阅读说明：本技术 钴蓝玻璃色料的制备方法 (Preparation method of cobalt blue glass pigment ) 是由 黄晓晨 朱海勇 王传虎 任建林 王虎 王佳杰 杨李林 于 2021-09-16 设计创作，主要内容包括：本发明涉及材料科学技术领域,具体涉及一种钴蓝玻璃色料的制备方法；包括将Na-(2)CO-(3)、SiO-(2)、Al-(2)O-(3)和Co-(2)O-(3)混合,处理所得混合物的粒径≤300nm,之后在不低于1000℃下煅烧不少于30分钟；本发明提供一种钴蓝的制备方法,具有工艺简单、成本低廉、对设备要求低、产品纯度高、杂质少的技术优势。(The invention relates to the technical field of material science, in particular to a preparation method of a cobalt blue glass pigment; comprises mixing Na 2 CO 3 、SiO 2 、Al 2 O 3 And Co 2 O 3 Mixing, treating the obtained mixture to obtain a mixture with a particle size of less than or equal to 300nm, and calcining at a temperature of not less than 1000 ℃ for not less than 30 minutes; the preparation method of cobalt blue provided by the invention has the technical advantages of simple process, low cost, low requirement on equipment, high product purity and less impurities.)

1. A preparation method of a cobalt blue glass pigment is characterized by comprising the following steps: mixing Na₂CO₃、SiO₂、Al₂O₃And Co₂O₃Mixing, treating the obtained mixture to obtain a mixture with a particle size of less than or equal to 300nm, and calcining at a temperature of not less than 1000 ℃ for not less than 30 minutes.

2. The method of claim 1The preparation method of the cobalt blue glass pigment is characterized by comprising the following steps: the Na is₂CO₃、SiO₂、Al₂O₃And Co₂O₃The mixing molar ratio of (1): (1-5): (0.01-1): (0.01-1), preferably 1: (2-3): (0.02-0.06): (0.02-0.06), preferably 1 (2.532-2.671): (0.0479-0.0561): (0.0427-0.0514).

3. The method for preparing a cobalt blue glass colorant according to claim 1, wherein: the treatment method comprises the steps of carrying out ball milling and drying treatment on the mixture, preferably, the ball milling equipment is a ball mill, preferably a high-speed ball mill, and comprises a stainless steel ball milling tank and grinding beads, wherein the ball loading of the ball mill is 20-40g, and the ball-to-material ratio is (10-7): (1-2), the rotation speed is 800-.

4. A method of producing a cobalt blue glass colorant according to claim 3, characterized in that: the grinding beads comprise large balls and small balls, the diameter of each large ball is 8-12mm, the diameter of each small ball is 3-7mm, and the number ratio of the large balls to the small balls is (10-7): 1-2.

5. A method of producing a cobalt blue glass colorant according to claim 3 or 4, characterized in that: the ball milling method comprises the following steps: ball milling for 20-30min, and suspending for 10-20min, wherein the ball milling is carried out in a circulating intermittent manner for 4-8 times.

6. A method of producing a cobalt blue glass colorant according to claim 3 or 4, characterized in that: the ball milling is carried out in a rare gas environment and/or in the presence of a dispersing agent, the rare gas is high-purity argon or nitrogen, the dispersing agent is absolute ethyl alcohol, and the mass volume ratio of the mixture to the dispersing agent is (2-5) to (1-2).

7. A method of producing a cobalt blue glass colorant according to claim 3, characterized in that: the drying temperature is less than or equal to 200 ℃, preferably 50-100 ℃, and also preferably 55-80 ℃, and the drying weight loss is more than or equal to 5%.

8. The method for preparing a cobalt blue glass colorant according to claim 1, wherein: the resulting mixture has a particle size of 150nm or less, preferably 100nm or less, and still preferably 50 to 90 nm.

9. The method for preparing a cobalt blue glass colorant according to claim 1, wherein: the calcination temperature is 1000-1400 ℃.

