阅读说明：本技术 一种耐磨数码陶瓷釉料 (Wear-resistant digital ceramic glaze ) 是由 黄大泱 叶建明 王礼 卢佩玉 于 2021-10-14 设计创作，主要内容包括：本发明涉及陶瓷生产领域,提供一种耐磨数码陶瓷釉料,用于提高陶瓷砖的耐磨性能。本发明提供的耐磨数码陶瓷釉料,包括：熔块50～60质量份,高岭土10～20质量份,硅酸锆10～15质量份,氧化锆1～3质量份,锆英石10～20质量份,硫酸钡1～3质量份。通过添加不同粒径的硅酸锆,并结合氧化锆,充分提高了釉料的耐磨性能。(The invention relates to the field of ceramic production, and provides a wear-resistant digital ceramic glaze for improving the wear resistance of ceramic tiles. The invention provides a wear-resistant digital ceramic glaze, which comprises the following components: 50-60 parts of clinker, 10-20 parts of kaolin, 10-15 parts of zirconium silicate, 1-3 parts of zirconium oxide, 10-20 parts of zirconite and 1-3 parts of barium sulfate. By adding zirconium silicate with different particle sizes and combining zirconium oxide, the wear resistance of the glaze is fully improved.)

1. A wear-resistant digital ceramic glaze is characterized by comprising: 50-60 parts of clinker, 10-20 parts of kaolin, 10-15 parts of zirconium silicate, 1-3 parts of zirconium oxide, 10-20 parts of zirconite and 1-3 parts of barium sulfate.

2. The abrasion-resistant digital ceramic glaze of claim 1 comprising: 55-60 parts of frit, 15-20 parts of kaolin, 12-15 parts of zirconium silicate, 2-3 parts of zirconium oxide, 13-20 parts of zirconite and 2-3 parts of barium sulfate.

3. The abrasion-resistant digital ceramic glaze of claim 1 comprising: 55 parts of clinker, 15 parts of kaolin, 12 parts of zirconium silicate, 2 parts of zirconia, 13 parts of zirconite and 2 parts of barium sulfate.

4. The abrasion-resistant digital ceramic glaze of claim 2 wherein the crystal size of the zirconium silicate is sub-micron.

5. The abrasion-resistant digital ceramic glaze material as set forth in claim 1, wherein the preparation method of zirconium silicate comprises:

taking 30-40 parts by mass of zirconium oxychloride, 15-25 parts by mass of tetraethoxysilane and 0.1-0.5 part by mass of lithium fluoride;

mixing zirconium oxychloride with 3-5 times of deionized water, uniformly stirring, adding lithium fluoride, and uniformly stirring to obtain a first mixed solution;

mixing tetraethoxysilane with deionized water in an amount which is 3-5 times that of tetraethoxysilane, uniformly stirring, and adjusting the pH value to be alkaline to obtain a second mixed solution;

and mixing the first mixed solution and the second mixed solution, adjusting the pH value to 9-11, stirring for 2-12 h to obtain a precursor, uniformly mixing the precursor with 0.8-1 times of deionized water, and drying to obtain the zirconium silicate.

6. The wear-resistant digital ceramic glaze material as claimed in claim 5, wherein the glaze material comprises 38-40 parts by mass of zirconium oxychloride, 20-25 parts by mass of tetraethoxysilane and 0.2-0.5 part by mass of lithium fluoride.

7. The abrasion-resistant digital ceramic glaze material as claimed in claim 1, wherein the glaze material comprises 38 parts by mass of zirconium oxychloride, 20 parts by mass of tetraethoxysilane and 0.2 part by mass of lithium fluoride.

8. The abrasion-resistant digital ceramic glaze of claim 1 wherein the frit is KT 1411.

9. The abrasion-resistant digital ceramic glaze material as claimed in claim 1, wherein the preparation method of the abrasion-resistant digital ceramic glaze material comprises:

uniformly mixing the frit, kaolin, zirconium silicate, zirconium oxide, zirconite and barium sulfate, adding water, ball-milling for 8-10 h, and drying to obtain the wear-resistant ceramic glaze.

