阅读说明：本技术 一种低温镉硒红釉粉及其制备方法和应用 (Low-temperature cadmium-selenium red glaze powder and preparation method and application thereof ) 是由 唐帆 李爱林 彭健辉 于 2020-12-15 设计创作，主要内容包括：本发明公开了一种低温镉硒红釉粉及其制备方法和应用,低温镉硒红釉粉的制备方法包括干磨红丹、硼酸、石英、碳酸镉、硼砂和高岭土,制得混合物；将混合物打粉、第一次煅烧、水冷、湿磨、过筛、干燥后再次打粉,制得低温熔块粉；将低温熔块粉与高岭土、氧化锆和镉硒红色料干磨混合后,打粉、第二次煅烧、水冷、湿磨、过筛、干燥后再次打粉,制得低温镉硒红釉粉；通过优化低温熔块的配方,再将低温熔块湿磨制成熔块粉,熔块粉再与镉硒红色料干磨均匀、煅烧、水淬、湿磨,得到低温镉硒红釉粉,通过二次烧成的工艺,使其中的易挥发物在烧制过程中充分挥发,从而使低温镉硒红釉粉应用在玻璃、搪瓷上不产生毛孔,使釉面的发色更鲜红、光泽度更高。(The invention discloses a low-temperature cadmium-selenium red glaze powder and a preparation method and application thereof, wherein the preparation method of the low-temperature cadmium-selenium red glaze powder comprises the steps of dry grinding red lead, boric acid, quartz, cadmium carbonate, borax and kaolin to prepare a mixture; pulverizing the mixture, calcining for the first time, cooling with water, wet grinding, sieving, drying, and pulverizing again to obtain low-temperature clinker powder; mixing the low-temperature clinker powder with kaolin, zirconium oxide and a cadmium-selenium red pigment through dry grinding, powdering, calcining for the second time, water cooling, wet grinding, sieving, drying and powdering again to prepare low-temperature cadmium-selenium red glaze powder; the low-temperature frit is prepared by optimizing the formula of the low-temperature frit, wet-grinding the low-temperature frit into frit powder, dry-grinding the frit powder and a cadmium-selenium red pigment uniformly, calcining, water quenching and wet-grinding to obtain the low-temperature cadmium-selenium red glaze powder, and fully volatilizing volatile substances in the low-temperature cadmium-selenium red glaze powder in the firing process through a secondary firing process, so that pores are not generated when the low-temperature cadmium-selenium red glaze powder is applied to glass and enamel, and the color development of the glaze surface is more bright red and has higher glossiness.)

1. A preparation method of low-temperature cadmium-selenium red glaze powder is characterized by comprising the following steps:

s001, dry grinding red lead, boric acid, quartz, cadmium carbonate, borax and kaolin to prepare a mixture;

s002, sequentially performing powder grinding, primary calcining, water cooling, wet grinding, sieving and drying on the mixture in the S001, and then performing powder grinding again to prepare low-temperature fusion cake powder;

and S003, dry-grinding and mixing the low-temperature clinker powder in the S002 with kaolin, zirconium oxide and a cadmium-selenium red pigment, and then sequentially carrying out powder grinding, secondary calcination, water cooling, wet grinding, sieving and drying, and then carrying out powder grinding again to prepare the low-temperature cadmium-selenium red glaze powder.

2. The method for preparing low-temperature cadmium-selenium red glaze powder according to claim 1, wherein the contents of the components in step S001 are, in mass percent: 59.5 to 62.3 percent of red lead, 17 to 17.9 percent of boric acid, 8.6 to 9.1 percent of quartz, 6.5 to 7 percent of cadmium carbonate, 3.5 to 4.2 percent of borax and 0 to 4.5 percent of kaolin.

3. The method for preparing low-temperature cadmium-selenium red glaze powder according to claim 1, wherein the contents of the components in the step S002 are respectively as follows by mass percent: 82% of low-temperature clinker powder, 5% of kaolin, 1% of zirconium oxide and 12% of cadmium-selenium red pigment.

