阅读说明：本技术 一种具有立体宝石颗粒感釉面的陶瓷砖及其制备方法 (Ceramic tile with stereoscopic gem particle feeling glaze and preparation method thereof ) 是由 潘利敏 郑贵友 杨元东 王贤超 邓来福 于 2020-11-25 设计创作，主要内容包括：本发明公开一种具有立体宝石颗粒感釉面的陶瓷砖及其制备方法。所述制备方法包括以下步骤：在坯体表面施面釉并喷墨打印图案；在喷墨打印图案后的坯体表面施干粒釉；所述干粒釉以重量份数计,包括透明干粒釉粉45～65份和宝石边角料10～20份；最后烧成以形成具有立体宝石颗粒感釉面的陶瓷砖。本发明通过使用彩色宝石边角料来实现立体宝石颗粒感釉面效果,加入的彩色宝石边角料和透明釉的融合性较好,不会出现气孔等缺陷,而且在烧成过程能够稳定存在且不会发生颜色扩散,同时对窑炉的烧成工艺不会产生影响或者影响较小。(The invention discloses a ceramic tile with a glaze surface with three-dimensional gem particle sense and a preparation method thereof. The preparation method comprises the following steps: applying a cover glaze on the surface of the blank and carrying out ink-jet printing on a pattern; applying dry grain glaze on the surface of the blank after the pattern is printed by ink jet; the dry particle glaze comprises, by weight, 45-65 parts of transparent dry particle glaze powder and 10-20 parts of gem leftover materials; finally, the ceramic tile with the glaze surface with the stereoscopic gem particle sense is formed by sintering. The invention realizes the glaze effect of three-dimensional gem particle sense by using the color gem leftover material, the added color gem leftover material and the transparent glaze have better fusion property, the defects of air holes and the like can not occur, the color can stably exist in the firing process, the color diffusion can not occur, and the firing process of the kiln can not be influenced or has less influence.)

1. A preparation method of a ceramic tile with a stereoscopic gem particle feeling glaze surface is characterized by comprising the following steps:

applying a cover glaze on the surface of the blank and carrying out ink-jet printing on a pattern;

applying dry grain glaze on the surface of the blank after the pattern is printed by ink jet; the dry particle glaze comprises, by weight, 45-65 parts of transparent dry particle glaze powder and 10-20 parts of gem leftover materials;

finally, the ceramic tile with the glaze surface with the stereoscopic gem particle sense is formed by sintering.

2. The method according to claim 1, wherein the transparent dry glaze powder has a melting start temperature of 1100 to 1200 ℃; preferably, the chemical composition of the transparent dry particle glaze powder comprises: by mass percent, SiO₂：40～45%，Al₂O₃: 14 to 18%, alkaline earth metal oxide: 19 to 25%, alkali metal oxide: 4-8%.

3. The method according to claim 1 or 2, wherein the starting melting temperature of the gemstone scraps is 1200 to 1300 ℃; preferably, the gem leftover materials are sapphire and/or ruby; more preferably, the chemical composition of the gemstone scraps comprises: by mass percentage, Al₂O₃：95～99.9%，CrO₃：1～5%，Fe₂O₃：0.01～0.05%。

4. The preparation method according to any one of claims 1 to 3, wherein the dry particle glaze has a specific gravity of 1.6 to 1.9g/cm³The glazing amount is 1000-1200 g/m²。

5. The preparation method according to any one of claims 1 to 4, characterized in that the dry particle glaze is applied by spraying glaze.

6. The method according to any one of claims 1 to 5, wherein the particle size of the gemstone scraps is 60 to 100 meshes.

7. The production method according to any one of claims 1 to 6, wherein the maximum firing temperature is 1150 to 1210 ℃ and the firing period is 55 to 65 minutes.

8. The method according to any one of claims 1 to 7, wherein the overglaze has a specific gravity of 1.50 to 1.53g/cm³The glazing amount is 500-550 g/m²。

9. Ceramic tile with a stereoscopic gem particle feel glaze obtained by the method of production according to any one of claims 1 to 8.

Technical Field

The invention belongs to the field of architectural ceramics, and particularly relates to a ceramic tile with a stereoscopic gem particle feeling glaze surface and a preparation method thereof.

