1. A preparation method of a three-dimensional large-size crystal flower decorative ceramic plate is characterized by comprising the following steps: distributing crystal glaze powder at the crystal texture position according to the decorative layout of the ceramic plate in a digital material distribution mode and forming to form a blank body; then, ink-jet printing design patterns on the surface of the blank and sintering to obtain the three-dimensional large-size crystal flower decorative ceramic plate; the crystal glaze powder forms crystal flowers with the diameter of 2-6 mm after being fired.

2. The method according to claim 1, wherein the chemical composition of the crystalline powder material comprises: by mass percent, SiO₂：33.0～38.0%、Al₂O₃：1.0～2.0%、TiO₂：9.5～11.5%、CaO：9.5～11.5%、K₂O：0.1～0.3%、Na₂O：3.0～5.0%、ZnO：28.0～33.0%。

3. The production method according to claim 1 or 2, wherein the main phase composition of the flower is zinc silicate.

4. The method according to any one of claims 1 to 3, wherein the raw material composition of the crystalline powder material comprises: by mass percentage, 30-45% of glass powder, 2-5% of kaolin, 8-16% of calcite, 10-15% of quartz powder, 10-15% of titanium dioxide and 30-40% of zinc oxide.

5. The method of claim 4The preparation method is characterized in that the chemical composition of the glass powder comprises the following steps: by mass percent, SiO₂：68.0～73.0%、Al₂O₃：1.0～2.0%、CaO：8.0～9.0%、MgO：3.5～4.5%、Na₂O：13.0～14.0%。

6. The production method according to any one of claims 1 to 5, wherein a raw material of the body includes an ultra-white powder in addition to the crystalline powder; the whiteness of the super-white powder is 55-75 degrees, and the chemical composition of the super-white powder comprises: by mass percent, SiO₂：62.0～67.0%、Al₂O₃：20.0～23.0%、K₂O：2.0～3.0%、Na₂O：3.0～4.0%、ZrO₂：1.0～2.0%。

7. The production method according to any one of claims 1 to 6, further comprising: applying protective glaze on the surface of the blank after the design pattern is printed by ink-jet printing before sintering; the chemical composition of the protective glaze comprises: by mass percent, SiO₂：46.0～52.0%、Al₂O₃：13.0～16.0%、CaO：6.0～9.0%、MgO：3.0～6.0%、K₂O：3.0～4.0%、Na₂O：2.5～3.5%、ZnO：3.0～6.0%。

8. The method according to claim 7, characterized in that the protective glaze is applied by spraying glaze; the specific gravity of the protective glaze is 1.20-1.30 g/cm³The glazing amount is 150-200 g/m²。

9. The production method according to any one of claims 1 to 8, wherein the firing is a low-temperature rapid firing, the maximum firing temperature is 1180 to 1120 ℃, and the firing period is 60 to 120 minutes.

10. A three-dimensional stereoscopic large-size crystallized decorative ceramic plate obtained by the production method according to any one of claims 1 to 9.

Background

At present, the crystal glaze is mostly used for decoration of daily porcelain, crystal flowers are naturally generated in a glaze layer, the decoration effect is three-dimensional and natural, and people's pursuit is obtained. However, the crystal pattern effect of the crystal glaze is greatly limited by the firing system. In order to form a three-dimensional natural decorative effect, crystal flower dry particles (crystal flower frits) can be glued and bonded on the surface of the blank body after the pattern is printed by ink jet. Although the decorative effect can be improved, the crystal flower decoration formed by the method only exists in the glaze layer, and the ceramic green brick needing grooving or chamfering on part cannot present the three-dimensional decoration similar to natural stone.

Disclosure of Invention

In a first aspect, the invention provides a preparation method of a three-dimensional large-size crystal flower decorative ceramic plate. The preparation method comprises the following steps: adopting a digital material distribution mode, distributing crystal glaze powder at the (required) crystal texture position according to the decorative layout of the ceramic plate and forming to form a blank body; then, ink-jet printing design patterns on the surface of the blank and sintering to obtain the three-dimensional large-size crystal flower decorative ceramic plate; the crystal glaze powder forms crystal flowers with the diameter of 2-6 mm after being fired.

The preparation method combines digital cloth and ink-jet printing technology, can well realize positioning texture crystallization, and has abundant three-dimensional decoration effect.

