阅读说明：本技术 一种金属干粒釉料、金属光泽瓷砖及其制备方法 (Metal dry particle glaze, metal luster ceramic tile and preparation method thereof ) 是由 钟华龙 梁泳 于 2020-08-05 设计创作，主要内容包括：本发明公开了一种金属干粒釉料、金属光泽瓷砖及其制备方法；所述金属干粒釉料包括金属干粒以及悬浮剂；所述金属干粒包括SiO<Sub>2</Sub>、Al<Sub>2</Sub>O<Sub>3</Sub>、CaO、MgO、K<Sub>2</Sub>O、Na<Sub>2</Sub>O、B<Sub>2</Sub>O<Sub>3</Sub>、Cr<Sub>2</Sub>O<Sub>3</Sub>、NiO、CoO、Fe<Sub>2</Sub>O<Sub>3</Sub>、CuO、SnO<Sub>2</Sub>、MnO；所述金属干粒釉料通过对基础釉料以及其它组分的协同优化,无需使用含铅这一种对人体、环境有危害的金属元素即可使釉料的稳定性好,耐腐蚀性能佳,抛光后的瓷砖砖面在光照下具有强烈的金属光泽,而且硬度达到6级、耐磨2100转以上；所述瓷砖的制备方法简单,一次烧成,有利于砖坯、面釉层、金属干粒釉层的同时成熟,有利于中间层的形成,提高瓷砖的刚性。(The invention discloses a metal dry particle glaze, a metal luster ceramic tile and a preparation method thereof; the metal dry particle glaze comprises metal dry particles and a suspending agent; the metal dry particles comprise SiO 2 、Al 2 O 3 、CaO、MgO、K 2 O、Na 2 O、B 2 O 3 、Cr 2 O 3 、NiO、CoO、Fe 2 O 3 、CuO、SnO 2 MnO; the metal dry particle glaze material has good stability and corrosion resistance through the cooperative optimization of the basic glaze material and other components without using a metal element containing lead which is harmful to human bodies and the environment, and the polished surface of the ceramic tile has strong metal luster under illumination, the hardness reaches 6 grades and the wear resistance is more than 2100 turns; the preparation method of the ceramic tile is simple, the ceramic tile is fired once, the simultaneous maturation of a green brick, a surface glaze layer and a metal dry grain glaze layer is facilitated, and the intermediate layer is facilitatedThe rigidity of the ceramic tile is improved.)

1. The metal dry particle glaze is characterized by comprising metal dry particles and a suspending agent; the metal dry particles comprise the following components in parts by weight: 30 to 33 parts of SiO₂9 to 11 parts of Al₂O₃0.5 to 2 parts of CaO, 0.2 to 0.8 part of MgO, and 0.5 to 2 parts of K₂O、1-2.5 parts of Na₂O, 2-3.5 parts of B₂O₃0 to 0.05 parts of Cr₂O₃2-5 parts of NiO, 0-0.05 part of CoO and 0.1-0.5 part of Fe₂O₃32 to 36 parts of CuO and 3.5 to 5.5 parts of SnO₂0 to 0.05 parts of MnO.

2. The dry metal particle glaze of claim 1, wherein the particle size of said CuO is 150-200 mesh; the particle size of the NiO is 80-100 meshes.

3. The dry metal particle glaze according to claim 2, wherein the particle size of said CuO is 150, 170, 200 mesh; wherein the weight ratio of 150 meshes to 170 meshes to 200 meshes is 2: 0.5-1.5: 1.

4. The dry metal particle glaze of claim 1, wherein the suspending agent is one of methyl glycol, sodium carboxymethyl cellulose, and polymethylsiloxane; the weight ratio of the metal dry particles to the suspending agent is 1: 2-3.

5. The dry metal particle glaze of claim 5, wherein the specific gravity of said dry metal particle glaze is 1.15-1.22g/cm³(ii) a The flow rate was 35-50 s.

6. The utility model provides a metallic luster ceramic tile which characterized in that, from last to down in proper order: a brick layer, a surface glaze layer, a printing layer and a metal dry grain glaze layer; the metal dry-grain glaze layer is formed by firing the metal dry-grain glaze material as set forth in any one of claims 1 to 5; the firing temperature is 1250-1300 ℃, and the firing period is 60-70 min.

