CN115124243A

CN115124243A - Overglaze for ceramic tiles, preparation method and ceramic tiles

Info

Publication number: CN115124243A
Application number: CN202210943022.6A
Authority: CN
Inventors: 庞远略; 巫汉生
Original assignee: Foshan Dianshi Glaze Technology Co ltd
Current assignee: Foshan Dianshi Glaze Technology Co ltd
Priority date: 2022-08-08
Filing date: 2022-08-08
Publication date: 2022-09-30
Anticipated expiration: 2042-08-08
Also published as: CN115124243B

Abstract

The invention provides a surface glaze for ceramic tiles, a preparation method thereof and the ceramic tiles, wherein the surface glaze for the ceramic tiles comprises silicon, aluminum, potassium, sodium, calcium, magnesium, barium and zinc, and is prepared by mixing raw materials and clinker, and the clinker is prepared by mixing calcined matte dry-grain glaze and soft dry-grain glaze. The overglaze for the ceramic tiles can enable the ceramic tiles to present special visual effects of distinct layering, full stereoscopic impression, clear texture and different degrees of concave-convex depth, and has fine glaze surface and strong antique texture.

Description

Overglaze for ceramic tiles, preparation method and ceramic tiles

Technical Field

The application relates to the field of glaze materials for ceramic tiles, in particular to overglaze for ceramic tiles, a preparation method of overglaze and ceramic tiles.

Background

In the current architectural ceramic market, glazed tiles are widely favored, have rich patterns, changeable colors, various styles, seepage prevention and convenient cleaning, and are applied to various occasions in daily life.

In the prior glazed tile, the antique tile needs to produce a special sinking level effect, the visual effect depends on the overglaze, but the prior overglaze has poor level and stereoscopic impression.

Disclosure of Invention

In view of the above, the invention provides a cover glaze for ceramic tiles, a preparation method and the ceramic tiles.

The technical scheme of the invention is as follows:

a surface glaze for ceramic tiles is prepared by mixing raw materials and clinker, wherein the clinker is prepared by mixing matte dry grain glaze and soft dry grain glaze;

the raw material comprises the following components in percentage by mass: 55 to 58 percent of silicon, 20 to 22 percent of aluminum, 0.8 to 2.2 percent of potassium, 0.8 to 2.2 percent of sodium, 2.5 to 5.0 percent of calcium, 0.15 to 0.60 percent of magnesium, 4.0 to 8.0 percent of barium and 0.5 to 2.0 percent of zinc;

the matte dry granular glaze comprises the following components in percentage by mass: 50-53% of silicon, 16-18% of aluminum, 3-5% of potassium, 1-3% of sodium, 5-8% of calcium, 0.2-0.5% of magnesium, 10-13% of barium and 4-7% of zinc;

the soft dry particle glaze comprises the following components in percentage by mass: 45 to 49 percent of silicon, 18 to 21 percent of aluminum, 0.5 to 1.5 percent of potassium, 0.1 to 0.4 percent of sodium, 14 to 16 percent of calcium, 0.3 to 1.0 percent of magnesium, 0.1 to 0.2 percent of barium and 13 to 15 percent of zinc.

Further, the glaze for ceramic tiles is characterized in that the raw material accounts for 70-85% by mass of the glaze for ceramic tiles, and the clinker accounts for 15-30% by mass of the glaze for ceramic tiles.

Further, the overglaze for the ceramic tiles is prepared from the matte dry-particle glaze and the soft dry-particle glaze in a mass ratio of 1:1-1: 2.

Further, the overglaze for ceramic tiles is characterized in that the silicon of the raw material, the matte dry grain glaze and the soft dry grain glaze is introduced by one or more of potassium feldspar, albite, washing kaolin, calcined kaolin, quartz powder, clinker powder and nepheline powder;

the aluminum of the raw material, the matte dry grain glaze and the soft dry grain glaze is introduced by one or more of potassium feldspar, albite, washing kaolin, calcined kaolin, aluminum oxide, fusion cake powder and nepheline powder;

the potassium of the raw material, the matt dry grain glaze and the soft dry grain glaze is introduced by one or more of the raw materials of potassium feldspar, fusion cake powder and nepheline powder;

the sodium of the raw material, the matte dry grain glaze and the soft dry grain glaze is introduced by one or more of potassium feldspar, sodium feldspar, fusion cake powder and nepheline powder;

calcium of the raw material, the matte dry grain glaze and the soft dry grain glaze is introduced by one or more of raw materials of calcite, dolomite, clinker powder and nepheline powder;

the magnesium of the raw material, the matte dry grain glaze and the soft dry grain glaze is introduced by one or more of raw materials of dolomite, clinker powder and nepheline powder;

the barium of the raw material, the matte dry particle glaze and the soft dry particle glaze is introduced by the raw material barium carbonate and/or the fusion cake powder;

the zinc of the raw material, the matte dry particle glaze and the soft dry particle glaze is introduced by the raw material zinc oxide and/or the fusion cake powder.