Background

Building ceramic tiles are widely used for home decoration as a decorative material with excellent performance. The ink-jet printing technology gives ceramic colors, however, the wide application of the ink-jet printing technology also leads to the increasingly serious homogenization of ceramic products, and personalized products are difficult to appear. In addition, the inkjet printed pattern decoration is a two-dimensional plane decoration. Granular crystal flowers are separated out from the glaze in a crystallization mode, and the ceramic tile with the three-dimensional glaze feeling can be prepared by matching with ink-jet printing patterns. However, the crystallization has high requirements on the temperature system of the kiln, and the expansion coefficients of different crystallization frits are different, so that the glaze surface cracks due to different expansion coefficients when different crystallization frits are mixed for use. It has also been reported that a mixture of colored frit and transparent frit is used to form a three-dimensional glaze effect, but the colored frit itself is added with a colorant to form a color dot on the basis of the transparent frit, so that the colorant in the colored frit diffuses at high temperature, which results in no granular effect, and even poor overall plate effect. Moreover, the traditional pigment is synthesized through a high-temperature solid-phase reaction, and the mixing of molecular levels is not realized in the synthesis process, so that the color is poor after the pigment is crushed and refined, and the coloring effect of colored particles is further limited.

Disclosure of Invention

Aiming at the problems brought forward by the background technology, the invention realizes the glaze effect of three-dimensional gem particle sense by using the color gem leftover material, the added color gem leftover material and the transparent glaze have better fusion performance, the defects of air holes and the like can not occur, the color can stably exist in the firing process, the color diffusion can not occur, and the firing process of the kiln can not be influenced or has less influence.

In a first aspect, the invention provides a method for preparing a ceramic tile with a glaze surface with a stereoscopic gem particle sense. The preparation method comprises the following steps:

applying a cover glaze on the surface of the blank and carrying out ink-jet printing on a pattern;

applying dry grain glaze on the surface of the blank after the pattern is printed by ink jet; the dry particle glaze comprises, by weight, 45-65 parts of transparent dry particle glaze powder and 10-20 parts of gem leftover materials;

finally, the ceramic tile with the glaze surface with the stereoscopic gem particle sense is formed by sintering.

Preferably, the specific gravity of the dry granular glaze is 1.6-1.9 g/cm³. The specific gravity of the gem leftover is larger, and is generally 4.0-4.1 g/cm³. In the dry grain glaze, the weight part of the gem leftover materials is not more than 20 parts, otherwise, the gem leftover materials and the dry grain glaze slip have larger specific gravity difference, which can cause the settlement of gem particles to cause the concave pits, the bubbles and the like on the glaze surface. The weight portion of the transparent dry grain glaze powder in the dry grain glaze is not less than 45, otherwise, the color difference and the color mark appear on the brick surface because the transparent dry grain glaze powder is too little.

Preferably, the melting temperature of the transparent dry particle glaze powder is 1100-1200 ℃.

Preferably, the chemical composition of the transparent dry particle glaze powder comprises: by mass percent, SiO₂：40～45％，Al₂O₃: 14 to 18%, alkaline earth metal oxide: 19 to 25%, alkali metal oxide: 4-8%.

Preferably, the melting starting temperature of the gem leftover materials is 1200-1300 ℃.

Preferably, the gemstone scraps are sapphire and/or ruby. More preferably, the chemical composition of the gemstone scraps comprises: by mass percentage, Al₂O₃：95～99.9％，CrO₃：1～5％，Fe₂O₃：0.01～0.05％。

The kinds of precious stones are many, such as pearls, emeralds, pearls, lapis, opals, etc. However, the chemical compositions of different kinds of gemstones are different, for example, the chemical composition of pearl includes calcium carbonate, magnesium carbonate, calcium phosphate, alumina, iron oxide and organic matter. However, the introduction of the chemical composition can affect the high-temperature performance and effect of the ceramic glaze. The invention adopts sapphire and ruby, has single and stable components, belongs to eight elements of ceramic raw materials, has stable structure, is not easy to react at high temperature, and can keep the decoration effect of the ceramic. Therefore, the components of the gem leftover materials are preferably high-temperature elements, the reaction cannot occur in the firing process, and the gem leftover materials cannot contain elements harmful to the glaze, such as boron, fluorine and the like, and the structure of the gem leftover materials is stable.

Preferably, the glazing amount of the dry granular glaze is 1000-1200 g/m². The low glazing amount of the dry particle glaze may cause poor fusion flatness of the gem particle material and the glaze material. Too high an amount of dry glaze particles will result in material waste and increased costs. In addition, the thickness of the glaze layer is too thick due to excessive application of dry granular glaze, bubbles are difficult to discharge at high temperature to generate bubbles, and more pores appear after polishing, so that the glaze effect is influenced.