7. A process for producing a metallic lustrous tile, characterized by using a metallic dry-grain glaze according to any one of claims 1 to 5; the preparation method of the metal luster ceramic tile comprises the following steps:

s1, preparing a metal dry particle glaze: weighing the raw materials according to the weight ratio, ball-milling the raw materials into slurry by a wet method, and sieving and ageing the slurry to obtain the metal dry particle glaze;

s2, distributing and applying a cover glaze on the dried and sprayed green brick to obtain a cover glaze layer;

s3, printing on the brick surface in the step S2 to obtain a printed layer;

s4, distributing metal dry grain glaze on the brick surface of the step S3 to obtain a metal dry grain glaze layer;

and S5, firing and polishing to obtain the metallic luster ceramic tile.

8. The method for producing a metallic lustrous tile according to claim 7, wherein the metallic dry glaze is applied in step S3 by bell jar glaze pouring; the glaze spraying amount is 94-140g/m²。

9. The method for preparing a metallic lustrous tile according to claim 7, wherein the overglaze of step S2 includes the following components in parts by weight: 47-50 parts of SiO₂8 to 11 parts of Al₂O₃8 to 11 parts of CaO, 3.5 to 4 parts of MgO, and 3.5 to 4 parts of K₂O, 1.0-1.5 parts of Na₂O, 8-11 parts of BaO, 7-10 parts of ZnO and 1-2 parts of SrO.

10. The method for manufacturing a metallic lustrous tile according to claim 9, c h a r a c t e r i z e d in that the specific gravity of the overglaze is 1.85-1.90g/cm³(ii) a The overglaze is distributed and applied by adopting a bell jar glaze pouring mode, and the glaze pouring amount is 375-one 435g/m²。

Technical Field

The invention relates to the technical field of glaze, ceramic tiles and preparation methods thereof, in particular to a metal dry particle glaze, a metal glossy ceramic tile and a preparation method thereof.

Background

The metal dry particle glaze is a special artistic glaze in ceramic industry glaze, and is mainly applied to archaized bricks, and also applied to porcelain pots, vases or artistic porcelain. The surface of the ceramic tile added with the metal dry particle glaze material can show metallic luster and various colors, and the metal dry particle glaze material can not only produce metallic elegant and gorgeous appearance effect, but also enhance the chemical stability of the ceramic tile glaze surface and the tolerance to acid and alkali.

In recent years, because of the elegant and heavy gas quality of the metal dry particle glaze, the ceramic industry and consumers are favored, in order to obtain a glaze effect with good luster, lead-containing fritted glaze needs to be used, but lead belongs to one of three heavy metal pollutants and is a heavy metal element harmful to human health and environment, and therefore, the products are gradually eliminated.

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 a lead-free metal dry particle glaze, a metal glossy ceramic tile and a preparation method thereof, and aims to solve the problems.

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

a metal dry particle glaze comprises metal dry particles and a suspending agent; the metal dry particles comprise the following components in parts by weight: 30 to 33 parts of SiO₂9 to 11 parts of Al₂O₃0.5 to 2 parts of CaO, 0.2 to 0.8 part of MgO, and 0.5 to 2 parts of K₂O, 1-2.5 parts of Na₂O, 2-3.5 parts of B₂O₃0 to 0.05 parts of Cr₂O₃2-5 parts of NiO, 0-0.05 part of CoO and 0.1-0.5 part of Fe₂O₃32 to 36 parts of CuO and 3.5 to 5.5 parts of SnO₂0 to 0.05 parts of MnO.

In the metal dry particle glaze, the particle size of the CuO is 150-200 meshes; the particle size of the NiO is 80-100 meshes.

In the metal dry particle glaze, the particle sizes of the CuO are respectively 150 meshes, 170 meshes and 200 meshes; wherein the weight ratio of 150 meshes to 170 meshes to 200 meshes is 2: 0.5-1.5: 1.

In the metal dry particle glaze, the suspending agent is one of methyl glycol, sodium carboxymethyl cellulose and polymethylsiloxane; the weight ratio of the metal dry particles to the suspending agent is 1: 2-3.

In the metal dry particle glaze, the specific gravity of the metal dry particle glaze is 1.15-1.22g/cm³(ii) a The flow rate was 35-50 s.

The utility model provides a metallic luster ceramic tile, is from last to down in proper order: a brick layer, a surface glaze layer, a printing layer and a metal dry grain glaze layer; the metal dry grain glaze layer is formed by firing the metal dry grain glaze; the firing temperature is 1250-1300 ℃, and the firing period is 60-70 min.