The invention also provides a preparation method of the overglaze for the ceramic tile, which comprises the following steps:

s1, weighing raw materials for introducing corresponding elements according to element proportions, and dividing the raw materials into raw materials, matte dry-particle glaze and soft dry-particle glaze;

s2, respectively calcining the matte dry-particle glaze and the soft dry-particle glaze to obtain the matte dry-particle glaze and the soft dry-particle glaze;

and S3, putting the raw material, the matte dry particle glaze and the soft dry particle glaze into a mixer to obtain the overglaze for the ceramic tile.

Further, the preparation method, wherein the calcination temperature of S2 is 1500-1600 ℃, and the calcination time is 24-25 hours.

Further, in the above preparation method, in the feeding process of S3, the raw material accounting for the largest mass percentage of the glaze for ceramic tiles is fed first, then the raw materials accounting for the third and the following mass percentages of the glaze for ceramic tiles are fed in no specific order, and finally the raw material accounting for the second largest mass percentage of the glaze for ceramic tiles is fed, and the mixer is set to 2800-.

The invention also provides a preparation method of the ceramic tile using the overglaze for the ceramic tile, which comprises the following steps:

A1. putting the ceramic tile overglaze into a ball mill, adding water, carboxymethyl cellulose and sodium tripolyphosphate for ball milling, and unloading the mixture into a container after the ball milling is finished to prepare glaze slurry;

A2. spraying base glaze on the ceramic blank after water spraying through a first glaze spraying cabinet;

A3. printing fine carving ink on the green body obtained in the step A2 through an ink jet printer;

A4. spraying glaze slip prepared from A1 on the green body obtained from A3 through a second glaze spraying cabinet;

A5. spraying protective glaze on the green body obtained in the step A4 through a third glaze spraying cabinet;

A6. feeding the green body obtained from A5 into a kiln for sintering;

A7. and (4) taking the ceramic tile obtained from the step A6 out of the kiln, and edging to obtain the ceramic tile.

Further, in the preparation method, in the step a1, the ball mill parameter is set to +325 mesh, and the mass percentages of the components in the mixture are as follows: 38-40% of water, 0.15-0.25% of carboxymethyl cellulose, 0.30-0.50% of sodium tripolyphosphate and the balance of cover glaze for ceramic tiles, wherein the ball milling is stopped when the screen allowance is less than or equal to 0.60%.

Further, in the preparation method, in the step A2, the bottom glaze is applied with a weight of 320-345 g per square meter and a specific gravity of 1.50 g/ml;

in the step A3, the ink jet quantity of the carved ink is 55 g/square meter;

in the step A4, the glazing weight of the glaze slip is 345g to 375g per square meter;

in the step A5, the weight of the protective glaze applied is 156-188 g per square meter, and the specific gravity is 1.30g per ml;

in the step A6, the sintering time is 80-120 minutes, and the sintering temperature is 1185-1205 ℃.

Further, the above preparation method, wherein between step a4 and step a5, further comprises a step of spraying coloring ink to the blank obtained in step a4 by an ink jet printer.

The invention has the following beneficial effects: the overglaze for the ceramic tiles can enable the ceramic tiles to present special visual effects of distinct layering, full stereoscopic impression, clear texture and different degrees of concave-convex depth, and has fine glaze surface and strong antique texture.

Drawings

The embodiments in the figures do not constitute any limitation of the invention, and other figures will be derived by a person skilled in the art without inventive effort from the following figures.

FIG. 1 is a colored ceramic tile fired using the formulation of example 1;

FIG. 2 is a plain color ceramic tile fired using the example 2 formulation;

FIG. 3 is a plain color ceramic tile fired using the example 3 formulation;

FIG. 4 is a colored ceramic tile fired with the formulation of comparative example 1.

Detailed Description

The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available raw materials and reagents used in the following examples unless otherwise specified, or can be prepared by known methods. The potassium feldspar and albite used in the following examples were purchased from jinying ceramics materials ltd, of foshan city; the washed kaolin and the calcined kaolin are purchased from Anju ceramic tile mining industry; quartz powder was purchased from Quandaxing New materials (Foshan) Inc.; nepheline powder is purchased from Sichuan Hongyi materials Co., Ltd; alumina was purchased from Jinxipeng trade, Inc., of Foshan; dolomite and calcite were purchased from yichunxuan new materials ltd; barium carbonate was purchased from wuhan Hao sky chemical Co., Ltd; zinc oxide was purchased from xinmeixing ceramics ltd, mountain fo. Experimental procedures without specific conditions noted in the following examples, molecular cloning is generally performed according to conventional conditions such as Sambrook et al: the conditions described in the Laboratory Manual (New York: Cold spring harbor Laboratory Press,1989), or according to the manufacturer's recommendations.

Example 1

(1) Preparing raw materials: weighing washed kaolin, potassium feldspar, albite, calcite, dolomite, barium carbonate, zinc oxide and clinker powder, and uniformly mixing to ensure that the raw material contains 56% of silicon, 21% of aluminum, 2.2% of potassium, 2.2% of sodium, 3% of calcium, 0.17% of magnesium, 7% of barium and 1.5% of zinc.

