which is the optimal particle size range determined after experimental optimization.

[0040] The present invention also provides a use of a high-temperature sea-blue pigment in the preparation of ceramic products. The high-temperature sea-blue pigment is the high-temperature sea-blue pigment described in the above technical solution.

[0041] In some specific embodiments of the present invention, the ceramic is high-temperature artistic porcelain. In some preferred embodiments of the present invention, the ceramic is Liling underglaze multicolored porcelain.

[0042] The sea blue high temperature pigment of the present invention provides a new material choice for the production of Liling underglaze multicolored porcelain with its excellent chemical stability, bright and long-lasting color development performance and adaptability to high temperature firing process. The pigment can maintain color stability and brightness at high temperature, and is integrated with other underglaze color materials and transparent glaze to make the porcelain present a harmonious, beautiful and layered pattern effect. This high-performance pigment not only enriches the blue color system of underglaze multicolored porcelain, expands the artist's expression space in the creation of themes such as flowers and birds, landscapes, and figures, but also further enhances the artistic value and market competitiveness of underglaze multicolored porcelain. At the same time, the pigment of the present invention adopts inorganic environmentally friendly ingredients, meets the requirements of green production, injects new vitality into the inheritance and innovation of Liling underglaze multicolored porcelain, and is of great significance to the sustainable development of Chinese ceramic art.

[0043] In order to further illustrate the present invention, the following examples are provided for detailed description. The raw materials used in the following examples of the present invention are all commercially available.

[0044] Example 1 A method for preparing a high-temperature blue pigment comprises the following steps:

[0045] S1. Weigh the raw materials according to the following mass percentages: 6% Co2O3, 22% (NH4)2Cr2O7, 10% ZnO, 33% Al2O3, 28% Na6Al4Si6S4O 20 and 1% Na2B4O7·10H2O, then dry-mix the raw materials, and after mixing, pass the mixed powder through a 300-mesh sieve;

[0046] S2, the mixed powder after sieving in S1 is heated to 1360°C at a rate of 5°C / min in a reducing flame atmosphere for high temperature calcination, and the holding time is 1 hour;

[0047] S3, the powder calcined at high temperature in S2 was mixed with 95% alcohol at a mass ratio of 0.6:1 between alcohol and calcined raw materials, and then ball milled for 72 hours at a ball-to-material ratio of 2:1 and a rotation speed of 200 rpm. After ball milling, the mixture was dried at 150°C for 24 hours, crushed, and sieved to obtain D 50 It is 1175 high temperature blue pigment with a diameter of 5μm.

[0048] Example 2 A method for preparing a high-temperature blue pigment, comprising the following steps:

[0049] S1. Weigh the raw materials according to the following mass percentages: 8% Co2O3, 28% (NH4)2Cr2O7, 7% ZnO, 26% Al2O3, 30% Na6Al4Si6S4O 20 and 1% Na2B4O7·10H2O, then dry-mix the raw materials, and after mixing, pass the mixed powder through a 300-mesh sieve;

[0050] S2, the mixed powder after sieving in S1 is heated to 1380°C at a rate of 5°C / min in a reducing flame atmosphere for high temperature calcination, and the holding time is 1 hour;

[0051] S3, the powder calcined at high temperature in S2 was mixed with 95% alcohol at a mass ratio of 0.6:1 between alcohol and calcined raw materials, and then ball milled for 72 hours at a ball-to-material ratio of 2:1 and a rotation speed of 200 rpm. After ball milling, the mixture was dried at 150°C for 24 hours, crushed, and sieved to obtain D 50 It is 1175 high temperature blue pigment with a diameter of 5μm.

[0052] Example 3 A method for preparing a high-temperature blue pigment, comprising the following steps:

[0053] S1. Weigh the raw materials according to the following mass percentages: 7% Co2O3, 24% (NH4)2Cr2O7, 8% ZnO, 27% Al2O3, 32.5% Na6Al4Si6S4O 20 and 1.5% Na2B4O7·10H2O, then dry-mix the raw materials, and after mixing, pass the mixed powder through a 300-mesh sieve;

[0054] S2, the mixed powder after sieving in S1 is heated to 1380°C at a rate of 5°C / min in a reducing flame atmosphere for high temperature calcination, and the holding time is 1 hour;

[0055] S3, the powder calcined at high temperature in S2 was mixed with 95% alcohol at a mass ratio of 0.6:1 between alcohol and calcined raw materials, and then ball milled for 72 hours at a ball-to-material ratio of 2:1 and a rotation speed of 200 rpm. After ball milling, the mixture was dried at 150°C for 24 hours, crushed, and sieved to obtain D 50 It is 1175 high temperature blue pigment with a diameter of 5μm.