Preferably, the chemical composition of the crystalline powder material comprises: by mass percent, SiO₂：33.0～38.0％、Al₂O₃：1.0～2.0％、TiO₂：9.5～11.5％、CaO：9.5～11.5％、K₂O：0.1～0.3％、Na₂O：3.0～5.0％、ZnO：28.0～33.0％。

Preferably, the main phase composition of the crystal flower is zinc silicate.

Preferably, the raw material composition of the crystalline powder material comprises: by mass percentage, 30-45% of glass powder, 2-5% of kaolin, 8-16% of calcite, 10-15% of quartz powder, 10-15% of titanium dioxide and 30-40% of zinc oxide.

Preferably, the chemical composition of the glass powder comprises: by mass percent, SiO₂：68.0～73.0％、Al₂O₃：1.0～2.0％、CaO：8.0～9.0％、MgO：3.5～4.5％、Na₂O：13.0～14.0％。

Preferably, the raw materials of the blank comprise ultra-white powder besides crystalline powder; the whiteness of the super-white powder is 55-75 degrees, and the chemical composition of the super-white powder comprises: by mass percent, SiO₂：62.0～67.0％、Al₂O₃：20.0～23.0％、K₂O：2.0～3.0％、Na₂O：3.0～4.0％、ZrO₂：1.0～2.0％。

Preferably, the preparation method further comprises: applying protective glaze on the surface of the blank after the design pattern is printed by ink-jet printing before sintering; the chemical composition of the protective glaze comprises: by mass percent, SiO₂：46.0～52.0％、Al₂O₃：13.0～16.0％、CaO：6.0～9.0％、MgO：3.0～6.0％、K₂O：3.0～4.0％、Na₂O：2.5～3.5％、ZnO：3.0～6.0％。

Preferably, the protective glaze is applied in a glaze spraying manner; the specific gravity of the protective glaze is 1.20-1.30 g/cm³The glazing amount is 150-200 g/m²。

Preferably, the firing is low-temperature rapid firing, the maximum firing temperature is 1180-1120 ℃, and the firing period is 60-120 minutes.

In a second aspect, the invention provides a three-dimensional large-size crystal flower decorative ceramic plate obtained by the preparation method.

Drawings

FIG. 1 is a flow chart of the preparation of a three-dimensional large-sized crystal decorative ceramic plate;

FIG. 2 is a view showing the effect of the brick surface of the three-dimensional large-sized crystal decorative ceramic plate according to example 1;

fig. 3 is a graph showing the brick effect of the ceramic plate of comparative example 1.

Detailed Description

The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention. Unless otherwise specified, each percentage means a mass percentage.

The following is an exemplary description of the preparation method of the three-dimensional large-sized crystal decorative ceramic plate according to the present invention.

Distributing the material to form a ceramic blank to be formed. And adopting a digital material distribution mode to distribute crystal glaze powder at the crystal texture position according to the decorative layout of the ceramic plate to form a ceramic blank.

The crystalline powder is a high-zinc high-titanium low-aluminum system. In some embodiments, the chemical composition of the crystalline powder material may comprise: by mass percent, SiO₂：33.0～38.0％、Al₂O₃：1.0～2.0％、TiO₂：9.5～11.5％、CaO：9.5～11.5％、K₂O：0.1～0.3％、Na₂O: 3.0-5.0%, ZnO: 28.0 to 33.0 percent. The glaze material with the composition has low high-temperature viscosity, and is beneficial to crystal flower growth. The high content of titanium oxide can promote the zinc silicate crystal to be better precipitated in the glaze layer and form larger-size crystal flowers under the condition of low-temperature quick firing. In addition, the crystalline powder of the invention also omits Li₂O、B₂O₃、P₂O₅The introduction of the isostrong fluxing agent ensures that the glaze surface performance is more stable, and is convenient for reducing the defects of glaze shrinkage, pinholes and the like.

In the experiment, the crystal powder of a high-silicon high-aluminum low-zinc system is tried, but the glaze material has high-temperature viscosity, large-size crystal flowers are difficult to precipitate, and small crystal flowers are precipitated to show the flowing color effect. The high-zinc high-titanium low-aluminum system crystal powder can separate out lobate large crystal flowers after being fired. For example, the crystal grains have a diameter of 2 to 6mm after firing.

In some embodiments, the chemical composition of the crystalline powder material comprises: by mass percent, SiO₂：33.0～38.0％、Al₂O₃：1.0～2.0％、Fe₂O₃：0.06～0.36％、TiO₂：9.5～11.5％、CaO：9.5～11.5％、MgO：0.5～1.4％、K₂O：0.1～0.3％、Na₂O：3.0～5.0％、ZnO: 28.0-33.0%, loss on ignition: 4.5 to 6.5 percent.