10. A method of producing a cobalt blue glass colorant according to claim 1 or 9, characterized in that: the calcination temperature adopts a gradient temperature rise mode, and specifically comprises the following steps: heating from room temperature to (100-; heating from (100-; heating from (600-; heating from (900- & ltSUB & gt) DEG C to (1300- & ltSUB & gt) DEG C at a heating rate of (10-15) & ltSUB & gt DEG C/min.

Technical Field

The invention relates to the technical field of material science, in particular to a preparation method of a cobalt blue glass pigment.

Background

Cobalt blue (CoAl)₂O₄) Is a metal oxide mixed phase pigment having a spinel structure, wherein Co²⁺In tetrahedral pores of spinel structure, Al³⁺Is positioned in the octahedral gap, the structure is highly symmetrical, and the stability is strong. The cobalt blue has strong coloring capability, stable color, excellent temperature resistance, weather resistance and chemical stability resistance, and can be widely applied to the fields of high-temperature resistant paint, ceramic pigment, engineering plastic, glass coloring and the like.

The traditional preparation method of cobalt blue is a solid phase method. The aluminum oxide and the cobalt oxide are fully mixed and sintered at high temperature to obtain the cobalt blue glass pigment. Because the reaction rate is influenced by diffusion kinetics, when cobalt blue is synthesized by a solid phase method, not only is the reaction process time and energy consumed, but also the reaction product is seriously agglomerated, the coloring capability is not strong, and the high-temperature stability is poor.

Disclosure of Invention

The invention aims to provide a preparation method of a cobalt blue glass pigment, which comprises the following steps:

Na₂CO₃、SiO₂、Al₂O₃and Co₂O₃Mixing, treating the obtained mixture to obtain a mixture with a particle size of less than or equal to 300nm, and calcining at a temperature of not less than 1000 ℃ for not less than 30 minutes.

In a preferred embodiment of the present invention, Na is₂CO₃、SiO₂、Al₂O₃And Co₂O₃The mixing molar ratio of (1): (1-5): (0.01-1): (0.01-1), preferably 1: (2-3): (0.02-0.06): (0.02-0.06), preferably 1 (2.532-2.671): (0.0479-0.0561): (0.0427-0.0514).

In a preferred technical scheme of the invention, the treatment method comprises the steps of performing ball milling and drying treatment on the mixture, preferably, the ball milling equipment is a ball mill, preferably a high-speed ball mill, and comprises a stainless steel ball milling tank and grinding beads, wherein the ball loading of the ball mill is 20-40g, and the ball-to-material ratio is (10-7): (1-2), the rotation speed is 800-.

In the preferred technical scheme of the invention, the grinding beads comprise large balls and small balls, the diameter of the large balls is 8-12mm, the diameter of the small balls is 3-7mm, and the number ratio of the large balls to the small balls is (10-7) to (1-2).

In a preferred technical scheme of the invention, the ball milling method comprises the following steps: ball milling for 20-30min, and suspending for 10-20min, wherein the ball milling is carried out in a circulating intermittent manner for 4-8 times.

In a preferred embodiment of the invention, the ball milling is carried out in a noble gas atmosphere and/or in the presence of a dispersant.

In the preferred technical scheme of the invention, the rare gas is high-purity argon or nitrogen.

In a preferred technical scheme of the invention, the dispersing agent is absolute ethyl alcohol.

In the preferable technical scheme of the invention, the mass volume ratio of the mixture to the dispersing agent is (2-5) to (1-2).

In the preferred technical scheme of the invention, the drying temperature is less than or equal to 200 ℃, preferably 50-100 ℃, and also preferably 55-80 ℃, and the drying weight loss is more than or equal to 5%, preferably more than or equal to 8%.

In the preferred technical scheme of the invention, the particle size of the obtained mixture is less than or equal to 150nm, preferably less than or equal to 100nm, and also preferably 50-90 nm.

In the preferable technical scheme of the invention, the calcination temperature is 1000-1400 ℃.