10. The abrasion-resistant digital ceramic glaze material as claimed in claim 1, wherein the preparation method of the abrasion-resistant digital ceramic glaze material comprises:

uniformly mixing zirconite and barium sulfate, firing at high temperature, and water quenching to obtain intermediate powder;

and uniformly mixing the intermediate powder with the frit, kaolin, zirconium silicate and zirconia, adding water, ball-milling for 8-10 hours, and drying to obtain the wear-resistant ceramic glaze.

Technical Field

The invention relates to the field of ceramic production, in particular to a wear-resistant digital ceramic glaze.

Background

The ceramic brick is a plate-shaped or block-shaped ceramic product produced by clay and other inorganic non-metallic raw materials through processes of molding, sintering and the like, and is used for decorating and protecting walls and floors of buildings and structures. Usually formed by dry pressing, extrusion or other forming methods at room temperature, then dried and fired at a certain temperature.

The abrasive wear that occurs with a glaze is mainly of the following form: the abrasive particles such as silt or dust move between the glaze and the surface of another friction pair (such as a sole, a furniture bottom and the like), and the abrasion on the glaze is called three-body abrasive particle abrasion. Generally, under the abrasion state, the abrasive particles and the glaze surface have larger contact stress, and the compressive stress causes brittle fracture or peeling of the surface of the glaze layer; the glaze and the other friction pair are abraded due to abrasion under the condition that no abrasive particles are arranged between the contact surfaces, the friction pair is equivalent to the active abrasive particles on the contact surfaces, and the abrasion is low-stress abrasive particle abrasion; the abrasion caused by the relative movement of abrasive particles on the surface of the glaze layer is called two-body abrasion, and the movement direction of the two-body abrasion can be decomposed into two directions of being parallel to and perpendicular to the glaze surface. The friction of the parallel glaze surface can scratch micro furrowing traces on the surface of the glaze layer; the friction of the vertical glaze may impact pits on the glaze, causing the material to fall off the glaze. It is clear that the three-part abrasive wear pattern is the most common form of glaze wear.

The glazed brick prepared from the glaze with low wear resistance is easy to grind, and after long-time use, the glazed brick can be worn to a greater or lesser extent by different degrees, the glossiness is reduced obviously, and the surface is dull.

At present, by introducing superfine corundum micropowder into glaze, the hardness of the glaze is correspondingly improved after the content of alumina in the glaze is increased, the wear resistance of the glaze can be improved to a certain extent, but the effect still needs to be further improved.

Disclosure of Invention

The invention solves the technical problem of improving the wear-resisting property of ceramic tiles and provides a wear-resisting digital ceramic glaze.

In order to solve the technical problems, the technical scheme provided by the invention is as follows:

wear-resisting digital ceramic glaze includes: 50-60 parts of clinker, 10-20 parts of kaolin, 10-15 parts of zirconium silicate, 1-3 parts of zirconium oxide, 10-20 parts of zirconite and 1-3 parts of barium sulfate.

The main component of the zircon is zirconium silicate, and the zirconium silicate with different grain diameters can be embedded into a glass melt in the firing process, so that the wear resistance of the glaze layer is fully improved.

By adding zirconium silicate with different particle sizes and combining zirconium oxide, the wear resistance of the glaze is fully improved.

Preferably, the method comprises the following steps: 55-60 parts of frit, 15-20 parts of kaolin, 12-15 parts of zirconium silicate, 2-3 parts of zirconium oxide, 13-20 parts of zirconite and 2-3 parts of barium sulfate.

Preferably, the method comprises the following steps: 55 parts of clinker, 15 parts of kaolin, 12 parts of zirconium silicate, 2 parts of zirconia, 13 parts of zirconite and 2 parts of barium sulfate.

Preferably, the crystal size of the zirconium silicate is 500-600 nm.

Preferably, the preparation method of the zirconium silicate comprises the following steps:

taking 30-40 parts by mass of zirconium oxychloride, 15-25 parts by mass of tetraethoxysilane and 0.1-0.5 part by mass of lithium fluoride;

mixing zirconium oxychloride with 3-5 times of deionized water, uniformly stirring, adding lithium fluoride, and uniformly stirring to obtain a first mixed solution;

mixing tetraethoxysilane with deionized water in an amount which is 3-5 times that of tetraethoxysilane, uniformly stirring, and adjusting the pH value to be alkaline to obtain a second mixed solution;

and mixing the first mixed solution and the second mixed solution, adjusting the pH value to 9-11, stirring for 2-12 h to obtain a precursor, uniformly mixing the precursor with 0.8-1 times of deionized water, and drying to obtain the zirconium silicate.

