阅读说明：本技术 一种双层花釉及其产品的制备方法 (Double-layer fancy glaze and preparation method of product thereof ) 是由 杨瑞强 周健儿 常启兵 汪永清 包启富 刘昆 于 2019-12-03 设计创作，主要内容包括：本发明公开了一种双层花釉,包括底釉和面釉；所述面釉为液-液分相乳浊釉,其原料为锂硅系、硼硅系、磷硅系、或钛硅系；所述底釉由透明釉原料、用量为透明釉原料0.5～12.0wt％的着色氧化物组成,所述着色氧化物为TiO<Sub>2</Sub>、V<Sub>2</Sub>O<Sub>5</Sub>、Cr<Sub>2</Sub>O<Sub>3</Sub>、MnO<Sub>2</Sub>、Fe<Sub>2</Sub>O<Sub>3</Sub>、Co<Sub>2</Sub>O<Sub>3</Sub>、NiO<Sub>2</Sub>、CuO中的一种或其组合；所述透明釉的半球温度H<Sub>T1</Sub>比面釉高10～50℃,其室温～800℃的热膨胀系数大于面釉。此外,还公开了上述双层花釉产品的制备方法。本发明以分相乳浊釉作为面釉,以透明釉结合着色氧化物作为底釉,通过配方组分设计控制底釉、面釉之间温度差、热膨胀系数差,使得釉面呈现丰富立体的艺术效果,同时也极大地降低了双层花釉制备成本,有利于行业的应用发展和技术进步。(The invention discloses a double-layer fancy glaze, which comprises a ground glaze and a surface glaze; the overglaze is liquid-liquid phase-splitting emulsion glaze, and the raw material of the overglaze is lithium silicon system, boron silicon system, phosphorus silicon system or titanium silicon system; the ground glaze is composed of a transparent glaze raw material and a coloring oxide with the dosage of 0.5-12.0 wt% of the transparent glaze raw material, wherein the coloring oxide is TiO 2 、V 2 O 5 、Cr 2 O 3 、MnO 2 、Fe 2 O 3 、Co 2 O 3 、NiO 2 One or a combination of CuO; the hemispherical temperature H of the transparent glaze T1 The thermal expansion coefficient of the glaze is higher than that of the overglaze by 10-50 ℃ and is higher than that of the overglaze at room temperature-800 ℃. In addition, a preparation method of the double-layer fancy glaze product is also disclosed. The invention takes the phase-separated opaque glaze as the overglaze, the transparent glaze combined with the coloring oxide as the ground glaze, and the temperature difference and the thermal expansion coefficient difference between the ground glaze and the overglaze are controlled by the formula component design, so that the glaze surface is in a shape of a glaze surfaceThe three-dimensional artistic effect is enriched, the preparation cost of the double-layer fancy glaze is greatly reduced, and the application development and the technical progress of the industry are facilitated.)

1. A double-layer fancy glaze comprises a ground glaze and a surface glaze; the method is characterized in that: the overglaze is liquid-liquid phase-splitting emulsion glaze, and the raw material of the overglaze is lithium silicon system, boron silicon system, phosphorus silicon system or titanium silicon system; the ground glaze is composed of a transparent glaze raw material and a coloring oxide with the dosage of 0.5-12.0 wt% of the transparent glaze raw material, wherein the coloring oxide is TiO₂、V₂O₅、Cr₂O₃、MnO₂、Fe₂O₃、Co₂O₃、NiO₂One or a combination of CuO; the hemispherical temperature H of the transparent glaze_T1The thermal expansion coefficient of the glaze is higher than that of the overglaze by 10-50 ℃ and is higher than that of the overglaze at room temperature-800 ℃.