[0056] Comparative Example 1

[0057] Same as Example 2, except that the raw materials are weighed according to the following mass percentages: 5% Co2O3, 19% (NH4)2Cr2O7, 13% ZnO, 38% Al2O3, 24% Na6Al4Si6S4O 20 and 1% Na2B4O7.10H2O.

[0058] Comparative Example 2

[0059] Same as Example 1, except that the calcination temperature is 1330°C.

[0060] Comparative Example 3

[0061] Same as Example 2, except that the following raw materials are weighed in mass percentage: 9% Co2O3, 31% (NH4)2Cr2O7, 5% ZnO, 17% Al2O3, 37% Na6Al4Si6S4O 20 and 1% Na2B4O7.10H2O.

[0062] Comparative Example 4

[0063] Same as Example 1, except that the heating rate of the high-temperature calcination is 10°C / min.

[0064] Test Example 1

[0065] The high-temperature pigments obtained in Examples 1-3 and Comparative Examples 1-3 were prepared into Fenshui pigments. The specific preparation method is as follows:

[0066] The pigments were mixed in a ratio of pigment: water: grinding ball of 1:0.8:2, and the materials were discharged after ball milling for 48 hours, passed through a 300-mesh sieve, and then aged for 7 days. The aged pigments were diluted with light tea water in a ratio of 97% light tea water: 3% aged pigment to obtain Fenshui pigment.

[0067] The prepared pigments were painted by hand using Fenshui method to make underglaze colored porcelain products. The appearance and performance of the finished products were evaluated. The results are shown in Table 1.

[0068] Table 1 Overview of the appearance of finished underglaze colored porcelain

[0069]

[0070] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A high-temperature blue pigment, characterized in that: The high-temperature pigment of sea blue is prepared by mixing raw materials, calcining at high temperature, ball milling, drying, crushing and screening. The raw materials include the following raw materials in the following mass percentages: Co2O3 6~8%、(NH4)2Cr2O7 20~30%、ZnO 6~10%、Al2O3 25~35%、Na6Al4Si6S4O 20 25~35%、Na2B4O7·10H2O 1~2%; The high-temperature calcination is carried out in a reducing flame atmosphere, the heating rate of the high-temperature calcination is 3°C / min-6°C / min, the calcination temperature is 1360°C-1380°C, and the holding time is 0.5-2 h; The ball milling medium is alcohol, the concentration of the alcohol is 95%, the mass ratio of alcohol to calcined raw materials is (0.5-0.8):1; the ball-to-material ratio of the ball mill is (1.5-2.5):1, the rotation speed is 150-250 rpm, and the ball milling time is 60-80 h.

2. A high-temperature blue pigment according to claim 1, characterized in that: The sea blue high temperature pigment D 50 2~8 μm.

3. The high-temperature blue pigment according to claim 1, characterized in that: The high temperature blue pigment is 1175 high temperature blue pigment.

4. The method for preparing the high-temperature blue pigment according to any one of claims 1 to 3, comprising the following steps: Weigh the raw materials in proportion, mix them evenly and sieve them, calcine the mixed raw materials at high temperature, ball mill the calcined raw materials, dry them, crush them and sieve them to obtain a high-temperature pigment of sea blue; The high-temperature calcination is carried out in a reducing flame atmosphere, the heating rate of the high-temperature calcination is 3°C / min-6°C / min, the calcination temperature is 1360°C-1380°C, and the holding time is 0.5-2 h; The ball milling medium is alcohol, the concentration of the alcohol is 95%, the mass ratio of alcohol to calcined raw materials is (0.5-0.8):1; the ball-to-material ratio of the ball mill is (1.5-2.5):1, the rotation speed is 150-250 rpm, and the ball milling time is 60-80 h.

5. Use of a high-temperature blue pigment in the preparation of ceramic products, characterized in that: The sea-blue high-temperature pigment is the sea-blue high-temperature pigment described in any one of claims 1 to 3 or the sea-blue high-temperature pigment prepared by the method described in claim 4.

6. The use according to claim 5, characterized in that The ceramics are high-temperature artistic porcelain.

7. The use according to claim 6, characterized in that The ceramics are Liling underglaze multicolored porcelain.

8. The use according to claim 7, characterized in that The high temperature pigment is used for handmade Fenshui in the preparation of Liling underglaze multicolored porcelain.

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