A preparation method of a ceramic tile with metal luster adopts the metal dry particle glaze; the preparation method of the metal luster ceramic tile comprises the following steps:

s1, preparing a metal dry particle glaze: weighing the raw materials according to the weight ratio, ball-milling the raw materials into slurry by a wet method, and sieving and ageing the slurry to obtain the metal dry particle glaze;

s2, distributing and applying a cover glaze on the dried and sprayed green brick to obtain a cover glaze layer;

s3, printing on the brick surface in the step S2 to obtain a printed layer;

s4, distributing metal dry grain glaze on the brick surface of the step S3 to obtain a metal dry grain glaze layer;

and S5, firing and polishing to obtain the metallic luster ceramic tile.

In the metallic luster ceramic tile, the metallic dry-particle glaze is distributed in the step S3 in a bell jar glaze spraying manner; the glaze spraying amount is 94-140g/m²。

In the metallic luster ceramic tile, the overglaze in the step S2 comprises the following components in parts by weight: 47-50 parts of SiO₂8 to 11 parts of Al₂O₃8 to 11 parts of CaO, 3.5 to 4 parts of MgO, and 3.5 to 4 parts of K₂O, 1.0-1.5 parts of Na₂O, 8-11 parts of BaO, 7-10 parts of ZnO and 1-2 parts of SrO.

In the metal luster ceramic tile, the specific gravity of the overglaze is 1.85-1.90g/cm³(ii) a The overglaze is distributed and applied by adopting a bell jar glaze pouring mode, and the glaze pouring amount is 375-one 435g/m²。

Has the advantages that:

the invention provides a metal dry grain glaze, a metal luster ceramic tile and a preparation method thereof, wherein the metal dry grain glaze is good in stability and corrosion resistance through the cooperative optimization of a basic glaze and other components without using a metal element containing lead which is harmful to human bodies and the environment, the polished surface of the ceramic tile has strong metal luster under illumination, the hardness reaches 6 grade, and the wear resistance is more than 2100 turns; the preparation method of the ceramic tile is simple, the ceramic tile is fired once, the simultaneous maturation of a green brick, a surface glaze layer and a metal dry grain glaze layer is facilitated, the formation of an intermediate layer is facilitated, and the rigidity of the ceramic tile is improved.

Drawings

Fig. 1 is a schematic structural view of a metallic luster ceramic tile provided by the invention.

Fig. 2 is a process flow chart of the metallic luster ceramic tile.

FIG. 3 is a schematic view of the metallic lustrous tile obtained in example 1 under no direct light.

Fig. 4 is a schematic view of the metallic luster ceramic tile obtained in example 1 under light.

Fig. 5 is a schematic view of the metallic luster ceramic tile obtained in example 2 under light.

Fig. 6 is a schematic view of the metallic luster ceramic tile obtained in example 3 under light.

Detailed Description

The invention provides a metal dry particle glaze, a metal luster ceramic tile and a preparation method 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 are not intended to limit the invention.

The invention provides a metal dry particle glaze, which comprises metal dry particles and a suspending agent; the metal dry particles comprise the following components in parts by weight: 30 to 33 parts of SiO₂9 to 11 parts of Al₂O₃0.5 to 2 parts of CaO, 0.2 to 0.8 part of MgO, and 0.5 to 2 parts of K₂O, 1-2.5 parts of Na₂O, 2-3.5 parts of B₂O₃、0～0.05Part of Cr₂O₃2-5 parts of NiO, 0-0.05 part of CoO and 0.1-0.5 part of Fe₂O₃32 to 36 parts of CuO and 3.5 to 5.5 parts of SnO₂0 to 0.05 parts of MnO.

SiO₂、Al₂O₃、CaO、MgO、K₂O、Na₂O is used as basic glaze, and Cr, Ni, Co, Fe, Cu and SnO are added into the basic glaze₂Mn, etc., transition metal oxides, usually coloured, Cr₂O₃Is light to dark green fine hexagonal crystal, NiO is green black cubic crystal, Fe₂O₃The CuO is amorphous powder from black to brown black, and is easily decomposed into yellow cuprous oxide at high temperature, and the MnO is cubic powder of grass green or gray green; the materials with the content reach saturation at high temperature, crystals are separated out, the fired metal dry particle glaze layer is yellow, and the polished metal dry particle glaze layer has metal luster texture and excellent decorative effect. B is₂O₃Can be combined with several metal oxides to form boron glass with characteristic color, and B is added₂O₃The miscibility with other components provides a metallic luster with richer colors. SnO₂The metal dry grain glaze layer has the characteristics of good permeability to visible light, stable chemical property, specific reflection of infrared radiation and the like, and has the advantages of improving the permeability of the metal dry grain glaze layer, facilitating the light to enter the metal dry grain glaze layer and enabling the refractive index of metal luster to be higher. The stability of the metal dry particle glaze is good and the corrosion resistance is good through the cooperative optimization of the basic glaze and other components; the polished glaze layer has strong metal luster, and forms contrast with the luster of the basic glaze layer, thereby improving the effect of matte metal luster. Furthermore, the components do not contain lead which is harmful to human bodies and the environment, so that the influence of the glaze added with lead on the human bodies, the environment and the like in the production process is avoided.