(2) Preparing matte dry granular glaze: weighing washed kaolin, potassium feldspar, albite, calcite, dolomite, barium carbonate and zinc oxide, uniformly mixing to ensure that the mixture contains 52% of silicon, 17% of aluminum, 5% of potassium, 3% of sodium, 6% of calcium, 0.3% of magnesium, 11% of barium and 5% of zinc, and calcining for 24.5 hours at 1550 ℃.

(3) Preparing soft dry grain glaze: the calcined kaolin, the quartz sand, the potassium feldspar, the albite, the calcite, the dolomite, the barium carbonate and the zinc oxide are weighed and evenly mixed, so that the mixture contains 46 percent of silicon, 21 percent of aluminum, 0.7 percent of potassium, 0.2 percent of sodium, 15 percent of calcium, 0.5 percent of magnesium, 0.15 percent of barium and 14 percent of zinc, and is calcined for 24.5 hours at 1550 ℃.

(4) Preparing a cover glaze: the raw material, matte dry granular glaze and soft dry granular glaze are put into a mixer, and the mixer is 3000 kg/groove and mixed for 35 minutes. The overglaze comprises 80% of raw materials, 20% of clinker and 1:1 of matte dry-grain glaze and soft dry-grain glaze. The feeding sequence is as follows: firstly, the raw material with the largest mass percentage is added, and then the matte dry-particle glaze and the soft dry-particle glaze are added in no specific sequence.

(5) Preparing glaze slip: putting 3000kg of overglaze into a ball mill, adding 2000kg of water, 10kg of carboxymethyl cellulose and 20kg of sodium tripolyphosphate, setting the parameters of the ball mill to be +325 meshes, starting ball milling, and discharging glaze slurry into a cylinder when the screen allowance is 0.50%. In the glaze slip, the mass percent of water is 40%, the mass percent of carboxymethyl cellulose is 0.2%, and the mass percent of sodium tripolyphosphate is 0.4%.

(6) Glazing: water is sprayed on the ceramic tile blank; spraying base coat through a first glaze spraying cabinet after water spraying, wherein the glazing weight is 330 g/square meter and the specific gravity is 1.50 g/ml; after spraying the ground glaze, spraying the carved ink by an ink-jet machine, drawing a pattern 1, wherein the ink-jet quantity is 55 g/square meter; spraying the finish carving ink, and then spraying ball milling to obtain glaze slip with the glazing weight of 360 g/square meter by using a second glaze spraying cabinet; spraying coloring ink through an ink jet machine after spraying the glaze slurry; spraying protective glaze through a third glaze spraying cabinet after spraying coloring ink, wherein the glazing weight is 170 g/square meter and the specific gravity is 1.30 g/ml.

(7) Firing: and (4) sending the ceramic tile blank subjected to glaze spraying into a kiln, and firing for 90 minutes at 1200 ℃.

(8) Preparing a ceramic tile: and discharging the fired ceramic tile out of the furnace, and edging to obtain a finished product.

Example 2

(1) Preparing raw materials: weighing water-washed kaolin, potassium feldspar, albite, calcite, dolomite, barium carbonate, zinc oxide, nepheline powder and clinker powder, and uniformly mixing to ensure that the raw material contains 55% of silicon, 20% of aluminum, 1% of potassium, 1% of sodium, 5% of calcium, 0.60% of magnesium, 8% of barium and 2% of zinc.

(2) Preparing matte dry granular glaze: weighing alumina, potassium feldspar, albite, calcite, dolomite, barium carbonate and zinc oxide, uniformly mixing to ensure that the mixture contains 50% of silicon, 16% of aluminum, 4% of potassium, 2% of sodium, 8% of calcium, 0.5% of magnesium, 13% of barium and 7% of zinc, and calcining for 25 hours at 1600 ℃.

(3) Preparing soft dry grain glaze: weighing water-washed kaolin, potassium feldspar, albite, calcite, dolomite, barium carbonate and zinc oxide, uniformly mixing to ensure that the mixture contains 45% of silicon, 18% of aluminum, 1.5% of potassium, 0.4% of sodium, 16% of calcium, 1.0% of magnesium, 0.2% of barium and 15% of zinc, and calcining for 25 hours at 1600 ℃.

(4) Preparing overglaze: the raw material, the matte dry granular glaze and the soft dry granular glaze are put into a mixer with the mixing speed of 3100 kg/groove and mixed for 40 minutes. The overglaze accounts for 3000kg, wherein the raw material accounts for 70 percent, the clinker accounts for 30 percent, and the ratio of the matte dry-grain glaze to the soft dry-grain glaze is 1: 2. The feeding sequence is as follows: firstly adding the raw material with the largest mass percentage, then adding the matte dry particle glaze with the third mass percentage, and finally adding the soft dry particle glaze with the second mass percentage.

(5) Preparing glaze slip: putting 3000kg of overglaze into a ball mill, adding 1800kg of water, 7.2kg of carboxymethyl cellulose and 14.4kg of sodium tripolyphosphate, setting the parameters of the ball mill to be +325 meshes, starting ball milling, and discharging glaze slurry into a cylinder when the screen allowance is 0.60%. In the glaze slip, the mass percent of water is 38%, the mass percent of carboxymethyl cellulose is 0.15%, and the mass percent of sodium tripolyphosphate is 0.3%.