4. The method for preparing low-temperature cadmium-selenium red glaze powder as claimed in claim 1, wherein the temperature of the first calcination in step S002 is 900-1000 ℃.

5. The method as claimed in claim 1, wherein the second calcination step S003 is carried out at a temperature of 750-850 ℃.

6. The method for preparing cadmium-selenium red glaze powder at low temperature as claimed in claim 1, wherein the mesh number of the sieving in steps S002 and S003 is 250 meshes, and the sieving requirement is that the sieving residue is less than 0.03%.

7. A low-temperature cadmium-selenium red glaze powder, which is characterized by being prepared by the preparation method of the low-temperature cadmium-selenium red glaze powder in any one of claims 1 to 6.

8. The application of the low-temperature cadmium-selenium red glaze powder is characterized in that the low-temperature cadmium-selenium red glaze powder prepared by the preparation method of the low-temperature cadmium-selenium red glaze powder in any one of claims 1 to 6 is applied to glass printing ink.

9. The application of the low-temperature cadmium-selenium red glaze powder is characterized in that the low-temperature cadmium-selenium red glaze powder prepared by the preparation method of the low-temperature cadmium-selenium red glaze powder in any one of claims 1 to 6 is applied to enamel glaze.

Technical Field

The invention relates to the technical field of glaze powder and a preparation method and application thereof, in particular to low-temperature cadmium-selenium red glaze powder and a preparation method and application thereof.

Background

The bright red is always well liked by the Chinese, the bright red pigment sold on the market at present mainly comprises cadmium sulfoselenide wrapped by zirconium silicate, but the heat resistance of the pigment in the heat treatment process is insufficient, the pigment is oxidized and decomposed from about 500 ℃, so that the pigment is easy to fade at high temperature, the color is not deep red enough, and some pigments are not even temperature-resistant, so that the glaze surface has the phenomena of bubbles or orange glaze and the like. The low-temperature red glaze powder on the market can obtain bright red color, and the common preparation method comprises the steps of firstly preparing the low-temperature frit glaze powder and then ball-milling and uniformly mixing the low-temperature frit glaze powder and the cadmium-selenium red pigment, but the glaze effect is not ideal, the glossiness is not high, and pores exist.

It is seen that improvements and enhancements to the prior art are needed.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide low-temperature cadmium-selenium red glaze powder, a preparation method and application thereof, and aims to solve the problem that the glaze surface effect of the cadmium-selenium red glaze powder prepared by the existing method is poor.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of low-temperature cadmium-selenium red glaze powder comprises the following steps:

s001, dry grinding red lead, boric acid, quartz, cadmium carbonate, borax and kaolin to prepare a mixture;

s002, sequentially performing powder grinding, primary calcining, water cooling, wet grinding, sieving and drying on the mixture in the S001, and then performing powder grinding again to prepare low-temperature fusion cake powder;

and S003, dry-grinding and mixing the low-temperature clinker powder in the S002 with kaolin, zirconium oxide and a cadmium-selenium red pigment, and then sequentially carrying out powder grinding, secondary calcination, water cooling, wet grinding, sieving and drying, and then carrying out powder grinding again to prepare the low-temperature cadmium-selenium red glaze powder.

In the preparation method of the low-temperature cadmium-selenium red glaze powder, the contents of the components in the step S001 are respectively as follows by mass percent: 59.5 to 62.3 percent of red lead, 17 to 17.9 percent of boric acid, 8.6 to 9.1 percent of quartz, 6.5 to 7 percent of cadmium carbonate, 3.5 to 4.2 percent of borax and 0 to 4.5 percent of kaolin.

In the preparation method of the low-temperature cadmium-selenium red glaze powder, the contents of the components in the step S002 are respectively as follows by mass percent: 82% of low-temperature clinker powder, 5% of kaolin, 1% of zirconium oxide and 12% of cadmium-selenium red pigment.

In the preparation method of the low-temperature cadmium-selenium red glaze powder, the temperature of the first calcination in the step S002 is 900-1000 ℃.