Further, the particle size of the CuO is 150-200 meshes; the particle size of the NiO is 80-100 meshes. The polishing solution has different metallic elements and different reflected luster colors of the polished metallic luster, and the CuO and NiO with different particle sizes are cooperatively matched to present different metallic luster colors and improve the decorative effect.

Further, the particle sizes of the CuO are respectively 150 meshes, 170 meshes and 200 meshes; wherein the weight ratio of 150 meshes to 170 meshes to 200 meshes is 2: 0.5-1.5: 1. CuO is a black oxide which is used as a main component of metallic luster, is black at normal temperature, is decomposed into yellow cuprous oxide at high temperature, and does not cause the CuO with small mesh number to have high content through the cooperative matching of different mesh numbers, so that the metallic luster under illumination is too dense; the CuO content with large mesh is not increased, so that the metallic luster under illumination is too sparse, and the visual effect of metallic luster flashing cannot be achieved.

Further, the suspending agent is one of methyl glycol, sodium carboxymethyl cellulose and polymethylsiloxane; the weight ratio of the metal dry particles to the suspending agent is 1: 2-3. The suspending agent is an organic matter suspending agent, can improve the suspending capacity of the metal dry particles, reduces the settling speed of the metal dry particles, ensures that the metal dry particle glaze has good fluidity and is easy to level, and avoids the phenomenon that the metal luster on the local part of the brick surface is stronger and weaker caused by the precipitation and agglomeration of components, so that the metal luster on the local part is not uniformly distributed on the brick surface. The ratio of the metal dry particles to the suspending agent

Further, the specific gravity of the metal dry particle glaze material is 1.15-1.22g/cm³(ii) a The flow rate was 35-50 s. The specific gravity of the metal dry particle glaze material has important influence on the glazing time and the thickness of the glaze layer. The glaze material has high specific gravity, a thicker glaze layer can be obtained in a short time, but the specific gravity of the glaze material is too high, namely the solid content in the metal dry particle glaze material is high, so that the metal luster is too strong easily to achieve the best visual effect by applying the glaze material, the thickness of the glaze layer is not uniform easily to influence the reflection and refraction of light, and further the integral visual effect is influenced; the glaze material has small specific gravity, and the glaze layer with certain thickness needs to be glazed for a plurality of times or glazed for a long time, thereby improving the production cost. The flow rate of the glaze is related to the viscosity, fluidity, etc. of the glaze; the flow rate is slow, namely the viscosity is high, the fluidity is poor, the effect of the glaze after leveling is poor, and the flatness of the brick surface is influenced; the flow velocity is fast, which affects the effect of metal dry particles on the brick surface and the glazing time, and is easy to cause the glaze layer and the surfaceThe glaze layers are layered, which affects the overall strength of the tile. The ranges of the specific gravity and the flow rate are most suitable, and the glaze is favorably applied.

Referring to fig. 1, a metallic luster ceramic tile sequentially includes, from top to bottom: a brick layer 1, a surface glaze layer 2, a printing layer 3 and a metal dry grain glaze layer 4; the metal dry grain glaze layer 4 is formed by firing the metal dry grain glaze; the firing temperature is 1250-1300 ℃, and the firing period is 60-70 min. The ceramic tile is easy to deform due to the excessively high firing temperature, the viscosity of glaze materials is increased, the exhaust is not facilitated, the phenomena of foaming, pinholes or glaze flowing are easy to occur on the glaze surface, and the quality, transparency, acid and alkali resistance, corrosion resistance, pollution resistance and the like of the glaze layer are influenced; the firing temperature is too low, the ceramic effect of the ceramic tile is incomplete, and the strength of the product is easily reduced; the melting point of the CuO is 1326 ℃, the firing temperature enables the CuO to be in a molten state, and the black CuO is decomposed into cuprous oxide at high temperature, so that the metal dry grain glaze layer 4 presents bright yellow; the above firing temperature ratio Cr₂O₃、Fe₂O₃、NiO、SnO₂Has a low melting point, does not burn and melt the metal having a metallic luster, and retains its own strong luster. Through the synergistic cooperation of the metal oxides, the brick surface presents colorful metallic luster.