2. The double-layer fancy glaze according to claim 1, wherein: the overglaze raw material is lithium silicon system, and the chemical component is Li₂O 3.2～10.3wt％、K₂O 1.2～3.5wt％、Na₂O 1.0～2.8wt％、CaO 4.8～7.9wt％、ZnO0.9～2.7wt％、Al₂O₃8.4～12.1wt％、SiO₂66.1 to 72.7 wt%; the chemical component of the transparent glaze raw material in the ground glaze is K₂O 2.5～4wt％、Na₂O 2.5～4wt％、CaO 8～10wt％、BaO 1～2wt％、B₂O₃1～3wt％、Al₂O₃6～10wt％、SiO₂68～73wt％。

3. The double-layer fancy glaze according to claim 1, wherein: the overglaze is made of boron-silicon system and has the chemical component K₂O 1.2～2.8wt％、Na₂O 2.5～4.7wt％、CaO 7.2～12.2wt％、BaO 0.8～1.5wt％、ZnO0.8～1.5wt％、MgO 0.8～1.5wt％、Al₂O₃6.2～11.3wt％、B₂O₃6.2～14.5wt％、SiO₂65.8-72 wt%; the chemical component of the transparent glaze raw material in the ground glaze is K₂O 4～7wt％、Na₂O 3～6wt％、CaO 2～5wt％、ZnO 1～3wt％、MgO 5～7wt％、B₂O₃2～3wt％、Al₂O₃8～12wt％、SiO₂60～70wt％。

4. The double-layer fancy glaze according to claim 3, wherein: the overglaze comprises the following raw materials in parts by weight: 6-10 parts of potash feldspar, 10-13 parts of albite, 8-12 parts of calcite, 1-3 parts of barium carbonate, 0.5-2 parts of zinc oxide, 0.5-4 parts of calcined talc, 10-22 parts of borocalcite, 1.5-5 parts of Suzhou soil and 35-40 parts of quartz; the transparent glaze in the ground glaze comprises the following raw materials in parts by weight: 10-13 parts of potash feldspar, 12-15 parts of albite, 13-15 parts of calcite, 6-9 parts of calcined talc, 3-5 parts of borocalcite, 4-6.5 parts of Suzhou soil, 0.5-1.5 parts of zinc oxide and 35-38 parts of quartz.

5. The double-layer fancy glaze according to claim 1, wherein: the overglaze is made of phosphorus-silicon series and comprises the chemical component K₂O 3.5～5.5wt％、Na₂O 1.5～4.2wt％、CaO 6.2～10.5wt％、BaO 1.0～5.2wt％、Al₂O₃6.8～14.2wt％、P₂O₅0.68～12.58wt％、SiO₂60.4-70.2 wt%; the chemical component of the transparent glaze raw material in the ground glaze is K₂O 2～4wt％、Na₂O 2～4wt％、CaO 8～15wt％、ZnO 0.5～2wt％、Al₂O₃8～12wt％、SiO₂72～78wt％。

6. The double-layer fancy glaze according to claim 1, wherein: the overglaze is made of titanium-silicon system and has the chemical component of K₂O 0.5～1.7wt％、Na₂O 3.2～5.0wt％、CaO 6.9～13.1wt％、ZnO 0.7～1.6wt％、Al₂O₃5.9～10.5wt％、TiO₂1.6～7.2wt％、SiO₂62.1 to 73.4 wt%; the chemical component of the transparent glaze raw material in the ground glaze is K₂O 1～3wt％、Na₂O 2～6wt％、CaO 12～15wt％、BaO 1～3wt％、ZnO 1～2wt％、B₂O₃1～3wt％、Al₂O₃8～12wt％、SiO₂62～73wt％。

7. The double-layer fancy glaze according to claim 6, wherein: the overglaze comprises the following raw materials in parts by weight: 8-11 parts of potash feldspar, 13-16 parts of albite, 6-8 parts of calcite, 7-10 parts of borocalcite, 4-7 parts of Suzhou soil, 2-6 parts of titanium dioxide and 45-49 parts of quartz; the transparent glaze in the ground glaze comprises the following raw materials in parts by weight: 14-16 parts of potash feldspar, 7-9 parts of albite, 18-22 parts of calcite, 4-6 parts of barium carbonate, 1-3 parts of zinc oxide, 4-6 parts of borocalcite, 5-8 parts of Suzhou soil and 35-38 parts of quartz.