In a preferred technical scheme of the invention, the calcination temperature adopts a gradient temperature rise mode, and specifically comprises the following steps: heating from room temperature to (100-; heating from (100-; heating from (600-; heating from (900- & ltSUB & gt) DEG C to (1300- & ltSUB & gt) DEG C at a heating rate of (10-15) & ltSUB & gt DEG C/min.

In a preferred technical scheme of the invention, the gradient temperature rise mode is as follows: heating from room temperature to 100 ℃, wherein the heating rate is 5 ℃/min; heating from 100 ℃ to 700 ℃, wherein the heating rate is 20 ℃/min; heating from 700 ℃ to 1000 ℃, wherein the heating rate is 15 ℃/min; the temperature is increased from 1000 ℃ to 1400 ℃, and the temperature increasing rate is 10 ℃/min.

In the preferable technical scheme of the invention, the calcining time is not less than 60 minutes.

Unless otherwise indicated, when the present invention relates to percentages between liquids, said percentages are volume/volume percentages; the invention relates to the percentage between liquid and solid, said percentage being volume/weight percentage; the invention relates to the percentages between solid and liquid, said percentages being weight/volume percentages; the balance being weight/weight percent.

Compared with the prior art, the invention has the following beneficial effects: the invention provides a preparation method of cobalt blue, which has the technical advantages of simple process, energy consumption reduction, low requirement on equipment, high product purity, less impurities and improvement on the coloring capacity of a glass pigment.

Drawings

FIG. 1 is an XRD pattern of a cobalt blue glass colorant prepared in example 1.

FIG. 2 is an XRD pattern of a cobalt blue glass colorant prepared in example 2.

FIG. 3 is an XRD pattern of a cobalt blue glass colorant prepared in example 3.

FIG. 4 is an XRD pattern of a cobalt blue glass colorant prepared in example 4.

FIG. 5 is an XRD pattern of a cobalt blue glass colorant prepared in example 6.

FIG. 6 is a diagram of the cobalt blue glass colorants prepared in examples 2-5.

Detailed Description

The present invention is further illustrated in detail by the following examples and experimental examples. These examples and experimental examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Examples 1 to 6

The preparation method of the cobalt blue glass pigment has the advantages that the molar ratio of a mixture, the gradient heating mode and the product detection results (purity, XRD pattern and morphology) are shown in the table 1, and the steps are as follows:

(1) preparation of Na₂CO₃、SiO₂、Al₂O₃、Co₂O₃The particle size is 100-300nm, and the mixture is obtained;

(2) providing a high-speed ball mill with the volume of 50ml, comprising a stainless steel ball milling tank and grinding beads, wherein the ball loading is 30g, and the ball-material ratio is 10: 1, the rotating speed is 1000 rpm; the grinding beads comprise big balls and small balls, the diameter of the big balls is 10mm, the diameter of the small balls is 6mm, and the number ratio of the big balls to the small balls is 5: 1;

introducing high-purity argon into a high-speed ball mill, completely replacing gas, putting 10g of the mixture and 2mL of absolute ethyl alcohol into the high-speed ball mill, performing ball milling for 30min, pausing for 15min, performing intermittent circulation for 5 times, standing for 5 hours, and taking out to obtain a mixture with the particle size of 50-90 nm;

(3) pouring the mixture obtained in the step (2) into a corundum crucible, covering the corundum crucible with tinfoil, placing the corundum crucible into a vacuum drying oven, and drying the corundum crucible at 65 ℃ for 8 hours to obtain mixture powder;

(4) and (3) placing the mixture powder obtained in the step (3) into a box-type furnace, performing gradient temperature rise according to the mode shown in the table 1, then preserving the temperature for 60min, and then cooling to room temperature to obtain the cobalt blue glass pigment, wherein the XRD (X-ray diffraction) pattern and the product morphology are shown in the attached drawing.

Table 1:

the above description of the specific embodiments of the present invention is not intended to limit the present invention, and those skilled in the art may make various changes and modifications according to the present invention without departing from the spirit of the present invention, which is defined in the appended claims.