Cyan green ceramic ink and method for preparing the same

Abstract

The present application relates to green ceramic ink and its preparation method. The preparation method of green ceramic ink comprises: (1) preparing ceramic green base fine powder; (2) adding organic solvent into a disperser, and stirring and dispersing at constant temperature; (3) according to weight parts, 35-45 parts of green base fine powder and 55-65 parts of organic solvent are dosed, the organic solution is added into the green base fine powder, and a nano sand mill is used for grinding, the rotating speed of the nano sand mill is 2300 revolutions per minute, and the grinding time is 3 hours, so that mixed organic slurry is obtained; (4) continuous series filtering is adopted, the filtering precision is less than 1 micron, and the green ceramic ink is obtained. The present application provides a green base fine powder prepared by using the method of processing narrow-band particle size distribution powder, the green base fine powder with narrow-band particle size distribution is obtained, the problem that the color development powder base is too coarse, the color uniformity is poor, and the color development is poor and impure when being fired too finely and being dissolved in glaze is avoided.

Description

Technical Field

[0001] This invention belongs to the field of ceramic ink technology, and specifically relates to a bluish-green ceramic ink and its preparation method. Background Technology

[0002] As a treasure passed down for thousands of years, Dunhuang elements have always influenced the trends of the times with their unique artistic charm. With the continuous improvement of national cultural confidence, traditional art elements have provided rich soil and endless inspiration for the creation and design of many trendy Chinese ceramic tiles. In particular, the cyan-green in Dunhuang elements is richer and more complex in color. It is not just a simple green, but contains a specific blue tone, between blue and green. This combination of colors makes cyan-green more vivid and unique visually. It represents vitality and growth, and is also closely related to China's natural landscape and traditional culture, showcasing the vast and misty landscape. It also profoundly reflects the unique understanding and application of cyan-green in traditional Chinese culture, and thus has become one of China's traditional colors.

[0003] Currently, most green ceramic inks on the market are either too yellow or too blue, failing to capture the rich, deep green hues of Dunhuang inks. CN116814113A discloses a method for preparing green ceramic ink and the ink itself. Its purpose is to provide a method and ink that address the problem of significant fluctuations in color development and color degradation in existing green ceramic inks. The technical solution involves a method for preparing green ceramic ink, comprising: selecting a cobalt blue pigment and a yellow-coated pigment, and determining a target solvent system; grinding the cobalt blue pigment into cobalt blue ink using the target solvent system, and grinding the yellow-coated pigment into yellow-coated ink using the target solvent system; and mixing the cobalt blue ink and the yellow-coated ink in a predetermined ratio to obtain green ceramic ink. Its shortcomings are: the scheme uses only blue and yellow to mix green without red, resulting in a bright green color, but the mixed green ink is a mixture, and the color development is greatly affected by the environment. Moreover, this bright green color is quite different from the cyan-green tone in Dunhuang elements. It focuses more on the brilliance of the color, while the cyan-green in Dunhuang elements focuses more on the depth and verdant color. Summary of the Invention

[0004] To address the shortcomings of the existing technology, the technical problem solved by this invention is to provide a method for preparing fine powder of blue-green ceramic ink base material by using narrow-band particle size distribution powder processing, resulting in fine powder of blue-green ceramic ink base material with a main particle size of 3 micrometers. This avoids the problems of the color powder base material being too coarse, resulting in poor color uniformity, and being too fine, dissolving in the glaze during firing, resulting in poor and impure color. This ensures that the blue-green ceramic ink can reflect the richness and verdant hue of the blue-green elements in Dunhuang, as well as the preparation method thereof.

[0005] The technical solution of the present invention is a method for preparing the cyan-green ceramic ink, which is characterized by including the following steps:

[0006] (1) Preparation of fine powder for green ceramic ink base;

[0007] (2) Add the organic solvent to the disperser and disperse it by stirring at a constant temperature;

[0008] (3) Prepare 35-45 parts by weight of fine powder of green ceramic ink base and 55-65 parts by weight of organic solvent. Add the organic solvent to the fine powder of green ceramic ink base and grind it with a nano-sand mill at a speed of 2300 rpm for 3 hours to obtain a mixed organic slurry.