Preferably, the glazing mode of the dry granular glaze is glaze pouring. The glaze spraying mode is not suitable for the technical scheme of the invention because the glaze spraying effect is not uniform due to the gravity of dry particle glaze, and the glaze spraying nozzle is easy to be blocked by the gem leftover materials to influence the brick surface effect, and the glaze spraying efficiency is low, so that the cost is increased. The above problems can be well avoided by adopting glaze pouring.

Preferably, the dry particle glaze further comprises 80-100 parts by weight of a dry particle suspending agent. The dry particle suspending agent is used for fixing dry particles, so that the glaze is prevented from being blown away by hot air of a kiln in the firing process due to poor dry particle glaze fluidity and adhesive force. In addition, the suspension property of the dry granular glaze can be increased, the occurrence of precipitation is reduced, and the glaze slip is more uniform.

The particle size of the gem leftover is preferably controlled to be 60-100 meshes. The particle size of the gemstone offcuts is tightly controlled. The gem leftover belongs to a high-temperature material, and the combination of the gem leftover and the glaze layer is not good due to too large grain diameter. Moreover, the gemstone scraps with large particle size can cause the agglomeration caused by insufficient dispersion of gemstone particles in the glazing process, resulting in uneven glazing, and consequently, glaze defects such as ripples. Too large a particle size will also exacerbate the settling of the gemstone particles. Moreover, when the brick surface is polished, the large particles of the polishing abrasive block easily bring out all or most of the gem leftover materials, and gem pits appear on the brick surface. The particle size of the gem leftover is too small, the decorative effect is not good enough, and a good stereoscopic gem particle feeling glaze surface cannot be generated.

Preferably, the maximum firing temperature is 1150-1210 ℃, and the firing period is 55-65 minutes.

Preferably, the specific gravity of the overglaze is 1.50-1.53 g/cm³The glazing amount is 500-550 g/m²。

In a second aspect, the invention also provides a ceramic tile with a stereoscopic glaze-like gem particle feeling, which is obtained by the preparation method.

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 preparation method of the ceramic tile with the glaze surface with the stereoscopic gem particle feeling is exemplified as follows.

And pressing and forming the blank by using the blank powder. The chemical composition of the green body powder is not limited, and the conventional green body powder can be adopted. For example, the chemical composition of the green body powder may include: by mass percent, SiO₂：60～65％、Al₂O₃：20～25％、K₂O：1～4％、Na₂O: 2-4%, loss on ignition: 1 to 5 percent.

And drying the green body. The drying time can be 1-1.5 h. Controlling the water content of the dried blank to be 0.1-0.5 wt%.

And applying surface glaze on the surface of the blank. The overglaze has the functions of covering the blank ground color flaws and enabling the color development effect of the ink-jet printed patterns to be better.

The chemical composition of the overglaze is not limited, and the overglaze composition conventional in the field can be adopted. The chemical composition of the overglaze may include: by mass percent, SiO₂：60～68％、Al₂O₃: 20-24%, alkaline earth metal oxide: 0 to 1%, alkali metal oxide: 4 to 9% of ZrO₂: 3.2-9.6%, loss on ignition: 1.3 to 1.7 percent. As an example, the chemical composition of the overglaze comprises: by mass percent, SiO₂：60～68％、Al₂O₃：20～24％、CaO：0.3～0.6％、MgO：0.1～0.3％、K₂O：1.5～2.5％、Na₂O：3～4％、ZrO₂: 3.2-9.6%, loss on ignition: 1.3 to 1.7 percent.

The glazing mode of the overglaze can be glaze spraying. The glazing process of the overglaze has little influence on the appearance of the effect of the gem particles. In some embodiments, the overglaze has a specific gravity of 1.50 to 1.53g/cm³The glazing amount is 500-550 g/m²。

And (4) carrying out ink-jet printing on the surface of the blank body after the overglaze is applied. And drying the blank after the pattern is printed by ink jet. The drying time may be 5 min.

And preparing dry grain glaze. The dry glaze particles may include transparent dry glaze powder, gemstone leftovers, and dry suspending agents. The "dry particle suspension" may also be referred to as "stamp-pad ink" or "glue". The stamp-pad ink has the function of enabling dry grain glaze to be better attached to the surface of the brick and reducing the defects of the glaze surface. Generally, the mass ratio of the total amount of the transparent dry-grain glaze powder and the gem leftover materials to the dry-grain suspending agent is preferably controlled to be 1: 1-1.5. In some embodiments, the dry particulate glaze may include: according to parts by weight, 45-65 parts of transparent dry grain glaze powder, 10-20 parts of gem leftover materials and 80-100 parts of dry grain suspending agents.