(6) Glazing: water is sprayed on the ceramic tile blank; spraying base glaze through a first glaze spraying cabinet after water spraying, wherein the glazing weight is 320 g/square meter and the specific gravity is 1.50 g/ml; after spraying the ground glaze, spraying the carved ink by an ink jet machine, and drawing a pattern 2, wherein the ink jet amount is 55 g/square meter; spraying refined carving ink, and then spraying and ball-milling by using a second glaze spraying cabinet to obtain glaze slip, wherein the glazing weight is 345g per square meter; and after the glaze slip is sprayed, the protective glaze is sprayed by a third glaze spraying cabinet, wherein the glazing weight is 156 g/square meter and the specific gravity is 1.30 g/ml.

(7) Firing: and (4) feeding the ceramic tile blank subjected to glaze spraying into a kiln, and firing at 1185 ℃ for 80 minutes.

(8) Preparing ceramic tiles: and discharging the fired ceramic tile out of the furnace, and edging to obtain a finished product.

Example 3

(1) Preparing raw materials: weighing water-washed kaolin, potassium feldspar, albite, calcite, dolomite, barium carbonate, zinc oxide, nepheline powder and clinker powder, and mixing uniformly. The raw material contains 58% of silicon, 22% of aluminum, 0.8% of potassium, 0.8% of sodium, 2.5% of calcium, 0.15% of magnesium, 4.0% of barium and 0.5% of zinc.

(2) Preparing matte dry granular glaze: weighing water-washed kaolin, potassium feldspar, albite, calcite, dolomite, barium carbonate, zinc oxide and nepheline powder, uniformly mixing to ensure that the mixture contains 53 percent of silicon, 18 percent of aluminum, 3 percent of potassium, 1 percent of sodium, 5 percent of calcium, 0.2 percent of magnesium, 10 percent of barium and 4 percent of zinc, and calcining for 24 hours at 1500 ℃.

(3) Preparing soft dry grain glaze: weighing water-washed kaolin, potassium feldspar, albite, calcite, dolomite, barium carbonate, zinc oxide and clinker powder, uniformly mixing to ensure that the mixture contains 49 percent of silicon, 21 percent of aluminum, 0.5 percent of potassium, 0.1 percent of sodium, 14 percent of calcium, 0.3 percent of magnesium, 0.1 percent of barium and 13 percent of zinc, and calcining for 24 hours at 1500 ℃.

(4) Preparing a cover glaze: the raw material, the matte dry particle glaze and the soft dry particle glaze are put into a mixer, and the mixer is 3100 kg/groove and mixed for 30 minutes. The overglaze accounts for 3000kg in total, wherein the raw material accounts for 85 percent, the clinker accounts for 15 percent, and the ratio of the matte dry grain glaze to the soft dry grain glaze is 1: 1.5. The feeding sequence is as follows: firstly adding the raw material with the largest mass percentage, then adding the matte dry particle glaze with the third mass percentage, and finally adding the soft dry particle glaze with the second mass percentage.

(5) Preparing glaze slip: putting 3000kg of overglaze into a ball mill, adding 1900kg of water, 12.25kg of carboxymethyl cellulose and 24.5kg of sodium tripolyphosphate, setting the parameters of the ball mill to be +325 meshes, starting ball milling, and discharging glaze slurry into a cylinder when the screen allowance is 0.60%. In the glaze slip, the mass percent of water is 39%, the mass percent of carboxymethyl cellulose is 0.25%, and the mass percent of sodium tripolyphosphate is 0.5%.

(6) Glazing: water is sprayed on the ceramic tile blank; spraying base coat through a first glaze spraying cabinet after water spraying, wherein the glazing weight is 345 g/square meter and the specific gravity is 1.50 g/ml; after spraying the ground glaze, spraying the carved ink by an ink-jet machine, drawing patterns 3, wherein the ink-jet quantity is 55 g/square meter; spraying the carved ink, and then spraying and ball-milling by a second glaze spraying cabinet to obtain glaze slip, wherein the glazing weight is 375g per square meter; after the glaze slip is sprayed, protective glaze is sprayed by a third glaze spraying cabinet, the glazing weight is 188 g/square meter, and the specific gravity is 1.30 g/ml.

(7) Firing: and (4) feeding the ceramic tile blank subjected to glaze spraying into a kiln, and firing for 120 minutes at 1205 ℃.

Comparative example 1

(2) Preparing matte dry granular glaze: weighing and uniformly mixing the water-washed kaolin, the potassium feldspar, the albite, the calcite, the dolomite, the barium carbonate and the zinc oxide. The matte dry granular glaze is not calcined, and contains 52% of silicon, 17% of aluminum, 5% of potassium, 3% of sodium, 6% of calcium, 0.3% of magnesium, 11% of barium and 5% of zinc.