In the preparation method of the low-temperature cadmium-selenium red glaze powder, the temperature of the second calcination in the step S003 is 750-850 ℃.

In the preparation method of the low-temperature cadmium-selenium red glaze powder, the sieving mesh number in the steps S002 and S003 is 250 meshes, and the sieving residue is required to be less than 0.03%.

A low-temperature cadmium-selenium red glaze powder is prepared by the preparation method of the low-temperature cadmium-selenium red glaze powder.

The low-temperature cadmium-selenium red glaze powder prepared by the preparation method of the low-temperature cadmium-selenium red glaze powder is applied to glass printing ink.

The application of the low-temperature cadmium-selenium red glaze powder is characterized in that the low-temperature cadmium-selenium red glaze powder prepared by the preparation method of the low-temperature cadmium-selenium red glaze powder is applied to enamel glaze.

Has the advantages that:

the invention provides a low-temperature cadmium-selenium red glaze powder and a preparation method and application thereof, wherein the formula of the low-temperature frit is optimized, the low-temperature frit is wet-milled to prepare frit powder, the frit powder is dry-milled uniformly with a cadmium-selenium red pigment, calcined, water-quenched and wet-milled to obtain the low-temperature cadmium-selenium red glaze powder, and the secondary firing process is adopted to fully volatilize volatile substances in the firing process.

Drawings

FIG. 1 is a graph showing the color development on glass for examples 1 to 3 and comparative example.

FIG. 2 is a comparison of the color development on enamels of examples 1 to 3 and comparative example.

Detailed Description

The invention provides a low-temperature cadmium-selenium red glaze powder and a preparation method and application thereof, and in order to make the purpose, technical scheme and effect of the invention clearer and more clear, the invention is further described in detail by referring to the attached drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the scope of the invention.

The invention provides a preparation method of low-temperature cadmium-selenium red glaze powder, which comprises the following steps:

(1) the components are weighed according to the proportion of 59.5 to 62.3 percent of red lead, 17 to 17.9 percent of boric acid, 8.6 to 9.1 percent of quartz, 6.5 to 7 percent of cadmium carbonate, 3.5 to 4.2 percent of borax and 0 to 4.5 percent of kaolin for standby.

(2) Dry grinding red lead, boric acid, quartz, cadmium carbonate, borax and kaolin for 10 minutes to obtain a mixture.

(3) Pulverizing the mixture, calcining at the temperature of 900-1000 ℃, quenching with water after reaching the set temperature, wet-grinding until the fineness is 250 meshes and the residual is less than 0.03%, drying (vacuum filtration), and pulverizing again to obtain the low-temperature clinker powder. At the temperature range of 900-.

(4) And (2) dry-grinding 82% of low-temperature clinker powder, 5% of kaolin, 1% of zirconium oxide and 12% of cadmium-selenium red pigment for 10 minutes, mixing, pulverizing, carrying out secondary calcination at the temperature of 750-850 ℃, water quenching, wet grinding until the fineness is 250 meshes and the residual is less than 0.03%, drying (vacuum filtration), and pulverizing again to obtain the low-temperature cadmium-selenium red glaze powder.

Red lead, namely, lead tetroxide, also called as red lead, mainly plays a role in cooling. The melting points of the minium, the boric acid and the borax are lower, and the effect of reducing the sintering temperature is achieved. Quartz is one of the constituents of the glaze. Cadmium carbonate has a promoting effect on the color development of cadmium sulfoselenide. Kaolin provides alumina and improves the suspensibility of the glaze slip. Preferably, the raw materials of each component in the low-temperature frit all adopt high-purity raw materials, so that the influence of impurities on the glaze effect is avoided.

Firstly, red lead, boric acid, quartz, cadmium carbonate, borax and kaolin are fired into frits, which is beneficial to reducing firing defects of the glaze and ensuring that the melting temperature of the glaze is more uniform. The low-temperature clinker powder is used as a low-temperature solvent, kaolin is added to improve the suspension property of the glaze, the zirconia can improve the high-temperature viscosity of the glaze, expand the temperature range of viscosity change and improve the anti-cracking performance of the glaze, and the zirconia is high-temperature resistant, stable in chemical property, capable of improving the chemical stability and acid and alkali resistance of the glaze and capable of playing a role of an opacifier.