8. Method for the preparation of a double-layer fancy glaze product according to any one of claims 1 to 7, characterized in that it comprises the following steps:

(1) preparation of double-layer fancy glaze ground glaze slurry

Mixing the transparent glaze raw material with coloring oxide, ball-milling uniformly by a wet method, and sieving to obtain the transparent glaze with the specific gravity of 1.6-1.7 g/cm³The colored glaze is double-layer fancy glaze ground glaze slurry;

(2) preparation of double-layer fancy glaze surface glaze slurry

Ball-milling and mixing the overglaze raw material by a wet method, and sieving to obtain the overglaze product with the specific gravity of 1.5-1.6 g/cm³The glaze slip is double-layer fancy glaze surface glaze slip;

(3) preparation of double-layer fancy glaze product

Applying the double-layer fancy glaze ground coat slurry to a blank body, and drying to form a ground coat layer; then the double-layer fancy glaze surface glaze slurry is applied on the ground glaze layer and dried to form a surface glaze layer; and calcining to obtain the double-layer fancy glaze product.

9. The method for preparing a double-layer fancy glaze product according to claim 8, wherein the method comprises the following steps: the thickness of the bottom glaze layer in the step (3) is 0.5-1.0 mm; the thickness of the overglaze layer is 0.2-1.0 mm.

10. Method for preparing a double-layer fancy glaze product according to claim 8 or 9, wherein: in the step (3), the calcination temperature is 1150-1280 ℃, and the heat preservation time is 5-30 min.

Technical Field

The invention relates to the technical field of ceramic glaze, in particular to a double-layer fancy glaze and a preparation method of a product thereof.

Background

The fancy glaze is a kind of artistic glaze with a glaze surface showing a combination of two or more colors, has a unique decorative effect, is applied to daily ceramics, building sanitary ceramics and the like from the initial display ceramics to the present, is rich in variety, and plays an increasingly important role in ceramic decoration. The double-layer fancy glaze is characterized in that two glazes with different colors, namely a ground glaze and a surface glaze, are sequentially applied to a blank body, and the glaze forms various effects with different patterns by physical and chemical reactions, component diffusion, bubble stirring and the like among the glazes at high temperature.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a double-layer fancy glaze with low cost and rich glaze surface effect, wherein split-phase opaque glaze is used as overglaze, transparent glaze is combined with coloring oxide to be ground glaze, and the temperature difference and the thermal expansion coefficient difference between the underglaze and the overglaze are controlled through the formula component design, so that the glaze surface presents rich three-dimensional artistic effect. The invention also aims to provide a preparation method of the double-layer fancy glaze product.

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

the invention provides a double-layer fancy glaze, which comprises a ground glaze and a cover glaze; the overglaze is liquid-liquid phase-splitting emulsion glaze, and the raw material of the overglaze is lithium silicon system, boron silicon system, phosphorus silicon system or titanium silicon system; the ground glaze is composed of a transparent glaze raw material and a coloring oxide with the dosage of 0.5-12.0 wt% of the transparent glaze raw material, wherein the coloring oxide is TiO₂、V₂O₅、Cr₂O₃、MnO₂、Fe₂O₃、Co₂O₃、NiO₂One or a combination of CuO; the hemispherical temperature H of the transparent glaze_T1The thermal expansion coefficient of the glaze is higher than that of the overglaze by 10-50 ℃, and the room temperature-800 ℃ is higher than that of the overglaze (the thermal expansion coefficient is 0.5 multiplied by 10 larger than that of the overglaze)^-6/(mm·℃^-1)～1.2×10^-6/(mm·℃^-1))。

Furthermore, the overglaze raw material is lithium silicon system, and the chemical component of the overglaze raw material is Li₂O 3.2～10.3wt％、K₂O1.2～3.5wt％、Na₂O 1.0～2.8wt％、CaO 4.8～7.9wt％、ZnO 0.9～2.7wt％、Al₂O₃8.4～12.1wt％、SiO₂66.1 to 72.7 wt%; the chemical component of the transparent glaze raw material in the ground glaze is K₂O 2.5～4wt％、Na₂O 2.5～4wt％、CaO 8～10wt％、BaO 1～2wt％、B₂O₃1～3wt％、Al₂O₃6～10wt％、SiO₂68～73wt％。