(3) Preparing soft dry grain glaze: weighing calcined kaolin, quartz sand, potassium feldspar, albite, calcite, dolomite, barium carbonate and zinc oxide, and uniformly mixing. The soft dry grain glaze is not calcined, and contains 46% of silicon, 21% of aluminum, 0.7% of potassium, 0.2% of sodium, 15% of calcium, 0.5% of magnesium, 0.15% of barium and 14% of zinc.

(4) Preparing a cover glaze: the raw material, matte dry granular glaze and soft dry granular glaze are put into a mixer, and the mixer is 3000 kg/groove and mixed for 35 minutes. The overglaze accounts for 3000kg in total, wherein the raw material accounts for 80 percent, the clinker accounts for 20 percent, and the ratio of the matte dry grain glaze to the soft dry grain glaze is 1:1. The feeding sequence is as follows: firstly adding the raw material with the largest mass percentage, and then adding the matte dry-particle glaze and the soft dry-particle glaze in no specific sequence.

(6) Glazing: water is sprayed on the ceramic tile blank; spraying base coat through a first glaze spraying cabinet after water spraying, wherein the glazing weight is 330 g/square meter and the specific gravity is 1.50 g/ml; after spraying the ground glaze, spraying the carved ink by an ink jet machine, and drawing the pattern 4, wherein the ink jet amount is 55 g/square meter; spraying the refined carving ink, and then spraying and ball-milling by using a second glaze spraying cabinet to obtain glaze slip, wherein the glazing weight is 360g per square meter; spraying coloring ink through an ink jet machine after spraying the glaze slurry; spraying protective glaze through a third glaze spraying cabinet after spraying coloring ink, wherein the glazing weight is 170 g/square meter and the specific gravity is 1.30 g/ml.

Comparative example 2

(3) Preparing a cover glaze: the raw materials and the matte dry granular glaze are put into a mixer, and the mixer is 3000 kg/groove and mixed for 35 minutes. The overglaze accounts for 3000kg, wherein the raw material accounts for 80 percent, the clinker accounts for 20 percent, and the clinker is all matte dry granular glaze. The feeding sequence is as follows: firstly, raw materials are added, and then the matte dry granular glaze is added.

(4) Preparing glaze slip: putting 3000kg of overglaze into a ball mill, adding 2000kg of water, 10kg of carboxymethyl cellulose and 20kg of sodium tripolyphosphate, setting the parameters of the ball mill to be +325 meshes, starting ball milling, and discharging glaze slurry into a cylinder when the screen allowance is 0.50%. In the glaze slip, the mass percent of water is 40%, the mass percent of carboxymethyl cellulose is 0.2%, and the mass percent of sodium tripolyphosphate is 0.4%.

(5) Glazing: water is sprayed on the ceramic tile blank; spraying base coat through a first glaze spraying cabinet after water spraying, wherein the glazing weight is 330 g/square meter and the specific gravity is 1.50 g/ml; spraying finishing carving ink through an ink jet printer after spraying the bottom glaze, and drawing the pattern 1, wherein the ink jet quantity is 55 g/square meter; spraying the refined carving ink, and then spraying and ball-milling by using a second glaze spraying cabinet to obtain glaze slip, wherein the glazing weight is 360g per square meter; and after the glaze slip is sprayed, protective glaze is sprayed by a third glaze spraying cabinet, the glazing weight is 170 g/square meter, and the specific gravity is 1.30 g/ml.

(6) And (3) firing: and (4) feeding the ceramic tile blank subjected to glaze spraying into a kiln, and firing for 90 minutes at 1200 ℃.

(7) Preparing a ceramic tile: and discharging the fired ceramic tile out of the furnace, and edging to obtain a finished product.

Comparative example 3

(2) Preparing soft dry grain glaze: the calcined kaolin, the quartz sand, the potassium feldspar, the albite, the calcite, the dolomite, the barium carbonate and the zinc oxide are weighed and uniformly mixed, so that the mixture contains 46% of silicon, 21% of aluminum, 0.7% of potassium, 0.2% of sodium, 15% of calcium, 0.5% of magnesium, 0.15% of barium and 14% of zinc, and is calcined for 24.5 hours at 1550 ℃.

(3) Preparing overglaze: the raw material and the soft dry grain glaze were put into a mixer at 3000 kg/tank and mixed for 35 minutes. The overglaze accounts for 3000kg, wherein the raw material accounts for 80%, the clinker accounts for 20%, and the clinker is soft dry grain glaze. The feeding sequence is as follows: firstly, the raw material is added, and then the soft dry grain glaze is added.

(5) Glazing: water is sprayed on the ceramic tile blank; spraying base coat through a first glaze spraying cabinet after water spraying, wherein the glazing weight is 330 g/square meter and the specific gravity is 1.50 g/ml; after spraying the ground glaze, spraying the carved ink by an ink-jet machine, drawing a pattern 1, wherein the ink-jet quantity is 55 g/square meter; spraying the refined carving ink, and then spraying and ball-milling by using a second glaze spraying cabinet to obtain glaze slip, wherein the glazing weight is 360g per square meter; and after the glaze slip is sprayed, the protective glaze is sprayed by a third glaze spraying cabinet, wherein the glazing weight is 170 g/square meter and the specific gravity is 1.30 g/ml.