Preferably, the mass ratio of the transparent dry-grain glaze powder to the gem leftover material can be 2: 1-4.5: 1. the mass ratio is controlled in the range, so that the enough consumption of the gem leftover materials can be ensured to obtain excellent glaze decoration effect, and the defects of color difference, color marks and the like caused by lower consumption of the transparent dry grain glaze powder can be avoided. In some embodiments, the chemical composition of the transparent dry glaze powder may include: by mass percent, SiO₂：40～45％，Al₂O₃：14～18％，CaO：3.5～4.5％，MgO：2.5～4％，BaO：14.5～16％，ZnO：3～3.8％，K₂O：2.1～3.5％，Na₂O：2.5～3.5％。

The gem leftover material can be ruby or sapphire leftover material. The main component of ruby is alumina, which is red in color because the ruby is formed by doping the alumina lattice with chromium oxide due to geological motion. The main component of sapphire is also alumina, which appears blue because the alumina lattice is doped with titanium oxide. Sapphire and ruby are colored by doping with impurity ions into alumina crystal lattices, so that the color generation effect does not change with the change of the particle size. The natural sapphire leftover materials in the nature can exist stably at high temperature, color diffusion cannot occur, and the stereoscopic impression after sintering is strong. And the cost of the red sapphire leftover material is lower, the processing and the use are convenient, and the industrial production is easy to realize.

The particle size of the gem leftover material particles can be 60-100 meshes.

And drying the glaze particles on the surface of the blank after ink-jet printing. In some embodiments, the chemical composition of the dry particulate glaze may include: by mass percent, SiO₂：40～45％，Al₂O₃：14～18％，CaO：3.5～4.5％，MgO：2.5～4％，BaO：14.5～16％，ZnO：3～3.8％，K₂O：2.1～3.5％，Na₂O：2.5～3.5％。

The bell jar can be used for pouring glaze. In some embodiments, the dry particle glaze has a specific gravity of 1.6-1.9 g/cm³The glazing amount is 1000-1200 g/m². The thick shower is adopted to ensure that the gem leftover particles are more uniformly distributed in the glaze layer, the fired glaze layer is transparent, and the gem particle particles exist in the glaze layer in a particle form by the thick glaze layer, so that a more three-dimensional brick surface effect is obtained. Preferably, the specific gravity of the dry granular glaze is 1.8-1.89 g/cm³。

And drying after the glaze pouring is finished, and firing in a kiln. Controlling the highest firing temperature to 1150-1210 ℃, firing time to 55-65 min, and taking out of the kiln to obtain a finished product.

It will be appreciated that the effect of the invention may also be achieved by adding gem stone leftover particles to the frit to produce dry frit pellets. In particular, in order to realize the three-dimensional property of glaze layer pattern decoration, the process of glue dry particles can be used for positioning the gem particles, thereby achieving a new decoration effect.

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

(1) And pressing and molding the blank powder to form a blank.

(2) And drying the green body. The drying time is 1h, and the water content of the dried ceramic body is 0.3 wt%.

(3) And applying surface glaze on the surface of the dried blank. The overglaze comprises the following chemical components: by mass percent, SiO₂：64％、Al₂O₃：22％、CaO：0.45％、MgO：0.2％、K₂O：2.0％、Na₂O：3.5％、ZrO₂: 6.5%, loss on ignition: 1.5 percent. The specific gravity of the overglaze is 1.52g/cm³The glazing amount is 500g/m²。

(4) And (4) printing a pattern on the surface of the blank in an ink jet mode.

(5) And drying the blank body after the pattern is printed by ink jet for 3 min.

(6) And preparing dry grain glaze. The dry particle glaze comprises: 45 parts of transparent dry grain glaze powder, 20 parts of gem leftover materials and 80 parts of stamp-pad ink. The chemical composition of the transparent dry particle glaze powder comprises: by mass percent, SiO₂：42.5％，Al₂O₃：16％，CaO：4.0％，MgO：3.25％，BaO：15％，ZnO：3.5％，K₂O：3.0％，Na₂O: 2.8 percent. The chemical composition of the gem leftover material comprises: by mass percentage, Al₂O₃：98％，CrO₃：1.95％，Fe₂O₃: 0.05 percent. The particle size of the gem leftover is 100 meshes.

