阅读说明：本技术 一种新型耐高温稳定钛酸铝基陶瓷色料的制备方法及其制得的产品 (Preparation method of novel high-temperature-resistant stable aluminum titanate-based ceramic pigment and product prepared by preparation method ) 是由 江峰 冯果 陈俊华 蓝善芳 江伟辉 赵迁迁 刘健敏 梁健 于 2020-08-21 设计创作，主要内容包括：本发明公开了一种新型耐高温稳定钛酸铝基陶瓷色料的制备方法,以钛源和铝源为原料、并结合氧供体,通过离子掺杂,采用非水解溶胶-凝胶工艺,在低温条件下制备出不同种类的、色差小且着色效果优异的新型钛酸铝基陶瓷色料。此外,还公开了利用上述新型耐高温稳定钛酸铝基陶瓷色料的制备方法制得的产品。本发明不仅拓展了耐高温陶瓷色料的色基种类,开发出具有优异性能的高温陶瓷色料新品种,而且能够实现不同离子、更广泛的高浓度掺杂,掺杂均匀性好,有利于提高色料的着色效果,减小色料的色差,而且能够在低温下合成陶瓷色料,有效克服了通常高温合成色料粒度大、难以控制颗粒大小以及色料团聚严重等问题。(The invention discloses a preparation method of a novel high-temperature-resistant stable aluminum titanate-based ceramic pigment, which takes a titanium source and an aluminum source as raw materials, combines an oxygen donor, adopts a non-hydrolytic sol-gel process through ion doping, and prepares the novel aluminum titanate-based ceramic pigment with different types, small color difference and excellent coloring effect under the low-temperature condition. In addition, a product prepared by the preparation method of the novel high-temperature-resistant stable aluminum titanate-based ceramic pigment is also disclosed. The invention not only expands the color base variety of the high-temperature resistant ceramic pigment, develops a new high-temperature ceramic pigment variety with excellent performance, but also can realize different ions and wider high-concentration doping, has good doping uniformity, is beneficial to improving the coloring effect of the pigment and reducing the color difference of the pigment, can synthesize the ceramic pigment at low temperature, and effectively overcomes the problems of large granularity, difficult control of particle size, serious pigment agglomeration and the like of the common high-temperature synthesized pigment.)

1. A preparation method of a novel high-temperature-resistant stable aluminum titanate-based ceramic pigment is characterized by comprising the following steps:

(1) preparation of precursor mixture

Taking a titanium source and an aluminum source as raw materials, combining an oxygen donor, mixing the titanium source, the aluminum source and the oxygen donor according to a molar ratio of 0.5-1: 1-2: 0-5, and heating and stirring the mixture to carry out pre-reaction to form a precursor mixed solution;

(2) preparation of precursor sol

Adding a solvent into the precursor mixed solution, uniformly stirring to obtain a precursor solution with the concentration of 0.05-2 mol/L, then adding a coloring ionic salt serving as a coloring stabilizer, and carrying out heating reflux to initiate a non-hydrolytic polycondensation reaction to form a precursor sol; wherein the doping amount of the coloring ionic salt is 0.5-60 mol% of the mole number of the titanium source;

(3) preparation of precursor xerogel

Drying and gelling the precursor sol to obtain a precursor xerogel;

(4) preparation of aluminium titanate-based ceramic pigment

After grinding, pre-sintering the precursor xerogel at the temperature of 250-800 ℃, and then performing heat treatment at the temperature of 1000-1450 ℃ to obtain the Al_2(1-x)M_xTi_1+xO₅Or Al₂M_xTi_1-xO₅(M is coloring ion) is the high temperature resistant stable aluminum titanate based ceramic pigment.

2. The method for preparing a novel high temperature resistant stable aluminum titanate-based ceramic colorant according to claim 1, characterized in that: the coloring stabilizer is one or a combination of the following coloring ion salts, and the coloring ion salts and the doping amount thereof are as follows: 0.5-60 mol% of chromium salt, 0.5-50 mol% of manganese salt, 1-50 mol% of iron salt, 1-30 mol% of molybdenum salt, 1-30 mol% of vanadium salt, 1-30 mol% of nickel salt, 1-40 mol% of cobalt salt, 1-40 mol% of praseodymium salt, 5-50 mol% of cerium salt, 5-50 mol% of cadmium salt, 1-40 mol% of copper salt and 5-40 mol% of magnesium salt.