(6) Firing: and (4) sending the ceramic tile blank subjected to glaze spraying into a kiln, and firing for 90 minutes at 1200 ℃.

Comparative example 4

(2) Preparing matte dry granular glaze: weighing water-washed kaolin, potassium feldspar, albite, calcite, dolomite, barium carbonate and zinc oxide, uniformly mixing to ensure that the mixture contains 52% of silicon, 17% of aluminum, 5% of potassium, 3% of sodium, 6% of calcium, 0.3% of magnesium, 11% of barium and 5% of zinc, and calcining for 24.5 hours at 1550 ℃.

(3) Preparing soft dry granular glaze: the calcined kaolin, the quartz sand, the potassium feldspar, the albite, the calcite, the dolomite, the barium carbonate and the zinc oxide are weighed and evenly mixed, so that the mixture contains 46 percent of silicon, 21 percent of aluminum, 0.7 percent of potassium, 0.2 percent of sodium, 15 percent of calcium, 0.5 percent of magnesium, 0.15 percent of barium and 14 percent of zinc, and is calcined for 24.5 hours at 1550 ℃.

(4) Preparing overglaze: the raw material, matte dry granular glaze and soft dry granular glaze are put into a mixer, and the mixer is 3000 kg/groove and mixed for 35 minutes. The overglaze accounts for 3000kg, wherein the raw material accounts for 60%, the clinker accounts for 40%, and the ratio of the matte dry-grain glaze to the soft dry-grain glaze is 1:1. The feeding sequence is as follows: firstly, the raw material with the largest mass percentage is added, and then the matte dry-particle glaze and the soft dry-particle glaze are added in no specific sequence.

(6) Glazing: water is sprayed on the ceramic tile blank; spraying base coat through a first glaze spraying cabinet after water spraying, wherein the glazing weight is 330 g/square meter and the specific gravity is 1.50 g/ml; after spraying the ground glaze, spraying the carved ink by an ink-jet machine, drawing a pattern 1, wherein the ink-jet quantity is 55 g/square meter; spraying the finish carving ink, and then spraying ball milling to obtain glaze slip with the glazing weight of 360 g/square meter by using a second glaze spraying cabinet; and after the glaze slip is sprayed, protective glaze is sprayed by a third glaze spraying cabinet, the glazing weight is 170 g/square meter, and the specific gravity is 1.30 g/ml.

Comparative example 5

(4) Preparing a cover glaze: the raw material, matte dry granular glaze and soft dry granular glaze are put into a mixer, and the mixer is 3000 kg/groove and mixed for 35 minutes. The overglaze accounts for 3000kg in total, wherein the raw material accounts for 90 percent, the clinker accounts for 10 percent, and the ratio of the matte dry grain glaze to the soft dry grain glaze is 1:1. The feeding sequence is as follows: firstly adding the raw material with the largest mass percentage, and then adding the matte dry-particle glaze and the soft dry-particle glaze in no specific sequence.

(6) Glazing: water is sprayed on the ceramic tile blank; spraying base coat through a first glaze spraying cabinet after water spraying, wherein the glazing weight is 330 g/square meter and the specific gravity is 1.50 g/ml; after spraying the ground glaze, spraying the carved ink by an ink-jet machine, drawing a pattern 1, wherein the ink-jet quantity is 55 g/square meter; spraying the refined carving ink, and then spraying and ball-milling by using a second glaze spraying cabinet to obtain glaze slip, wherein the glazing weight is 360g per square meter; and after the glaze slip is sprayed, protective glaze is sprayed by a third glaze spraying cabinet, the glazing weight is 170 g/square meter, and the specific gravity is 1.30 g/ml.

(7) And (3) firing: and (4) feeding the ceramic tile blank subjected to glaze spraying into a kiln, and firing for 90 minutes at 1200 ℃.

Comparative example 6

(4) Preparing a cover glaze: the raw material, the matte dry particle glaze and the soft dry particle glaze are put into a mixer, and the mixer is 3000 kg/groove and mixed for 35 minutes. The overglaze accounts for 3000kg in total, wherein the raw material accounts for 80 percent, the clinker accounts for 20 percent, and the ratio of the matte dry grain glaze to the soft dry grain glaze is 2: 1. The feeding sequence is as follows: firstly adding the raw material with the largest mass percentage, then adding the soft dry granular glaze with the third mass percentage, and finally adding the matte dry granular glaze with the second mass percentage.

Comparative example 7

(4) Preparing a cover glaze: the raw material, the matte dry particle glaze and the soft dry particle glaze are put into a mixer, and the mixer is 3000 kg/groove and mixed for 35 minutes. The overglaze accounts for 3000kg, wherein the raw material accounts for 80%, the clinker accounts for 20%, and the ratio of the matte dry-grain glaze to the soft dry-grain glaze is 1: 3. The feeding sequence is as follows: firstly adding the raw material with the largest mass percentage, then adding the matte dry particle glaze with the third mass percentage, and finally adding the soft dry particle glaze with the second mass percentage.