[0009] (4) By using continuous series filtration with a filtration accuracy of <1μm, cyan-green ceramic ink can be obtained.

[0010] As a preferred embodiment, the green ceramic ink base material in step (1) is composed of the following components by weight: 10-15 parts green waste glass, 5-10 parts cobalt oxide, 3-5 parts chromium slag, 22-25 parts chromium oxide, 1-3 parts praseodymium oxide, 25-35 parts zirconium oxide, 10-15 parts quartz, and 4-8 parts aluminum hydroxide.

[0011] As a preferred embodiment, the green ceramic ink base material in step (1) is composed of the following components by weight: 12 parts green waste glass, 5 parts cobalt oxide, 5 parts chromium slag, 25 parts chromium oxide, 3 parts praseodymium oxide, 31 parts zirconium oxide, 13 parts quartz, and 6 parts aluminum hydroxide.

[0012] Preferably, the chemical composition of the bluish-green ceramic ink base consists of the following components by weight percentage: SiO2 23.29%, Al2O3 5.73%, ZrO2 31.31%, CaO 3.07%, Cr2O3 25.76%, CoO 5.05%, Pr6O 11 3.03%, Na2O 1.82%, Fe2O3 0.05%, MgO 0.84%, LOI: 0.05%.

[0013] Preferably, the chemical composition of the green waste glass consists of the following components by weight percentage: SiO2 62-68%, Al2O3 3-6%, Fe2O3 0-0.1%, CaO 10-15%, Na2O 12-17%, Cr2O3 0.3-1%; more preferably: SiO2 66.14%, Al2O3 5.01%, Fe2O3 0.08%, CaO 13.52%, Na2O 14.71%, Cr2O3 0.54%.

[0014] Preferably, the chromium slag is composed of the following components by weight percentage: SiO2 40-45%, Al2O3 3-5%, Fe2O3 0.5-1%, CaO 25-30%, MgO 15-20%, and Cr2O3 5-10%; more preferably: SiO2 43.08%, Al2O3 4.21%, Fe2O3 0.85%, CaO 28.26%, MgO 16.36%, and Cr2O3 7.24%.

[0015] As a preferred option: before being introduced into the formulation, the raw materials of the green ceramic ink base are differentiated by gradation.

[0016] Green waste glass has a fineness range of 150-250 mesh;

[0017] Cobalt oxide and praseodymium oxide have a fineness range of 400–600 mesh;

[0018] Chromium slag and quartz with a fineness range of 300-500 mesh;

[0019] Chromium oxide fineness ranges from 700 to 1000 mesh.

[0020] As a preferred embodiment, the preparation of the bluish-green ceramic ink base powder in step (1) includes the following steps:

[0021] (1.1) The raw materials of the green ceramic ink base are mixed according to the gradation and thoroughly mixed using a dry mixer;

[0022] (1.2) The mixed material is loaded into a sagger and fired in an intermittent shuttle kiln at a temperature of 1250℃ for 10-11 hours. The fired material is the green ceramic ink base material with Lab values ​​of L: 65, a: -31, b: 13.

[0023] (1.3) After firing, a wet ball mill is used for preliminary ball milling. The fineness of the balls produced by ball milling is controlled to pass through a 300-mesh standard sieve. Then, hot water is used for repeated washing to clean the soluble salts in the base material and then drying.

[0024] (1.4) An inert gas-protected airflow pulverizer and classifier is used to perform secondary processing on the washed and dried green ceramic base material. The green ceramic ink base material is finely ground into powder using an impact airflow. The chamber pressure is 1.0 MPa. The sorting wheel speed is adjusted to 5000 rpm to collect the fine powder in the green ceramic ink base material powder. The sorting wheel speed is adjusted to 4000 rpm to classify the green ceramic ink base material powder. The collected classified material is the narrow-band particle size distribution green ceramic ink base material fine powder.