The raw material composition of the crystallization powder material can comprise: by mass percentage, 30-45% of glass powder, 2-5% of kaolin, 8-16% of calcite, 10-15% of quartz powder, 10-15% of titanium dioxide and 30-40% of zinc oxide. The glass powder is mainly used for providing SiO₂The high temperature viscosity of the crystal glaze powder can be controlled in a proper range, so that the precipitation and growth of zinc silicate crystals are facilitated, and the zinc silicate crystals are not melted again in the sintering process. The purpose of zinc oxide is to promote the precipitation of zinc silicate crystals by allowing excess ZnO to be present in the glaze layer. The high-content titanium dioxide is introduced to mainly promote the precipitation of zinc silicate crystals in the glaze layer. The above steps are all to ensure that the high-temperature viscosity of the glaze is moderate, the glaze is suitable for the growth of crystal flowers, and the large crystal flowers in the shape of leaves are separated out. The main phase composition of the crystal flower is zinc silicate.

The kind of the glass powder is not limited, and the glass powder waste materials commonly used in the field can be adopted. For example, the chemical composition of the waste glass frits includes: by mass percent, SiO₂：68.0～73.0％、Al₂O₃：1.0～2.0％、CaO：8.0～9.0％、MgO：3.5～4.5％、Na₂O: 13.0 to 14.0 percent. In some embodiments, the chemical composition of the waste glass frits comprises: by mass percent, SiO₂：68.0～73.0％、Al₂O₃：1.0～2.0％、Fe₂O₃：0.06～0.36％、TiO₂：0.06～0.36％、CaO：8.0～9.0％、MgO：3.5～4.5％、K₂O：0.1～0.3％、Na₂O: 13.0-14.0%, loss on ignition: 0.1 to 0.5 percent.

The ceramic blank comprises ultra-white powder besides crystalline powder. The mass percentage of the crystalline powder in the ceramic blank can be adaptively changed according to the actual layout effect, and the preferred mass percentage of the crystalline powder in the ceramic blank is 3-30%. The difference in expansion coefficient between the crystalline glaze powder and the ultra-white powder is large, so that the deformation of the green brick is easily caused by the excessively high usage amount of the crystalline powder.

Preferably, the depth of the distribution of the crystalline powder should not exceed one third of the thickness of the body (in the direction from the surface to the bottom). The surface layer refers to a position closer to the inkjet-printed pattern. In addition, the distribution of the crystalline powder should not penetrate the green body layer because the crystalline glaze powder has a lower melting temperature than the ultra-white powder (base material), and thus the crystalline glaze powder is easily bonded to the roller in the high temperature region of the kiln, which is not favorable for sintering and forming the green brick.

The super white powder has higher whiteness and lower impurity content, and is more favorable for the decorative effect of brick surface bricks. The use of the super white powder can enhance the artistic aesthetic feeling of the ceramic plate, so that the texture and the pattern of the layout are better and softer. For example, the chemical composition of the ultrafast powder may include: by mass percent, SiO₂：62.0～67.0％、Al₂O₃：20.0～23.0％、K₂O：2.0～3.0％、Na₂O：3.0～4.0％、ZrO₂: 1.0 to 2.0 percent. In some embodiments, the chemical composition of the ultra-white powder comprises: by mass percent, SiO₂：62.0～67.0％、Al₂O₃：20.0～23.0％、Fe₂O₃：0.1～0.5％、TiO₂：0.1～0.5％、CaO：0.1～0.5％、MgO：0.8～1.3％、K₂O：2.0～3.0％、Na₂O：3.0～4.0％、ZrO₂: 1.0-2.0%, loss on ignition: 5.0 to 6.0 percent.

And pressing and molding the blank powder to obtain the blank. The size of the green body is not particularly limited, as it is a ceramic slab size commonly used in the art. The invention uses the crystal powder as part of the ceramic blank to realize the positioning of the material distribution and form the suitable texture layout by the digital material distribution. Thus obtaining the lobate crystal flower decoration on the green body, rather than obtaining the corresponding decoration on the surface of the green brick. The glossiness of the glaze surface can be changed according to the number of crystal flowers at different positions. As an example, the chemical composition of the ceramic blank may include, in mass percent, SiO₂：62.0～67.0％、Al₂O₃：20.0～23.0％、Fe₂O₃：0.1～0.5％、TiO₂：0.1～0.5％、CaO：0.1～0.5％、MgO：0.8～1.3％、K₂O：2.0～3.0％、Na₂O：3.0～4.0％、ZrO₂: 1.0-2.0%, loss on ignition: 5.0 to 6.0 percent.