Performance testing

(1) Appearance of the product

The ceramic tiles fired in examples 1 to 3 and comparative example 1 were left standing on a horizontal surface at room temperature, and the glazed state was visually observed. And simultaneously testing the glossiness of the ceramic tile fired by each sample and the standard overglaze through a glossiness tester, and calculating the difference value between the sample and the standard ceramic tile.

TABLE 1 gloss of tiles obtained by different preparation processes

Numbering	Preparation process	Degree of gloss
			A	Standard overglaze	0
B	Example 1	0
			C	Example 2	+1
D	Example 3	-1
			E	Comparative example 1	-3
F	Comparative example 2	-2
			G	Comparative example 3	+3
H	Comparative example 4	+3
			I	Comparative example 5	+2
J	Comparative example 6	-2
			K	Comparative example 7	-2

As shown in FIGS. 1-4, the ceramic tiles fired in examples 1-3 have similar gloss, with a gloss difference of + -1 from that of the ceramic tiles fired with the standard overglaze, meeting quality standards; the difference between the glossiness of the ceramic tiles fired in each proportion and the glossiness of the ceramic tiles fired with the standard overglaze is 2-3. When the fired ceramic tiles of examples 1 to 3 and comparative example 1 were visually observed, the ceramic tiles of examples 1 to 3 had a vivid pattern and a strong uneven feeling. The above results show that whether clinker is calcined or not, the raw clinker ratio and the matte dry grain glaze/soft dry grain glaze ratio all affect the glossiness and concave-convex feeling of the prepared ceramic tile.

(2) Screen allowance

Accurately weighing 100g (accurate to 0.01g) of overglaze prepared in each example and each comparative example, drying, putting the dried overglaze (the weight of the overglaze is recorded as m) into a standard sieve, putting the standard sieve into a clean water basin with the water depth larger than the sieve height, slightly shaking, and slowly washing with clean water when the residue in the sieve is less until the washing water is clear and transparent.

Keeping the temperature of the sieved materials in an oven at 200 ℃ for 40min, taking out, cooling and weighing m 1. The rest of the sieve is m1/m 100%

TABLE 2 overglaze screen allowance obtained by different preparation processes

Preparation process	Screen allowance (%)
		Example 1	5.58
Example 2	7.62
		Example 3	6.73
Comparative example 1	13.54
		Comparative example 2	8.98
Comparative example 3	9.29
		Comparative example 4	8.55
Comparative example 5	9.41
		Comparative example 6	8.23
Comparative example 7	9.07

The granularity of the reaction overglaze powder on the screen residue can reduce the ball milling efficiency when the screen residue is too coarse, and increase the ball milling time and cost. The screen residue of the examples 1 to 3 is less than 8 percent, the screen residue of the comparative examples 2 to 7 is 8 to 10 percent, and the screen residue of the comparative example 1 is more than 10 percent. The results of the above screen residue tests show that the overglaze powder of examples 1-3 is finer, the ball milling efficiency is high, and the prepared glaze slip is finer.

(3) Iron chip content

200g of sample to be measured is accurately weighed in a clean large plastic basin, and about two thirds of the basin is added with water. Stirring the slurry with a magnetic bar for 2min, and taking out. The magnetic material on the surface of the magnetic rod was gently rinsed with water and transferred to a dry filter paper weighed m. After repeating the operation for 4-5 times, the filter paper is kept at the constant temperature of 80 ℃ for 120min, and then the filter paper is taken out and weighed to be m 1. Iron filings m1-m/100 x 100%.

TABLE 3 iron content of overglaze obtained by different preparation processes

Preparation process	Iron chip content (%)
		Example 1	0.012
Example 2	0.010
		Example 3	0.011
Comparative example 1	0.029
		Comparative example 2	0.031
Comparative example 3	0.028
		Comparative example 4	0.027
Comparative example 5	0.033
		Comparative example 6	0.025
Comparative example 7	0.032

The iron chip content is related to the whiteness of the ceramic tile glaze, and the excessive value of the iron chip content can cause deviation of the whiteness of the ceramic tile glaze. The iron chip contents of examples 1 to 3 and comparative examples 1 to 7 were less than 0.040%. The test results show that the components of each embodiment and each comparative example can effectively control the content of scrap iron and ensure the whiteness of the glaze; within the allowable range, the iron chip content of each embodiment is lower than the comparative proportion, and the whiteness of the glaze surface is better.

(4) Flow rate of flow

The glaze slip and the standard glaze slip prepared in each example and each comparative example are taken, evenly stirred and poured into a clean flow cup until the glaze slip is level with the upper edge of the flow cup. And starting timing when a switch at the lower end of the flow velocity cup is opened, finishing timing when the outlet of the cup bottom is just seen, and recording the time Tn, wherein the flow velocity T is the sample glaze slurry time Tn-the standard glaze slurry time T0.