The low-temperature clinker powder composed of the components is firstly calcined when the low-temperature clinker powder is prepared, and then the low-temperature clinker powder is mixed with the cadmium-selenium red pigment and then is calcined for the second time, so that the volatile matter of the glaze powder after the secondary calcination is volatilized at high temperature, sulfur dioxide is volatilized at high temperature, and selenium dioxide is sublimated at high temperature (sublimation at 315 ℃), so that the volatile matter cannot be generated when the glaze powder is applied to firing of glass and enamel at the temperature of 750 plus materials and 850 ℃, and the glaze surface of the glass and enamel is smooth and has no air holes, high glossiness and deep red color development; the preparation method widens the application range of the cadmium-selenium red glaze powder, and prevents cadmium and selenium from being oxidized into cadmium oxide and selenium dioxide at high temperature (generally, pigment or glaze is required to keep good color generation at 800 ℃) and changing into grey black substances to lose the special deep red color thereof.

A low-temperature cadmium-selenium red glaze powder is prepared by the preparation method of the low-temperature cadmium-selenium red glaze powder.

The application of low-temperature cadmium-selenium red glaze powder is characterized by applying the low-temperature cadmium-selenium red glaze powder to glass printing ink and enamel glaze; the glaze surface has fine, bright and red color and no pores.

Example 1

The formula of the low-temperature frit comprises the following components: 59.5 percent of red lead, 17.2 percent of boric acid, 8.6 percent of quartz, 6.7 percent of cadmium carbonate, 3.5 percent of borax and 4.5 percent of kaolin.

Proportioning, dry grinding for 10 minutes, pulverizing, calcining at 950 ℃, water quenching after the set temperature is reached, wet grinding until the fineness is 250 meshes and the residual is less than 0.03%, vacuum filtering, drying and pulverizing to obtain the clinker powder.

Secondly, dry grinding 82% of the clinker powder, 5% of kaolin, 1% of zirconium oxide and 12% of cadmium-selenium red pigment for 10 minutes, powdering, calcining at 750 ℃, quenching in water after reaching the set temperature, wet grinding until the fineness is 250 meshes and the residual is less than 0.03%, vacuum filtering, drying and powdering to obtain the low-temperature cadmium-selenium red glaze powder.

Example 2

The formula of the low-temperature frit comprises the following components: 60% of red lead, 17% of boric acid, 9% of quartz, 7% of cadmium carbonate, 4% of borax and 2% of kaolin.

Proportioning, dry grinding for 10 minutes, pulverizing, calcining at 1000 ℃, water quenching after the set temperature is reached, wet grinding until the fineness is 250 meshes and the residual is less than 0.03%, vacuum filtering, drying and pulverizing to obtain the clinker powder.

Secondly, dry grinding 82% of the clinker powder, 5% of kaolin, 1% of zirconium oxide and 12% of cadmium-selenium red pigment for 10 minutes, powdering, calcining at 800 ℃, quenching in water after the set temperature is reached, wet grinding until the fineness is 250 meshes and the residual is less than 0.03%, vacuum filtering, drying and powdering to obtain the low-temperature cadmium-selenium red glaze powder.

Example 3

The formula of the low-temperature frit comprises the following components: 62.3 percent of red lead, 17.9 percent of boric acid, 9.1 percent of quartz, 6.5 percent of cadmium carbonate, 4.2 percent of borax and 0 percent of kaolin.

Proportioning, dry grinding for 10 minutes, pulverizing, calcining at 900 ℃, water quenching after the set temperature is reached, wet grinding until the fineness is 250 meshes and the residual is less than 0.03%, vacuum filtering, drying and pulverizing to obtain the clinker powder.