[0025] Preferably, the organic solvent in step (2) is composed of the following components by weight: 40-50 parts of resin solvent, 3-8 parts of humectant, 5-10 parts of dispersant, and 1-5 parts of surfactant; more preferably, it is composed of 45 parts of resin solvent, 5 parts of humectant, 5 parts of dispersant, and 3 parts of surfactant.

[0026] Another technical solution of the present invention is the cyan-green ceramic ink, which is characterized in that the cyan-green ceramic ink is prepared by the preparation method of the cyan-green ceramic ink described in any of the preceding claims.

[0027] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0028] (1) The green ceramic ink base material formula of the present invention contains green waste glass. This green waste glass has good melting properties, which can effectively reduce the sintering temperature of the formula, accelerate the diffusion rate of reactant ions, promote the formation of green base material eutectic, and ensure the purity of ink color to a certain extent.

[0029] (2) The fine powder of the blue-green ceramic ink base material of the present invention is prepared by a narrow-band particle size distribution powder processing method. The main particle size is 3 micrometers. This avoids the problem that the color powder base material is too coarse, resulting in poor color uniformity, while the powder material is too fine and dissolves in the glaze during firing, resulting in poor and impure color. This further ensures the purity and stability of the ink color, and ensures that the ink color can reflect the richness and verdant hue of the blue-green in Dunhuang elements.

[0030] (3) The green ceramic ink base of this invention is a single component, which avoids the instability of color due to the large influence of the environment when the colorant is a mixture, thus ensuring the purity and stability of the ink color.

[0031] (4) The cobalt oxide, chromium oxide, calcined zinc oxide, and calcined aluminum oxide in the formulation of this invention are industrial-grade materials. When chemically pure materials are introduced, the green base materials will have better color.

[0032] (5) The green waste glass of this invention mainly uses waste beer bottle glass, which is widely available and inexpensive. Detailed Implementation

[0033] The present invention will be further described in detail below with reference to embodiments:

[0034] Example 1

[0035] The preparation method of cyan-green ceramic ink includes the following steps:

[0036] (1) Preparation of fine powder of bluish-green ceramic ink base; the bluish-green ceramic ink base is composed of the following components by weight: 12 parts of green waste glass, 5 parts of cobalt oxide, 5 parts of chromium slag, 25 parts of chromium oxide, 3 parts of praseodymium oxide, 31 parts of zirconium oxide, 13 parts of quartz, and 6 parts of aluminum hydroxide; the chemical composition of the bluish-green ceramic ink base is composed of the following components by weight percentage: SiO2 23.29%, Al2O3 5.73%, ZrO2 31.31%, CaO 3.07%, Cr2O3 25.76%, CoO 5.05%, Pr6O 11 3.03%, Na2O1.82%, Fe2O3 0.05%, MgO 0.84%, LOI: 0.05%;

[0037] The green waste glass mentioned in step (1) is composed of the following components by weight percentage: SiO2 66.14%, Al2O3 5.01%, Fe2O3 0.08%, CaO 13.52%, Na2O 14.71%, Cr2O3 0.54%; the green waste glass is mainly composed of waste beer bottle glass, and its glass formula is sodium-calcium-silicon glass; the chromium slag is chromium slag after iron removal, and chromium slag is the tailings after chromate production from chromium ore. The chemical composition of the chromium slag is composed of the following components by weight percentage: SiO2 43.08%, Al2O3 4.21%, Fe2O3 0.85%, CaO 28.26%, MgO 16.36%, Cr2O3 7.24%; the chromium slag is a high-calcium-magnesium composite silicate mineral, and the chromium element is introduced into the formula, while also acting as a mineralizer;

[0038] The raw materials for the cyan-green ceramic ink base formula described in step (1) are differentiated by gradation as follows:

[0039] Green waste glass has a fineness range of 150-250 mesh;

[0040] Cobalt oxide and praseodymium oxide have a fineness range of 400–600 mesh;