TABLE 4 glaze slip flow rates obtained by different preparation processes

Preparation process	Flow rate(s)
		Standard glaze slip	0
Example 1	-1
		Example 2	+2
Example 3	-2
		Comparative example 1	+3
Comparative example 2	+1
		Comparative example 3	-1
Comparative example 4	+3
		Comparative example 5	-2
Comparative example 6	+2
		Comparative example 7	+1

The fluidity of the glaze slip influences the glaze spraying effect, and the contrast difference value with the standard is required to be not more than 5 seconds. The difference of the flow rates of the glaze slips obtained in examples 1-3 and comparative examples 1-7 is less than 5 seconds. The above results show that the glaze slip prepared in each example and comparative example meets the requirement of glaze spraying and can achieve better glaze spraying effect.

Although embodiments of the present application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present application, and that changes, modifications, substitutions and alterations in the above embodiments may be made by those of ordinary skill in the art within the scope of the present application.

Claims

1. The overglaze for ceramic tiles is formed by mixing raw materials and clinker, wherein the clinker is formed by mixing matte dry grain glaze and soft dry grain glaze, and is characterized in that:

the raw material comprises the following components in percentage by mass: 55 to 58 percent of silicon, 20 to 22 percent of aluminum, 0.8 to 2.2 percent of potassium, 0.8 to 2.2 percent of sodium, 2.5 to 5.0 percent of calcium, 0.15 to 0.60 percent of magnesium, 4.0 to 8.0 percent of barium and 0.5 to 2.0 percent of zinc; the matte dry granular glaze comprises the following components in percentage by mass: 50-53% of silicon, 16-18% of aluminum, 3-5% of potassium, 1-3% of sodium, 5-8% of calcium, 0.2-0.5% of magnesium, 10-13% of barium and 4-7% of zinc;

2. The overglaze for ceramic tiles according to claim 1, wherein the mass percentage of the raw materials in the overglaze for ceramic tiles is 70-85%, and the mass percentage of the clinker in the overglaze for ceramic tiles is 15-30%.

3. The overglaze for ceramic tiles as claimed in claim 1, wherein the mass ratio of the matte dry-grain glaze to the soft dry-grain glaze is 1:1-1: 2.

4. The overglaze for ceramic tiles according to claim 1, wherein the silicon of the raw material, the matte dry-grain glaze and the soft dry-grain glaze is introduced from one or more of the raw materials potassium feldspar, sodium feldspar, water-washed kaolin, calcined kaolin, quartz powder, clinker powder, nepheline powder;

the aluminum of the raw material, the matte dry particle glaze and the soft dry particle glaze is introduced by one or more of potassium feldspar, albite, washing kaolin, calcined kaolin, aluminum oxide, clinker powder and nepheline powder; the potassium of the raw material, the matte dry particle glaze and the soft dry particle glaze is introduced by one or more of potassium feldspar, fusion cake powder and nepheline powder;

the sodium of the raw material, the matte dry grain glaze and the soft dry grain glaze is introduced by one or more of potassium feldspar, albite, clinker powder and nepheline powder;

the calcium of the raw material, the matte dry grain glaze and the soft dry grain glaze is introduced by one or more of raw materials of calcite, dolomite, clinker powder and nepheline powder;

the barium of the raw material, the matte dry particle glaze and the soft dry particle glaze is introduced by raw material barium carbonate and/or fusion cake powder;

5. A method of preparing a cover glaze for ceramic tiles as claimed in claim 1, comprising the steps of:

6. The method as claimed in claim 5, wherein the calcination temperature of S2 is 1500-1600 ℃, and the calcination time is 24-25 hours.

7. The preparation method according to claim 5, wherein in the feeding process of S3, the raw material with the largest mass percentage of the ceramic tile overglaze is firstly fed, then the raw materials with the third and the following mass percentages of the ceramic tile overglaze are fed without specific sequence, and finally the raw material with the second largest mass percentage of the ceramic tile overglaze is fed, and the mixer is set to be 2800-.

8. A method of making ceramic tiles using the overglaze for ceramic tiles of claim 1, comprising the steps of:

A3. printing fine carving ink on the blank obtained in the step A2 through an ink jet printer;

A6. feeding the green body obtained from A5 into a kiln for sintering;

9. The preparation method according to claim 8, wherein in the step A1, the parameters of the ball mill are set to +325 mesh, and the mass percentages of the components in the mixture are as follows: 38-40% of water, 0.15-0.25% of carboxymethyl cellulose, 0.30-0.50% of sodium tripolyphosphate and the balance of the ceramic tile overglaze, wherein the ball milling is stopped when the screen balance is less than or equal to 0.60%.

10. The preparation method according to claim 8, wherein in step A2, the bottom glaze has a weight of 320-345 g per square meter and a specific gravity of 1.50 g/ml;

in the step A3, the ink jet quantity of the refined carving ink is 55 g/square meter;

in the step A6, the sintering time is 80-120 minutes, and the sintering temperature is 1185-.

11. The method for preparing a ceramic tile according to claim 8, wherein between the step A4 and the step A5, the method further comprises a step of spraying coloring ink on the blank obtained in the step A4 through an ink jet printer.