Preferably, 38-40 parts by mass of zirconium oxychloride, 20-25 parts by mass of tetraethoxysilane and 0.2-0.5 part by mass of lithium fluoride.

Preferably, 38 parts by mass of zirconium oxychloride, 20 parts by mass of tetraethoxysilane and 0.2 part by mass of lithium fluoride.

Preferably, the frit is KT 1411.

Preferably, the preparation method of the wear-resistant digital ceramic glaze comprises the following steps:

uniformly mixing the frit, kaolin, zirconium silicate, zirconium oxide, zirconite and barium sulfate, adding water, ball-milling for 8-10 h, and drying to obtain the wear-resistant ceramic glaze.

Preferably, the preparation method of the wear-resistant digital ceramic glaze comprises the following steps:

uniformly mixing zirconite and barium sulfate, firing at high temperature, and water quenching to obtain intermediate powder;

and uniformly mixing the intermediate powder with the frit, kaolin, zirconium silicate and zirconia, adding water, ball-milling for 8-10 hours, and drying to obtain the wear-resistant ceramic glaze.

Compared with the prior art, the invention has the beneficial effects that: by adding zirconium silicate with different particle sizes and combining zirconium oxide, the wear resistance of the glaze is fully improved. The hard crystal is introduced into the glaze, can improve the strength, hardness and fracture toughness of the glaze layer, and can play a role in resisting grinding by covering the glaze layer. Meanwhile, the zirconia and the zirconium silicate coexist in the glaze layer, so that the wear-resisting effect is effectively improved.

Detailed Description

The following examples are further illustrative of the present invention and are not intended to be limiting thereof.

Example 1

Wear-resisting digital ceramic glaze includes: 550g of clinker, 150g of kaolin, 120g of zirconium silicate, 20g of zirconium oxide, 130g of zirconite and 20g of barium sulfate.

The preparation method of the zirconium silicate comprises the following steps:

taking 380g of zirconium oxychloride, 200g of tetraethoxysilane and 2g of lithium fluoride;

mixing zirconium oxychloride with 2000g of deionized water, uniformly stirring, adding lithium fluoride, and uniformly stirring to obtain a first mixed solution;

mixing tetraethoxysilane with 1000g of deionized water, uniformly stirring, and adjusting the pH value to be alkaline to obtain a second mixed solution;

and mixing the first mixed solution and the second mixed solution, adjusting the pH to 9, stirring for 10h to obtain a precursor, uniformly mixing the precursor with 3500g of deionized water, heating to 200 ℃, reacting for 24h, and drying to obtain the zirconium silicate. The frit is KT 1411. The preparation method of the wear-resistant digital ceramic glaze comprises the following steps:

uniformly mixing the frit, kaolin, zirconium silicate, zirconium oxide, zirconite and barium sulfate, adding water, ball-milling for 9 hours, and drying to obtain the wear-resistant ceramic glaze.

The main component of the zircon is zirconium silicate, and the zirconium silicate with different grain diameters can be embedded into a glass melt in the firing process, so that the wear resistance of the glaze layer is fully improved.

By adding zirconium silicate with different particle sizes and combining zirconium oxide, the wear resistance of the glaze is fully improved.

Example 2

Wear-resisting digital ceramic glaze includes: 550g of clinker, 150g of kaolin, 120g of zirconium silicate, 20g of zirconium oxide, 130g of zirconite and 20g of barium sulfate.

The preparation method of the zirconium silicate comprises the following steps:

taking 380g of zirconium oxychloride, 200g of tetraethoxysilane and 2g of lithium fluoride;

mixing zirconium oxychloride with 2000g of deionized water, uniformly stirring, adding lithium fluoride, and uniformly stirring to obtain a first mixed solution;

mixing tetraethoxysilane with 1000g of deionized water, uniformly stirring, and adjusting the pH value to be alkaline to obtain a second mixed solution;

and mixing the first mixed solution and the second mixed solution, adjusting the pH to 9, stirring for 10h to obtain a precursor, uniformly mixing the precursor with 3500g of deionized water, heating to 200 ℃, reacting for 24h, and drying to obtain the zirconium silicate. The frit is KT 1411.