And drying the green body. Drying in a drying kiln may be used. The drying time can be 1-1.5 h, and the moisture of the dried blank is controlled within 0.3-0.5 wt%.

And ink-jet printing a design pattern on the surface of the dried blank. The color and pattern of the ink jet printed pattern are adaptively changed depending on the design effect. The invention does not need to apply base coat on the surface of the blank. The purpose of the ground coat is to cover up blank flaws and to promote color development. However, if the base coat is applied to the body, the crystal patterns cannot be separated out.

And applying protective glaze on the blank after the design pattern is printed by ink jet. The purpose of applying the protective glaze is to improve the antifouling performance of the brick surface and protect the pattern from being easily abraded. In some embodiments, the chemical composition of the protective glaze may include: SiO in mass percent₂：46.0～52.0％、Al₂O₃：13.0～16.0％、CaO：6.0～9.0％、MgO：3.0～6.0％、K₂O：3.0～4.0％、Na₂O: 2.5-3.5%, ZnO: 3.0 to 6.0 percent. By controlling the chemical composition of the protective glaze within the range, the precipitation and growth of crystal flowers on the surface of the brick are not influenced, and the antifouling and abrasion conditions of the surface of the brick can be improved.

In some embodiments, the chemical composition of the protective glaze comprises: by mass percent, SiO₂：46.0～52.0％、Al₂O₃：13.0～16.0％、Fe₂O₃：0.1～0.5％、TiO₂：0.1～0.5％、CaO：6.0～9.0％、MgO：3.0～6.0％、K₂O：3.0～4.0％、Na₂O: 2.5-3.5%, ZnO: 3.0 to 6.0 percent. Loss on ignition: 7.0 to 10.0 percent.

The protective glaze can be applied by spraying glaze. The specific gravity of the protective glaze is 1.20-1.30 g/cm³The glazing amount is 150-200 g/m². By controlling the glazing parameters of the protective glaze within the range, the precipitation and growth of crystal flowers on the surface of the brick can be not influenced, and the antifouling and abrasion conditions of the surface of the brick can be improved.

And drying the blank body after the protective glaze is applied. Either electric drying or hot air oven drying may be used. The drying temperature is 100-150 ℃, and the moisture of the dried blank is controlled within 0.9 wt%.

And sintering the dried green body. Preferably, the firing method is low-temperature rapid firing. The low-temperature quick firing is more energy-saving and environment-friendly, and the application range is wider. The maximum firing temperature can be 1180-1120 ℃, and the firing period can be 60-120 minutes.

According to the invention, by adjusting the formula of the crystal glaze powder and combining a digital material distribution technology, more crystal flowers with the diameter of about 2-6 mm can grow on the brick surface at a fixed (specific) position under the condition of low-temperature quick firing. The ink-jet decoration technology can be combined to realize the crystal flower effect of different colors and enhance the glaze decoration.

The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.

Example 1

The preparation method of the three-dimensional large-size crystal flower decorative ceramic plate comprises the following steps:

(1) and (4) digitally distributing to form a ceramic blank to be formed. The specific process is as follows: distributing crystal glaze powder at the position of the required texture according to the decorative layout of the ceramic plate by adopting a digital material distribution mode (through a digital material distributor) to form a ceramic blank; dry-pressing the ceramic blank to form a blank; the crystal glaze powder comprises the following raw materials: by mass percentage, 31.3 percent of waste glass powder, 2.7 percent of kaolin, 12.5 percent of calcite, 11.5 percent of quartz powder, 10.7 percent of titanium dioxide and 31.3 percent of zinc oxide; the chemical composition of the crystalline powder material comprises: by mass percent, SiO₂：33.0～38.0％、Al₂O₃：1.0～2.0％、TiO₂：9.5～11.5％、CaO：9.5～11.5％、K₂O：0.1～0.3％、Na₂O：3.0～5.0％、ZnO：28.0～33.0％；

(2) Dry-pressing the ceramic blank to form a blank;

(3) drying the blank for 1-1.5 h, wherein the water content of the dried blank is within 0.3-0.5 wt%;

(4) printing a design pattern on the surface of the dried blank in an ink-jet mode;

(5) applying protective glaze on the surface of the blank after ink-jet printing of the designed pattern, wherein the specific gravity of the protective glaze is 1.25g/cm³The glazing amount is 170g/m²；

(6) Drying the green body after the protective glaze is applied; the drying temperature is 100-150 ℃, and the moisture of the dried blank is controlled within 0.9 wt%;

(7) and (4) sintering, wherein the maximum sintering temperature is 1220 ℃, and the sintering period is 60-120 minutes.