Secondly, dry grinding 82% of the clinker powder, 5% of kaolin, 1% of zirconium oxide and 12% of cadmium-selenium red pigment for 10 minutes, powdering, calcining at 850 ℃, quenching in water after the set temperature is reached, wet grinding until the fineness is 250 meshes and the residual is less than 0.03%, vacuum filtering, drying and powdering to obtain the low-temperature cadmium-selenium red glaze powder.

Verification test

Sample preparation: the low-temperature cadmium-selenium red glaze powder prepared in the embodiments 1 to 3 and the cadmium-selenium red glaze powder on the market.

Color development on glass

The glass detection process comprises the following steps: putting 8g of water-based resin, 14g of cadmium-selenium red glaze powder and 100g of 5 mm-diameter zirconium beads into a 100ml small plastic tank, quickly ball-milling for 30 minutes to prepare glass ink, then using a 250-mesh screen, screen-printing the glass ink on glass by a scraper, baking the glass by an oven at 120 ℃, then placing the glass into the oven at about 750 ℃, baking for 4-5 minutes (until the glass just deforms), quickly taking out, and cooling.

The color development ratio on the glass is shown in FIG. 1 (in FIG. 1, from left to right, example 1, comparative example, example 2, comparative example, example 3, and comparative example, respectively).

The detection results of the color difference meter are shown in table 1 below:

color difference value	L	a	b
				Comparative example	23.5	44.5	35.2
Example 1	25.2	47.4	37
				Example 2	27.9	50.9	40
Example 3	26.1	48.3	38.4

The results of the gloss measurements are shown in Table 2 below:

degree of gloss	Degree of degree/° c
		Comparative example	63
Example 1	67
		Example 2	73
Example 3	69

As can be seen from FIG. 1 and tables 1-2, the glass of examples 1-3 of the present invention has better effect than the comparative example, wherein the color development effect of example 2 is the best, more bright red, better covering power, and the glaze of examples 1-3 has high glossiness and no pores.

Secondly, color development in the enamel glaze

The enamel detection process comprises the following steps: 10g of cadmium-selenium red glaze powder and 10ml of water are put into a mortar to be ground evenly, evenly coated on a clean enamel sheet, baked at 120 ℃ in an oven, put into an electric furnace at 840 ℃ to be burnt for about 50 seconds, taken out and cooled.

The color development ratio on the enamel is shown in FIG. 2 (from left to right in FIG. 2: example 1, example 2, example 3, comparative example, respectively).

The results of the colorimeter are shown in table 3 below:

color difference value	L	a	b
				Comparative example	33	59.9	50.8
Example 1	33.6	60.4	53.8
				Example 2	34.8	61.7	55.6
Example 3	34.1	61	55.1

The results of the gloss measurements are shown in Table 4 below:

degree of gloss	Degree of degree/° c
		Comparative example	80
Example 1	85
		Example 2	90
Example 3	88

As can be seen from FIG. 2 and tables 3-4, the enamel of examples 1-3 of the present invention is superior to the comparative example, wherein the color development of example 2 is the best, more bright red, better hiding power, and the glaze of examples 1-3 has high glossiness and no pores.

In conclusion, the invention optimizes the formula of the low-temperature frit, wetly grinds the low-temperature frit to prepare frit powder, the frit powder is uniformly dry-ground with the cadmium-selenium red pigment, calcined, water-quenched and wet-ground to obtain the low-temperature cadmium-selenium red glaze powder, and the secondary sintering process is adopted to ensure that volatile matters in the frit powder are fully volatilized in the sintering process, and the preparation method of the low-temperature cadmium-selenium red glaze powder widens the application range of the cadmium-selenium red glaze powder, so that the low-temperature cadmium-selenium red glaze powder does not generate pores when being applied to glass and enamel at the temperature of 850 ℃, the color development of the glaze is more bright red, the glossiness of the glaze is higher, the glossiness of the glaze is more than 67 degrees when being applied to the glass, and the glossiness of the glaze is more than 85 degrees when being applied to the enamel.

It should be understood that equivalents and modifications of the technical solution and inventive concept thereof may occur to those skilled in the art, and all such modifications and alterations should fall within the protective scope of the present invention.