The preparation method of the wear-resistant digital ceramic glaze comprises the following steps:

uniformly mixing zirconite and barium sulfate, firing at high temperature, quenching with water, and crushing to obtain intermediate powder;

and uniformly mixing the intermediate powder with the frit, kaolin, zirconium silicate and zirconia, adding water, ball-milling for 9 hours, and drying to obtain the wear-resistant ceramic glaze.

Example 3

Wear-resisting digital ceramic glaze includes: 550g of clinker, 150g of kaolin, 120g of zirconium silicate, 20g of zirconium oxide, 130g of zirconite and 20g of barium sulfate.

The preparation method of the zirconium silicate comprises the following steps:

taking 150g of zirconite, ball-milling and drying to obtain powder containing zirconium silicate. The frit is KT 1411. The preparation method of the wear-resistant digital ceramic glaze comprises the following steps:

uniformly mixing the frit, kaolin, zirconium silicate, zirconium oxide, zirconite and barium sulfate, adding water, ball-milling for 9 hours, and drying to obtain the wear-resistant ceramic glaze.

Comparative example 1

Wear-resisting digital ceramic glaze includes: 550g of frit, 150g of kaolin, 120g of zirconium silicate and 20g of zirconium oxide.

The preparation method of the zirconium silicate comprises the following steps:

taking 380g of zirconium oxychloride, 200g of tetraethoxysilane and 2g of lithium fluoride;

mixing zirconium oxychloride with 2000g of deionized water, uniformly stirring, adding lithium fluoride, and uniformly stirring to obtain a first mixed solution;

mixing tetraethoxysilane with 1000g of deionized water, uniformly stirring, and adjusting the pH value to be alkaline to obtain a second mixed solution;

and mixing the first mixed solution and the second mixed solution, adjusting the pH to 9, stirring for 10h to obtain a precursor, uniformly mixing the precursor with 3500g of deionized water, heating to 200 ℃, reacting for 24h, and drying to obtain the zirconium silicate. The frit is KT 1411. The preparation method of the wear-resistant digital ceramic glaze comprises the following steps:

uniformly mixing the frit, kaolin, zirconium silicate and zirconia, adding water, ball-milling for 9 hours, and drying to obtain the wear-resistant ceramic glaze.

Comparative example 2

Wear-resisting digital ceramic glaze includes: 550g of frit, 170g of kaolin, 120g of zirconium silicate, 130g of zirconite and 20g of barium sulfate.

The preparation method of the zirconium silicate comprises the following steps:

taking 380g of zirconium oxychloride, 200g of tetraethoxysilane and 2g of lithium fluoride;

mixing zirconium oxychloride with 2000g of deionized water, uniformly stirring, adding lithium fluoride, and uniformly stirring to obtain a first mixed solution;

mixing tetraethoxysilane with 1000g of deionized water, uniformly stirring, and adjusting the pH value to be alkaline to obtain a second mixed solution;

and mixing the first mixed solution and the second mixed solution, adjusting the pH to 9, stirring for 10h to obtain a precursor, uniformly mixing the precursor with 3500g of deionized water, heating to 200 ℃, reacting for 24h, and drying to obtain the zirconium silicate. The frit is KT 1411. The preparation method of the wear-resistant digital ceramic glaze comprises the following steps:

uniformly mixing the frit, kaolin, zirconium silicate, zirconite and barium sulfate, adding water, ball-milling for 9 hours, and drying to obtain the wear-resistant ceramic glaze.

Comparative example 3

Wear-resisting digital ceramic glaze includes: 550g of frit, 150g of kaolin, 120g of zirconium silicate, 20g of zirconium oxide, 130g of zirconite, 20g of barium sulfate, 25g of kaolin, 5g of calcined talc, 2g of quartz, 3g of fluorite and 3g of barium sulfate. The frit is KT 1411.

The preparation method of the wear-resistant digital ceramic glaze comprises the following steps:

25g of kaolin, 5g of calcined talc, 2g of quartz, 3g of fluorite and 3g of barium sulfate are uniformly mixed and crushed, and the temperature is raised to 300 ℃ from the normal temperature for 60 min; heating from 300 deg.C to 1100 deg.C for 60 min; heating from 1100 deg.C to 1400 deg.C for 35 min; heating from 1400 deg.C to 1520 deg.C for 5 min; cooling from 1520 deg.C to 1400 deg.C for 10 min; keeping the temperature at 1400 ℃ for 20 min; cooling from 1400 deg.C to 900 deg.C, and taking 40 min; obtaining intermediate powder after water quenching.