(8) Edging and grading;

(9) and (6) packaging and warehousing.

Fig. 2 is a brick surface effect diagram of a three-dimensional large-size crystal flower decorative ceramic plate. The large crystal flowers with the diameter of 2-6 mm grow on the local part of the brick surface.

Example 2

Essentially the same as example 1, except that: the crystal glaze powder comprises the following raw materials: 33.3 percent of waste glass powder, 2.7 percent of kaolin, 11.5 percent of calcite, 11.5 percent of quartz powder, 10.7 percent of titanium dioxide and 30.3 percent of zinc oxide.

Example 3

Essentially the same as example 1, except that: the crystal glaze powder comprises the following raw materials: by mass percentage, 34.3 percent of waste glass powder, 2.7 percent of kaolin, 8.5 percent of calcite, 11.5 percent of quartz powder, 11.7 percent of titanium dioxide and 31.3 percent of zinc oxide.

Comparative example 1

Essentially the same as example 1, except that: the crystal glaze powder comprises the following raw materials: by mass percentage, 45.0 percent of glass powder, 2.6 percent of kaolin, 12.3 percent of calcite, 10.0 percent of titanium dioxide and 30.1 percent of zinc oxide.

As shown in FIG. 3, under the same firing conditions, the ceramic plate of the present invention partially formed a low-temperature transparent glaze layer, and the surface of the tile did not have any crystal grains observed, and had a local gloss of 104.5 °. This is because the firing temperature of the crystalline glaze material of this comparative example is lowered, the high-temperature viscosity is too low, and the crystal grains precipitated on the glaze surface are re-melted.

Comparative example 2

The preparation method of the three-dimensional large-size crystal flower decorative ceramic plate comprises the following steps:

(1) dry-pressing and molding the ceramic blank to form an ultra-white blank;

(2) drying the blank for 1-1.5 h, wherein the water content of the dried blank is within 0.3-0.5 wt%;

(3) printing a design pattern on the surface of the dried blank in an ink-jet mode;

(4) melting the crystallized glaze powder at 1500 ℃, and then cooling the liquid by water to form a frit; crushing the frit into crystalline dry particles with the particle size of 40-80 meshes; spraying digital glue on the ultra-white blank according to the layout effect (for fixing), and then distributing crystallized dry particles by a dry particle machine; about 100 to 500g/m of crystallized dry particles per square meter of cloth²；

(5) Applying protective glaze on the surface of the blank after the crystal dry particles are fixed, wherein the specific gravity of the protective glaze is 1.25g/cm³The glazing amount is 170g/m²；

(6) Drying the green body after the protective glaze is applied; the drying temperature is 100-150 ℃, and the moisture of the dried blank is controlled within 0.9 wt%;

(7) and (4) sintering, wherein the maximum sintering temperature is 1220 ℃, and the sintering period is 60-120 minutes.

(8) Edging and grading;

(9) and (6) packaging and warehousing.

The large crystal flowers are locally formed on the ceramic plate under the same firing conditions, but the crystal flowers only exist on the brick surface and are not blended into the green brick, so that the crystal flower decorative effect is not three-dimensional enough, and the decorative effect is poor.

Comparative example 3

Essentially the same as example 1, except that: the crystal glaze powder comprises the following raw materials: by mass percentage, 28.1 percent of glass powder, 2.6 percent of kaolin, 10.3 percent of calcite, 11.0 percent of titanium dioxide, 31.5 percent of zinc oxide, 11.5 percent of quartz and 5.0 percent of calcined talc.

Most of the brick surfaces of the comparative example have more needle-shaped crystal patterns with very small diameters (0.1-0.5 mm), and the local part has a plurality of crystal patterns with larger diameters which are continuously staggered, so as to form a fine brick surface with the texture similar to forged glaze. This is because the introduction of the burnt talc reduces the high-temperature viscosity of the glaze, and a large number of fine crystal patterns are separated out from the glaze surface, but the crystal patterns are connected with each other, and the crystal nucleus is too dense, so that the crystal patterns do not have a long condition.