Hale blue high-temperature pigment as well as preparation method and application thereof

Abstract

The invention provides a sea blue high-temperature pigment as well as a preparation method and application thereof, and relates to the technical field of high-temperature pigments. The sea blue high-temperature pigment disclosed by the invention is prepared from raw materials such as Co2O3, (NH4) 2Cr2O7, ZnO, Al2O3, Na6Al4Si6S4O20, Na2B4O7. 10H2O and the like through processes such as high-temperature calcination, ball milling and the like. The raw material composition can form a chromium-cobalt spinel phase, an aluminum-cobalt spinel phase and blue ultramarine in the preparation process so as to realize composite color generation, so that the high-temperature pigment is bright in color, high in chemical stability and not easy to fade, and is particularly suitable for preparing high-temperature ceramics, especially Liling underglaze five-color ceramics. And meanwhile, the preparation process of the high-temperature pigment is green and environment-friendly, is low in energy consumption, and has important significance on inheritance and innovation of high-temperature art porcelain, especially Liling underglaze five-color porcelain.

Description

Technical Field

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

[0002] High-temperature art porcelain is a kind of ceramic artwork made by high-temperature firing technology, which has unique artistic value and craft characteristics. High-temperature art porcelain not only has extremely high artistic value, but is also widely used in home decoration, art collection and practical utensils. It is also loved for its environmental protection and durability, becoming a model of the combination of traditional porcelain making technology and modern art design.

[0003] Liling underglaze colored porcelain originated in the early 20th century and is an important branch of Liling porcelain. After nearly a hundred years of inheritance and development, Liling underglaze colored porcelain has become an important part of Chinese ceramic art and is known as the "treasure of oriental art". Unlike traditional overglaze painting, Liling underglaze colored porcelain is made by first painting patterns on semi-finished blanks, then glazing and firing in high-temperature kilns. The special feature is that high-temperature pigments are mixed into a variety of colors, using the unique technique of "double hook Fenshui" in traditional Chinese painting, and then fired. Its porcelain is delicate, the glaze is crystal clear and transparent, and it has extremely high aesthetic and artistic value. The colors of underglaze colored porcelain are rich and colorful, and the common ones are red, green, yellow, blue, purple, etc. The colors are harmoniously matched and full of artistic sense. The patterns are mostly based on flowers, birds, landscapes, and figures. The lines are smooth and the images are vivid, which has high artistic value.

[0004] Liling underglaze colorful pigments played a crucial 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 colorful porcelain designed with 1175 sea blue pigment has clear, bright, grand pictures, bright colors, strong national characteristics, and contemporary atmosphere. It is one of the most important pigments in Liling underglaze colorful porcelain.

[0006] However, the preparation of traditional high-temperature blue pigments, especially 1175 high-temperature blue pigments, has problems such as complex preparation process and environmental pollution. For example, the invention patent with publication number CN 108360289 A discloses a series of pigments for underglaze small film flower paper and its preparation method, which involves the use of light powder - Hg2Cl2. Although high-temperature calcination can volatilize Hg, the preparation process is harsh and complicated and is not environmentally friendly during use, which does not meet the needs of green development. Summary of the invention

[0007] In view of this, the present invention provides a high-temperature sea-blue pigment and a preparation method and application thereof. The high-temperature sea-blue pigment of the present invention is prepared by high-temperature calcination of raw materials, ball milling and other processes to form a composite color of chromium-cobalt spinel phase, aluminum-cobalt spinel phase and blue ultramarine, and has the characteristics of bright color, high chemical stability, not easy to fade, etc., and meets the requirements of manual Fenshui process for pigments. At the same time, the pigment preparation process provided by the present invention is green and environmentally friendly, with low energy consumption, and is of great significance to the inheritance and innovation of high-temperature art porcelain, especially Liling underglaze colorful 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, and the raw materials include the following raw materials in percentage by mass:

[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 blue pigment is 1175 high temperature 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 the sea blue high temperature pigment.

[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 2h.

[0015] Preferably, the ball milling medium is alcohol, the concentration of the alcohol is 95%, and the mass ratio of 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 an application 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 pigment of the present invention is 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 the high-temperature calcination process to make the high-temperature pigment stable in color, bright in color, high in artistic level, 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 produced high-temperature pigment particles 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 pigment of the present invention is suitable for high-temperature art porcelain, especially Liling underglaze colorful porcelain, showing high artistic value and practicality. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0023] Figure 2 This is a real picture 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 applied to blue crabapple edge flower tableware. DETAILED DESCRIPTION

[0025] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work 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, and the raw materials include the following raw materials in percentage by mass:

[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 is decomposed into Cr2O3, N2 and H2O at a temperature above 190°C. In 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 being oxidized; ZnO, Al2O3 and Co2O3 react to form a blue aluminum-cobalt spinel Zn·Al2O3 (Co) phase; Na6Al4Si6S4O 20 It is a bright blue powder, transparent, with weak covering power and high brightness, which plays a role in color enhancement; Na2B4O7·10H2O melts into a glassy substance at high temperature, which can dissolve the spinel phase and promote the stable color of the finished product. The present invention has been verified by a large number of experiments, combined with the multi-technical coupling of raw material selection and control of the proportion of each component, high-temperature reducing flame calcination and ball milling dispersion process, and successfully combines the cyan chrome cobalt spinel phase, the blue aluminum cobalt spinel phase and the blue ultramarine to produce a blue 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 high temperature pigment of the sea blue color 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 according to the proportion and dry mix them, and sieve the mixed powder after mixing;

[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, and at the same time ensures that the decomposition of other components such as Co2O3 and ZnO is carried out synchronously with the reaction. However, too fast heating may cause partial incomplete reaction or local overheating, thereby affecting the quality and color stability of the generated spinel phase (such as chrome 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 due to too fast heating, and ensure the uniformity and color consistency of the final pigment particles. The specific holding time can ensure that the chrome cobalt spinel phase and the aluminum cobalt spinel phase in the raw material are fully generated, and at the same time Na6Al4Si6S4O 20 and Na2B4O7·10H2O can fully melt and promote the uniform distribution of 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 the effect will be limited. Therefore, the present invention defines an appropriate holding time to ensure that the spinel crystals are fully developed, reduce the defects inside the crystals, and improve the color vividness and stability of the pigment, which not only meets the requirements of reaction sufficiency and product quality consistency, but also takes into account the economy and operability of the process.

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

[0039] In some specific embodiments of the present invention, the D of the high temperature pigment of the sea blue color 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 up 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 maintains the gloss and delicate feeling of the glaze layer. In a large number of experiments of the present invention, it is found that when the D 50 When the particle size is in 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 an application 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 art 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 colored porcelain with its excellent chemical stability, bright and lasting color performance and adaptability to high temperature firing process. The pigment can maintain the stability and brightness of the color at high temperature, and blends 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 colored porcelain, expands the expression space of artists in the creation of themes such as flowers, birds, landscapes, and figures, but also further enhances the artistic value and market competitiveness of underglaze colored 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 colored 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] Embodiment 1 A method for preparing a high temperature blue pigment, the steps are as follows:

[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, sieve the mixed powder through a 300-mesh sieve;

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

[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 material, 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, it 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 5 μm.

[0048] Embodiment 2 A method for preparing a high temperature blue pigment, the steps are as follows:

[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, sieve the mixed powder through a 300-mesh sieve;

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

[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 material, 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, it 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 5 μm.

[0052] Example 3 A method for preparing a high temperature blue pigment, the steps are as follows:

[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, sieve the mixed powder through a 300-mesh sieve;

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

[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 material, 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, it 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 5 μm.

[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 are 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 48 hours of ball milling, 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 obtained pigments were painted by hand using Fenshui method to make underglaze colored porcelain products. The appearance performance of the finished products was evaluated. The results are shown in Table 1.

[0068] Table 1 Appearance of finished underglaze colored porcelain

[0069]

[0070] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A high temperature blue pigment, characterized in that: The high temperature pigment of the sea blue color is prepared by mixing raw materials, calcining at high temperature, ball milling, drying, crushing and screening, and the raw materials include the following raw materials in mass percentage: Co2O36~8%、(NH4)2Cr2O720~30%、ZnO 6~10%、Al2O325~35%、Na6Al4Si6S4O 20 25~35%、Na2B4O7·10H2O 1~2%。 2. A high temperature pigment of sea blue color according to claim 1, characterized in that: The high temperature pigment D 50 2~8μm.

3. A high temperature pigment of sea blue color according to claim 1, characterized in that: The high temperature pigment of the sea blue is 1175 high temperature pigment of the sea blue.

4. The method for preparing the high temperature blue pigment according to any one of claims 1 to 3, comprising the following steps: 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 the sea blue high temperature pigment.

5. The preparation method according to claim 4, characterized in that: 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 insulation time is 0.5 to 2h.

6. The preparation method according to claim 4, characterized in that: 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 hours.

7. Use of a high temperature blue pigment in the preparation of ceramic products, characterized in that: The high temperature sea blue pigment is the high temperature sea blue pigment described in any one of claims 1 to 3 or the high temperature sea blue pigment prepared by the method described in any one of claims 4 to 6.

8. The use according to claim 7, characterized in that: The ceramics are high-temperature artistic ceramics.

9. The use according to claim 8, characterized in that: The ceramics are Liling underglaze multicolored porcelain.

10. The use according to claim 9, characterized in that: The high temperature pigment is used for handmade Fenshui in the preparation of Liling underglaze multicolored porcelain.

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