[0041] Chromium slag and quartz with a fineness range of 300-500 mesh;

[0042] Chromium oxide fineness range: 700–1000 mesh;

[0043] The preparation of the fine powder of the green ceramic ink base mentioned in step (1) includes the following steps:

[0044] (1.1) The raw materials of the green ceramic ink base material are mixed according to the gradation and thoroughly mixed using a dry mixer;

[0045] (1.2) The mixed material is loaded into a sagger and fired in an intermittent shuttle kiln at a temperature of 1250℃ for 11 hours. The fired material is the green ceramic ink base material with Lab values ​​of L: 65, a: -31, b: 13.

[0046] (1.3) After firing, the green ceramic ink base material is initially ball-milled using a wet ball mill. The fineness of the ball milled material is controlled to pass through a 300-mesh standard sieve. Then, it is repeatedly washed with hot water to clean the soluble salts in the base material and prevent the soluble salts from being introduced into the ceramic ink. Finally, it is dried.

[0047] (1.4) The washed and dried green ceramic ink base material is processed by an inert gas protective airflow pulverizer and classifier. The green ceramic ink base material is finely ground into powder by impact airflow. The chamber pressure is 1.0 MPa. The sorting wheel speed is adjusted to 5000 rpm to collect the fine powder in the green ceramic ink base material powder. The sorting wheel speed is adjusted to 4000 rpm to classify the green ceramic ink base material powder. The classified material is the narrow-band particle size distribution green ceramic ink base material fine powder. The main particle size of the fine powder collected after fine grinding and classification is 3 μm.

[0048] (2) Add organic solvent (45 parts resin solvent, 5 parts humectant, 5 parts dispersant, and 3 parts surfactant) to a disperser and stir at a constant temperature to disperse.

[0049] (3) According to the weight, 42 parts of fine powder of green ceramic ink base and 58 parts of organic solvent (45 parts of resin solvent, 5 parts of humectant, 5 parts of dispersant and 3 parts of surfactant) are prepared. The organic solution is added to the fine powder of green ceramic ink base and ground with a nano-sand mill at a speed of 2300 rpm for 3 hours to obtain a mixed organic slurry.

[0050] (4) By using continuous series filtration with a filtration accuracy of <1μm, a bluish-green ceramic ink can be obtained. The inorganic components in the obtained bluish-green ceramic ink have a main particle size of 300-400 nanometers.

[0051] Another technical solution of the present invention is that the cyan-green ceramic ink is prepared by any of the aforementioned methods for preparing cyan-green ceramic ink.

[0052] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be covered by the claims of the present invention.

Claims

1. A method for preparing a bluish-green ceramic ink, characterized in that, Includes the following steps: (1) Preparation of fine powder for green ceramic ink base; The green ceramic ink base material is composed of the following components by weight: 10-15 parts green waste glass, 5-10 parts cobalt oxide, 3-5 parts chromium slag, 22-25 parts chromium oxide, 1-3 parts praseodymium oxide, 25-35 parts zirconium oxide, 10-15 parts quartz, and 4-8 parts aluminum hydroxide. Step (1) involves the following steps in preparing the fine powder of the green ceramic ink base: (1.1) The raw materials of the green ceramic ink base are mixed according to the gradation and thoroughly mixed using a dry mixer; (1.2) The mixed material is loaded into a sagger and fired in an intermittent shuttle kiln at a temperature of 1250℃ for 10-11 hours. The fired material is the green ceramic ink base material with Lab values ​​of L: 65, a: -31, b:

13. (1.3) After firing, a wet ball mill is used for preliminary ball milling. The fineness of the balls produced by ball milling is controlled to pass through a 300-mesh standard sieve. Then, hot water is used for repeated washing to clean the soluble salts in the base material and then drying. (1.4) An inert gas-protected airflow pulverizer and classifier is used to perform secondary processing on the washed and dried green ceramic base material. The green ceramic ink base material is finely ground into powder using an impact airflow. The chamber pressure is 1.0 MPa. The sorting wheel speed is adjusted to 5000 rpm to collect the fine powder in the green ceramic ink base material powder. The sorting wheel speed is adjusted to 4000 rpm to classify the green ceramic ink base material powder. The collected classified material is the narrow-band particle size distribution green ceramic ink base material fine powder. (2) Add the organic solvent to the disperser and disperse it by stirring at a constant temperature; (3) Prepare 35-45 parts by weight of fine powder of green ceramic ink base and 55-65 parts by weight of organic solvent. Add the organic solvent to the fine powder of green ceramic ink base and grind it with a nano-sand mill at a speed of 2300 rpm for 3 hours to obtain a mixed organic slurry. (4) By using continuous series filtration with a filtration accuracy of <1μm, cyan-green ceramic ink can be obtained.

2. The method for preparing the cyan-green ceramic ink according to claim 1, characterized in that, Step (1) The green ceramic ink base material is composed of the following components by weight: 12 parts green waste glass, 5 parts cobalt oxide, 5 parts chromium slag, 25 parts chromium oxide, 3 parts praseodymium oxide, 31 parts zirconium oxide, 13 parts quartz, and 6 parts aluminum hydroxide.

3. The method for preparing the cyan-green ceramic ink according to claim 2, characterized in that, The chemical composition of the green ceramic ink base is as follows by weight percentage: SiO2 23.29%, Al2O3 5.73%, ZrO2 31.31%, CaO 3.07%, Cr2O3 25.76%, CoO 5.05%, Pr6O 11 3.03%, Na2O 1.82%, Fe2O3 0.05%, MgO 0.84%, LOI: 0.05%.

4. The method for preparing the cyan-green ceramic ink according to claim 1, characterized in that, The chemical composition of the green waste glass consists of the following components by weight percentage: SiO2 62-68%, Al2O3 3-6%, Fe2O3 0-0.1%, CaO 10-15%, Na2O 12-17%, and Cr2O3 0.3-1%.

5. The method for preparing the cyan-green ceramic ink according to claim 4, characterized in that, The chemical composition of the green waste glass consists of the following components by weight percentage: SiO2 66.14%, Al2O3 5.01%, Fe2O3 0.08%, CaO 13.52%, Na2O 14.71%, Cr2O3 0.54%.

6. The method for preparing the cyan-green ceramic ink according to claim 2, characterized in that, The chemical composition of the chromium slag is as follows by weight percentage: SiO2 40-45%, Al2O3 3-5%, Fe2O3 0.5-1%, CaO 25-30%, MgO 15-20%, Cr2O3 5-10%.

7. The method for preparing the cyan-green ceramic ink according to claim 6, characterized in that, The chromium slag is composed of the following components by weight percentage: SiO2 43.08%, Al2O3 4.21%, Fe2O3 0.85%, CaO 28.26%, MgO 16.36%, and Cr2O3 7.24%.

8. The method for preparing the cyan-green ceramic ink according to claim 2, characterized in that, Before being introduced into the formulation, the raw materials of the green ceramic ink base are differentiated by gradation: Green waste glass has a fineness range of 150-250 mesh; Cobalt oxide and praseodymium oxide have a fineness range of 400–600 mesh; Chromium slag and quartz with a fineness range of 300-500 mesh; Chromium oxide fineness ranges from 700 to 1000 mesh.

9. The method for preparing the cyan-green ceramic ink according to claim 1, characterized in that, The organic solvent in step (2) consists of the following components by weight: 40-50 parts resin solvent, 3-8 parts humectant, 5-10 parts dispersant, and 1-5 parts surfactant.

10. The method for preparing the cyan-green ceramic ink according to claim 9, characterized in that, The organic solvent in step (2) consists of the following components by weight: 45 parts resin solvent, 5 parts humectant, 5 parts dispersant, and 3 parts surfactant.

11. A bluish-green ceramic ink, characterized in that, The cyan-green ceramic ink is prepared by the method for preparing cyan-green ceramic ink according to any one of claims 1 to 10.