3. The method for producing a novel high temperature resistant stable aluminum titanate-based ceramic colorant according to claim 1 or 2, characterized in that: the coloring ionic salt is halide, alkoxide or anhydrous organic acid salt of coloring ions.

4. The method for preparing a novel high temperature resistant stable aluminum titanate-based ceramic colorant according to claim 1, characterized in that: the temperature of the heating pre-reaction in the step (1) is 50-90 ℃, and the time is 15-60 min; the heating reflux reaction in the step (2) is carried out at the temperature of 90-150 ℃ for 2-24 h; in the step (3), the drying temperature is 90-200 ℃, and the drying time is 4-12 h.

5. The method for preparing a novel high temperature resistant stable aluminum titanate-based ceramic colorant according to claim 1, characterized in that: the titanium source is anhydrous inorganic titanium or titanium alkoxide, the aluminum source is anhydrous inorganic aluminum salt or aluminum alkoxide, and the oxygen donor is anhydrous low-carbon alcohol.

6. The method for preparing a novel high temperature resistant stable aluminum titanate-based ceramic colorant according to claim 5, characterized in that: the anhydrous low-carbon alcohol is alcohol containing 2-4 carbon atoms except tertiary butanol.

7. The method for preparing a novel high temperature resistant stable aluminum titanate-based ceramic colorant according to claim 1, characterized in that: the solvent is xylene, ethyl acetate and chloroform.

8. A product obtained by the method for producing a novel high temperature resistant stable aluminum titanate-based ceramic color according to any one of claims 1 to 7.

Technical Field

The invention relates to the technical field of ceramic pigments, in particular to a preparation method of a novel high-temperature-resistant stable aluminum titanate-based ceramic pigment and a product prepared by the same.

Background

Ceramic colour is a material used for colouring and decorating ceramic products, and it includes overglaze, under glaze and colour for colouring glaze and blank. The ceramic coloring material must have the following conditions: (1) the high temperature is stable, and the ceramic product is not decomposed and volatilized in the firing temperature range of the ceramic product; (2) the structure is stable, and the glass can bear the erosion of a molten glass body or a solvent in the firing process; (3) stable chemical property and no reaction with glaze or solvent. The ceramic coloring material can be classified into a low temperature type (600 to 1000 ℃) and a high temperature type (1000 to 1400 ℃) according to the use temperature. At present, the low-temperature pigments are various in types, such as sulfides HgS and unencapsulated CdS_xSe_1-xColoring materials, and the like. However, the pigment with stable color at high temperature is relatively less (zirconium-based pigment is a common high-temperature pigment at present), and especially, the pigment with the use temperature higher than 1300 ℃ is less. The high-temperature pigment is characterized in that the pigment is synthesized into one or an isomorphous mixed crystal after being calcined at high temperature, and the pigment with the crystal structure is added into the base glaze, so that the crystal can not be decomposed in the glaze firing process. Therefore, the development of the chromophore of the high temperature resistant ceramic pigment is actively promoted, and the development of a new variety of the high temperature resistant ceramic pigment is urgent and necessary. In addition, the existing preparation method of the high-temperature ceramic pigment is mainly based on a solid phase method, and has the problems of large color difference of the pigment, difficult regulation and control of particle size, non-uniform doping of coloring ions and the like, so that the high-temperature ceramic pigment with controllable particle size, small color difference, uniform doping and rich color is urgently needed at present.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a preparation method of a novel high-temperature-resistant stable aluminum titanate-based ceramic pigment. The invention also aims to provide a product prepared by the preparation method of the novel high-temperature-resistant stable aluminum titanate-based ceramic pigment.

The purpose of the invention is realized by the following technical scheme:

the invention provides a preparation method of a novel high-temperature-resistant stable aluminum titanate-based ceramic pigment, which comprises the following steps:

(1) preparation of precursor mixture

Taking a titanium source and an aluminum source as raw materials, combining an oxygen donor, mixing the titanium source, the aluminum source and the oxygen donor according to a molar ratio of 0.5-1: 1-2: 0-5, and heating and stirring the mixture to carry out pre-reaction to form a precursor mixed solution;

(2) preparation of precursor sol

Adding a solvent into the precursor mixed solution, uniformly stirring to obtain a precursor solution with the concentration of 0.05-2 mol/L, then adding a coloring ionic salt serving as a coloring stabilizer, and carrying out heating reflux to initiate a non-hydrolytic polycondensation reaction to form a precursor sol; wherein the doping amount of the coloring ionic salt is 0.5-60 mol% of the mole number of the titanium source;