Furthermore, the overglaze raw material of the invention is a boron-silicon system, and the chemical component of the overglaze raw material is K₂O 1.2～2.8wt％、Na₂O2.5～4.7wt％、CaO 7.2～12.2wt％、BaO 0.8～1.5wt％、ZnO 0.8～1.5wt％、MgO 0.8～1.5wt％、Al₂O₃6.2～11.3wt％、B₂O₃6.2～14.5wt％、SiO₂65.8-72 wt%; the chemical component of the transparent glaze raw material in the ground glaze is K₂O 4～7wt％、Na₂O 3～6wt％、CaO 2～5wt％、ZnO 1～3wt％、MgO 5～7wt％、B₂O₃2～3wt％、Al₂O₃8～12wt％、SiO₂60～70wt％。

In the scheme, when the overglaze raw material is a boron-silicon system, the overglaze comprises the following mineral components in parts by weight: 6-10 parts of potash feldspar, 10-13 parts of albite, 8-12 parts of calcite, 1-3 parts of barium carbonate, 0.5-2 parts of zinc oxide, 0.5-4 parts of calcined talc, 10-22 parts of borocalcite, 1.5-5 parts of Suzhou soil and 35-40 parts of quartz; the transparent glaze in the ground glaze comprises the following raw materials in parts by weight: 10-13 parts of potash feldspar, 12-15 parts of albite, 13-15 parts of calcite, 6-9 parts of calcined talc, 3-5 parts of borocalcite, 4-6.5 parts of Suzhou soil, 0.5-1.5 parts of zinc oxide and 35-38 parts of quartz.

Furthermore, the overglaze raw material is a phosphorus-silicon system, and the chemical component of the overglaze raw material is K₂O 3.5～5.5wt％、Na₂O1.5～4.2wt％、CaO 6.2～10.5wt％、BaO 1.0～5.2wt％、Al₂O₃6.8～14.2wt％、P₂O₅0.68～12.58wt％、SiO₂60.4-70.2 wt%; the chemical component of the transparent glaze raw material in the ground glaze is K₂O 2～4wt％、Na₂O2～4wt％、CaO 8～15wt％、ZnO 0.5～2wt％、Al₂O₃8～12wt％、SiO₂72～78wt％。

Furthermore, the overglaze raw material of the invention is titanium silicon system, and the chemical component is K₂O 0.5～1.7wt％、Na₂O3.2～5.0wt％、CaO 6.9～13.1wt％、ZnO 0.7～1.6wt％、Al₂O₃5.9～10.5wt％、TiO₂1.6～7.2wt％、SiO₂62.1 to 73.4 wt%; the chemical component of the transparent glaze raw material in the ground glaze is K₂O 1～3wt％、Na₂O 2～6wt％、CaO 12～15wt％、BaO 1～3wt％、ZnO 1～2wt％、B₂O₃1～3wt％、Al₂O₃8～12wt％、SiO₂62～73wt％。

In the scheme, when the overglaze raw material is a titanium-silicon system, the overglaze comprises the following mineral components in parts by weight: 8-11 parts of potash feldspar, 13-16 parts of albite, 6-8 parts of calcite, 7-10 parts of borocalcite, 4-7 parts of Suzhou soil, 2-6 parts of titanium dioxide and 45-49 parts of quartz; the transparent glaze in the ground glaze comprises the following raw materials in parts by weight: 14-16 parts of potash feldspar, 7-9 parts of albite, 18-22 parts of calcite, 4-6 parts of barium carbonate, 1-3 parts of zinc oxide, 4-6 parts of borocalcite, 5-8 parts of Suzhou soil and 35-38 parts of quartz.