Referring to fig. 2, a method for preparing a ceramic tile with metallic luster is characterized in that the metallic dry-particle glaze is adopted; the preparation method of the metal luster ceramic tile comprises the following steps:

(1) preparing a metal dry particle glaze material: weighing the raw materials according to the weight ratio, ball-milling the raw materials into slurry by a wet method, and sieving and ageing the slurry to obtain the metal dry particle glaze;

(2) spreading a cover glaze on the dried and sprayed green brick to obtain a cover glaze layer 2;

(3) printing on the overglaze layer to obtain a printed layer 3;

(4) applying a metal dry grain glaze material on the printing layer to obtain a metal dry grain glaze layer 4;

(5) firing and polishing to obtain the metallic luster ceramic tile.

Further, the green brick comprises the following components in parts by weight: 65E67 parts of SiO₂19 to 21 parts of Al₂O₃1.9-2.5 parts of Na₂O, 2.3-3.3 parts of K₂O, 0.6-1.2 parts of MgO, CaO less than or equal to 1 part, and Fe₂O₃、TiO₂The total parts are less than or equal to 1 part. The green bricks ensure the basic strength of the product; the expansion coefficient of the green brick is 210-220, so that the green brick cannot have large volume change in the drying and firing processes, the shrinkage probability of the green brick is reduced, and waste products are reduced.

Furthermore, the temperature of the green bricks at the tail of the drying kiln is 80-90 ℃ during the first drying, the moisture of the green bricks is volatilized, free water is removed, the strength of the green bricks is improved, and the cracking and brick frying are reduced; the temperature of the green brick before water spraying is 70-80 ℃, the temperature of the green brick is beneficial to opening capillary pores on the green brick surface, the infiltration speed and depth of the overglaze are improved, the integral patterns and textures of the green brick surface are clearer, the effect is richer, and the temperature of the green brick enables the capillary pores to absorb the glaze more uniformly and the overglaze layer to be smoother; the water spraying amount is 75-94g/m²The water spraying range can improve the binding capacity of the green brick and the overglaze, reduce the cracking probability, avoid excessive water spraying, prevent excessive water from permeating into capillary pores, improve the water content of the green brick, reduce the primary drying effect and improve the production cost.

Further, distributing the metal dry particle glaze material in a bell jar glaze spraying mode; the glaze spraying amount is 94-140g/m². (corresponding to a tile with the specification of 800X 800mm, the cloth application amount is 50-80 g); the temperature of the brick surface before the metal dry particle glaze is sprayed is 50-60 ℃, and the temperature of the brick surface is controlled to be in the range, so that the combination degree of the metal dry particle glaze and the surface glaze is favorably improved, and the probability of brick cracking is reduced; the metal dry glaze is distributed by adopting a bell jar glaze spraying mode, so that the metal dry glaze can be more uniformly leveled on the surface glaze layer, the flatness of the brick surface is improved, and the mirror surface effect is super-flat. When the specific gravity of the glaze material is constant, the glaze pouring amount influences the thickness of the glaze layer, the combination degree of the glaze layer and the overglaze layer, the formation of the intermediate crystal layer is influenced, the permeability of the glazed tile, the entering quantity of light, the refraction condition, the color development and the glossiness of the printing layer are further influenced, the glaze pouring amount is most suitable,the visual effect of the metallic luster is optimized.

Further, the overglaze comprises the following components in parts by weight: 47-50 parts of SiO₂8 to 11 parts of Al₂O₃8 to 11 parts of CaO, 3.5 to 4 parts of MgO, and 3.5 to 4 parts of K₂O, 1.0-1.5 parts of Na₂O, 8-11 parts of BaO, 7-10 parts of ZnO and 1-2 parts of SrO. The overglaze has high transparency and good binding capacity with green bricks, and the formed intermediate layer is thicker and has a smooth glaze surface, thereby providing a smooth and flat glaze surface for the subsequent application of metal dry-particle glaze materials.

Further, the specific gravity of the overglaze is 1.85-1.90g/cm³(ii) a The overglaze is distributed and applied by adopting a bell jar glaze pouring mode, and the glaze pouring amount is 375-one 435g/m²(corresponding to a tile with the specification of 400 x 400mm, the cloth application amount is 60-70 g); the performance is most suitable, a protective surface glaze layer with proper thickness, good viscosity and good fluidity is formed, and the integral visual effect of the ceramic tile is improved.