(3) preparation of precursor xerogel

Drying and gelling the precursor sol to obtain a precursor xerogel;

(4) preparation of aluminium titanate-based ceramic pigment

After grinding, pre-sintering the precursor xerogel at the temperature of 250-800 ℃, and then performing heat treatment at the temperature of 1000-1450 ℃ to obtain the Al_2(1-x)M_xTi_1+xO₅Or Al₂M_xTi_1-xO₅(M is coloring ion) is the high temperature resistant stable aluminum titanate based ceramic pigment.

Further, the coloring stabilizer of the invention is one or a combination of the following coloring ion salts, and the coloring ion salts and the doping amount thereof are as follows: 0.5-60 mol% of chromium salt, 0.5-50 mol% of manganese salt, 1-50 mol% of iron salt, 1-30 mol% of molybdenum salt, 1-30 mol% of vanadium salt, 1-30 mol% of nickel salt, 1-40 mol% of cobalt salt, 1-40 mol% of praseodymium salt, 5-50 mol% of cerium salt, 5-50 mol% of cadmium salt, 1-40 mol% of copper salt and 5-40 mol% of magnesium salt. The coloring ionic salt is halide, alkoxide or anhydrous organic acid salt of coloring ions.

Further, the temperature of the heating pre-reaction in the step (1) is 50-90 ℃, and the time is 15-60 min; the heating reflux reaction in the step (2) is carried out at the temperature of 90-150 ℃ for 2-24 h; in the step (3), the drying temperature is 90-200 ℃, and the drying time is 4-12 h.

In the scheme, the titanium source is anhydrous inorganic titanium or titanium alkoxide, and the aluminum source is anhydrous inorganic aluminum salt or aluminum alkoxide; the oxygen donor is anhydrous low-carbon alcohol, specifically, alcohol containing 2-4 carbon atoms except tertiary butanol. The solvent is xylene, ethyl acetate and chloroform.

The product prepared by the preparation method of the novel high-temperature-resistant stable aluminum titanate-based ceramic pigment.

The invention has the following beneficial effects:

(1) the invention takes a titanium source and an aluminum source as raw materials, combines an oxygen donor, adopts a non-hydrolytic sol-gel process through ion doping, and prepares the novel aluminum titanate-based ceramic pigment with different types, small color difference and excellent coloring effect under the low temperature condition. Aluminum titanate (Al)₂TiO₅) Has the advantages of high melting point (1860 ℃), no infiltration to glass melt, alkali resistance, hot salt corrosion resistance and the like. Compared with ceramic pigments such as zirconium-based ceramic pigments, tin-based ceramic pigments and the like, the aluminum titanate-based ceramic pigment disclosed by the invention contains trivalent aluminum ions and tetravalent titanium ions, and can adapt to doping positions of different coloring ions, so that different ions and wider high-concentration doping (high coloring effect) can be realized.

(2) Although aluminum titanate is easy to decompose at medium temperature (800-1250 ℃), the invention effectively inhibits the medium-temperature instability through ion doping, and the ion doping of the solid-solution type pigment can also effectively inhibit the medium-temperature decomposition of the aluminum titanate. Therefore, compared with spinel type, corundum type, rutile type and other pigments, the aluminum titanate-based ceramic pigment has better glass melt corrosion resistance and high temperature stability, is an ideal high-temperature ceramic color-based material, expands the color-based variety of the high-temperature ceramic pigment and develops a new high-temperature ceramic pigment variety with excellent performance.

(3) The precursor is prepared based on a non-hydrolytic sol-gel (NHSG) method, and non-hydrolytic heterogeneous polycondensation reaction is easy to form heterogeneous bonding, so that atomic-level uniform mixing is realized. Therefore, the invention has high doping concentration and good doping uniformity, is beneficial to improving the coloring effect of the pigment and reducing the color difference of the pigment, can synthesize the ceramic pigment at low temperature, and is beneficial to overcoming the problems of large granularity, difficult control of particle size, serious pigment agglomeration and the like of the common high-temperature synthesized pigment.

(4) The method has the advantages of simple process, short period, easy control, low synthesis temperature, low cost and easy popularization and use.

The present invention will be described in further detail with reference to examples.

Detailed Description