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

the preparation method of the double-layer fancy glaze product provided by the invention comprises the following steps:

(1) preparation of double-layer fancy glaze ground glaze slurry

Mixing the transparent glaze raw material with coloring oxide, ball-milling uniformly by a wet method, and sieving to obtain the transparent glaze with the specific gravity of 1.6-1.7 g/cm³The colored glaze is double-layer fancy glaze ground glaze slurry;

(2) preparation of double-layer fancy glaze surface glaze slurry

Ball-milling and mixing the overglaze raw material by a wet method, and sieving to obtain the overglaze product with the specific gravity of 1.5-1.6 g/cm³The glaze slip is double-layer fancy glaze surface glaze slip;

(3) preparation of double-layer fancy glaze product

Applying the double-layer fancy glaze ground coat slurry to a blank body, and drying to form a ground coat layer; then the double-layer fancy glaze surface glaze slurry is applied on the ground glaze layer and dried to form a surface glaze layer; and calcining to obtain the double-layer fancy glaze product.

Further, in the preparation method, the thickness of the bottom glaze layer in the step (3) is 0.5-1.0 mm; the thickness of the overglaze layer is 0.2-1.0 mm. In the step (3), the calcination temperature is 1150-1280 ℃, and the heat preservation time is 5-30 min.

The invention has the following beneficial effects:

(1) richen the kind of double-layer fancy glaze and its glaze effect

The surface glaze of the existing double-layer fancy glaze is mostly added with an opacifier or a coloring agent, and the adjustment of the surface glaze and the final fancy glaze coloring effect are realized by adjusting the type and the addition amount of the opacifier or the coloring agent. However, this method has an effect on the adjustment of the shade change of a certain color without a large change in the final glazing effect. The invention adopts the liquid-liquid phase-splitting emulsion glaze as the overglaze of the double-layer fancy glaze, and because of the special phenomena of phase separation and component segregation in the phase-splitting glaze, under the condition that the ground glaze is not changed, the type of the overglaze is changed by changing the phase-splitting system of the phase-splitting emulsion glaze overglaze, and the glaze layer with different components of phase-splitting liquid drops and different sizes and volume fractions can be obtained, thereby realizing the richer and more colorful effect of the double-layer fancy glaze surface. Meanwhile, under the condition that the phase splitting opacified glaze is not changed, the color hue, the lightness and the saturation of the ground glaze are changed by adjusting the type and the addition amount of the coloring oxide of the ground glaze, and the components, the size and the volume fraction of phase splitting liquid drops in the glaze can be changed by the reaction, the diffusion, the bubble stirring and other actions between the ground glaze and the glaze, so that double-layer fancy glaze with different glaze effects is obtained, and the type and the glaze effect of the double-layer fancy glaze are enriched.

(2) Improve the glaze effect of the double-layer fancy glaze ceramic product

The traditional preparation method of the double-layer fancy glaze is to mix two kinds of single-color glaze, so that the obtained glaze surface has poor color effect and stereoscopic impression. The invention uses the liquid-liquid phase-splitting emulsion glaze as the double-layer fancy glaze overglaze, and uses the scattering and refraction effects of phase-splitting liquid drops generated by phase splitting of a glaze melt on incident light to make the overglaze present the effects of milky white, milky blue and the like with strong three-dimensional property.

(3) Reduce the preparation cost of the double-layer fancy glaze

A large amount of opacifiers with high price are mostly required to be added into the overglaze of the traditional double-layer fancy glaze, so that the preparation cost of the double-layer fancy glaze is high. The invention adopts common minerals as main raw materials, utilizes the scattering and refraction effects of spherical liquid drops generated by phase separation of glaze melt on incident light to ensure that the overglaze presents the effects of milky white, milky blue and the like with strong stereoscopy, and can cause the overglaze to present blue and white opacification without adding an opacifier with high price, thereby reducing the preparation cost of the double-layer fancy glaze.

Drawings

The invention will now be described in further detail with reference to the following examples and black and white figures:

FIG. 1 is a microscopic structural diagram of a section of a glaze layer of a double-layer fancy glaze product prepared in the first embodiment of the invention (1-1: a white area of the glaze layer; 1-2: a blue-green area of the glaze layer);

FIG. 2 is a microscopic structural diagram of a section of a glaze layer of a double-layer fancy glaze product prepared in the second embodiment of the invention (2-1: a blue-white area of the glaze and 2-2: a yellowish-brown area of the glaze).

Detailed Description