(7) And drying the grain glaze on the surface of the blank after the pattern is printed by ink jet. The specific gravity of the dry granular glaze is 1.8g/cm³The glazing amount is 1000g/m²。

(8) And drying the green body after the glaze particles are sprayed and dried, and firing. The highest firing temperature is 1150-1210 ℃, the firing time is 55-65 min, and the ceramic tile with the glaze surface with the stereoscopic gem particle sense is obtained after the ceramic tile is taken out of the kiln.

Example 2

(1) And pressing and molding the blank powder to form a blank.

(2) And drying the green body. The drying time is 1.5h, and the water content of the dried ceramic body is 0.1 wt%.

(3) And applying surface glaze on the surface of the dried blank. The overglaze comprises the following chemical components: by mass percent, SiO₂：60％、Al₂O₃：20％、CaO：0.3％、MgO：0.1％、K₂O：1.5％、Na₂O：3％、ZrO₂: 3.2%, loss on ignition: 1.3 percent. The specific gravity of the overglaze is 1.50g/cm³The glazing amount is 550g/m²。

(4) And (4) printing a pattern on the surface of the blank in an ink jet mode.

(5) And drying the blank body after the pattern is printed by ink jet for 3 min.

(6) And preparing dry grain glaze. The dry particle glaze comprises: 50 parts of transparent dry grain glaze powder, 16 parts of gem leftover materials and 85 parts of stamp-pad ink. The chemical composition of the transparent dry particle glaze powder comprises: by mass percent, SiO₂：45％，Al₂O₃：18％，CaO：4.5％，MgO：4％，BaO：16％，ZnO：3.8％，K₂O：3.5％，Na₂O: 3.5 percent. The chemical composition of the gem leftover material comprises: by mass percentage, Al₂O₃：98％，CrO₃：1.95％，Fe₂O₃: 0.05 percent. The particle size of the gem leftover is 100 meshes.

(7) And drying the grain glaze on the surface of the blank after the pattern is printed by ink jet. The specific gravity of the dry granular glaze is 1.6g/cm³The glazing amount is 1200g/m²。

(8) And drying the green body after the glaze particles are sprayed and dried, and firing. The highest firing temperature is 1150-1210 ℃, the firing time is 55-65 min, and the ceramic tile with the glaze surface with the stereoscopic gem particle sense is obtained after the ceramic tile is taken out of the kiln.

Example 3

(1) And pressing and molding the blank powder to form a blank.

(2) And drying the green body. The drying time is 1h, and the water content of the dried ceramic body is 0.3 wt%.

(3) And applying surface glaze on the surface of the dried blank. The overglaze comprises the following chemical components: by mass percent, SiO₂：68％、Al₂O₃：24％、CaO：0.6％、MgO：0.3％、K₂O：2.5％、Na₂O：4％、ZrO₂: 9.6%, loss on ignition: 1.7 percent. The specific gravity of the overglaze is 1.52g/cm³The glazing amount is 530g/m²。

(4) And (4) printing a pattern on the surface of the blank in an ink jet mode.

(5) And drying the blank body after the pattern is printed by ink jet for 3 min.

(6) And preparing dry grain glaze. The dry particle glaze comprises: 60 parts of transparent dry grain glaze powder, 15 parts of gem leftover materials and 90 parts of stamp-pad ink. The chemical composition of the transparent dry particle glaze powder can comprise: by mass percent, SiO₂：40％，Al₂O₃：14％，CaO：3.5％，MgO：.5％，BaO：14.5％，ZnO：3％，K₂O：2.1％，Na₂O: 2.5 percent. The chemical composition of the gem leftover material comprises: by mass percentage, Al₂O₃：98％，CrO₃：1.95％，Fe₂O₃: 0.05 percent. The particle size of the gem leftover is 100 meshes.

(7) And drying the grain glaze on the surface of the blank after the pattern is printed by ink jet. The specific gravity of the dry granular glaze is 1.89g/cm³The glazing amount is 1100g/m²。

(8) And drying the green body after the glaze particles are sprayed and dried, and firing. The highest firing temperature is 1150-1210 ℃, the firing time is 55-65 min, and the ceramic tile with the glaze surface with the stereoscopic gem particle sense is obtained after the ceramic tile is taken out of the kiln.