Uniformly mixing the frit, kaolin, zirconium silicate, zirconite, zirconium oxide, barium sulfate and intermediate powder, adding water, ball-milling for 9 hours, and drying to obtain the wear-resistant ceramic glaze.

Comparative example 4

Wear-resisting digital ceramic glaze includes: 550g of frit, 150g of kaolin, 120g of zirconium silicate, 20g of zirconium oxide, 130g of zirconite, 20g of barium sulfate, 25g of kaolin, 5g of calcined talc, 2g of quartz, 3g of fluorite and 3g of barium sulfate. The frit is KT 1411.

The preparation method of the wear-resistant digital ceramic glaze comprises the following steps:

uniformly mixing 25g of kaolin, 5g of calcined talc, 2g of quartz, 3g of fluorite and 3g of barium sulfate, crushing, heating to 300 ℃ from normal temperature, and taking for 60 min; heating from 300 deg.C to 1100 deg.C for 60 min; heating from 1100 deg.C to 1400 deg.C for 35 min; heating from 1400 deg.C to 1520 deg.C for 5 min; cooling from 1520 deg.C to 1400 deg.C for 10 min; keeping the temperature at 1400 ℃ for 20 min; cooling from 1400 deg.C to 900 deg.C, and taking 40 min; obtaining intermediate powder after water quenching.

Uniformly mixing 130g of zirconite and 20g of barium sulfate, heating to 300 ℃ from normal temperature, and taking for 60 min; heating from 300 deg.C to 1100 deg.C for 60 min; heating from 1100 deg.C to 1400 deg.C for 35 min; heating from 1400 deg.C to 1520 deg.C for 5 min; cooling from 1520 deg.C to 1400 deg.C for 10 min; keeping the temperature at 1400 ℃ for 20 min; cooling from 1400 deg.C to 900 deg.C, and taking 40 min; and water quenching to obtain mixed powder.

Uniformly mixing the frit, kaolin, zirconium silicate, zirconium oxide, intermediate powder and mixed powder, adding water, ball-milling for 9 hours, and drying to obtain the wear-resistant ceramic glaze.

Examples of the experiments

The glaze fired glazed tiles of the above examples and comparative examples were tested with reference to the glazed tile surface abrasion method (ISO 10545-7: 1996 Determination of resistance to surface abrasion for glazed tiles). The abrasive material used was steel balls of the grade specified in ISO10545-7 and 20ml of deionized water plus 3.0g of 80 mesh corundum or 3.0g of 80 mesh quartz sand. The samples prepared by the embodiments are cleaned before and after the wear resistance test, dried to constant weight and then recorded with the weight. The wear results for each embodiment were determined from the weighing results before and after the test.

TABLE 1 abrasion results for the various embodiments

As can be seen from Table 1, the wear resistance of examples 1 and 2 is better, the size of the zirconium silicate powder prepared by the hydrothermal method can reach below 300nm, and the zirconium silicate powder can be used with zirconium oxide to effectively improve the wear resistance.

In example 3, zirconium silicate was obtained by milling zircon, and the size thereof was reduced to the micron level, but not further reduced, and the wear resistance thereof was not sufficiently improved.

In comparative example 1, no zircon or barium sulfate was used, and additional zircon or barium sulfate was added to provide viscosity to the melt during firing, while facilitating partial zircon insertion into the glass melt. The comparative example 2 does not adopt the zirconium oxide, the wear-resisting effect is further reduced, and the zirconium oxide and the zirconium silicate can generate a certain synergistic effect to form the zirconium silicate wear-resisting glaze with part of the zirconium oxide coexisting.

In comparative examples 3 and 4, a new mixed powder is added to form cordierite crystals, but the mixed powder has a poor effect of being used in combination with other components, and the wear resistance of the glaze cannot be further improved.

The above detailed description is specific to possible embodiments of the present invention, and the above embodiments are not intended to limit the scope of the present invention, and all equivalent implementations or modifications that do not depart from the scope of the present invention should be included in the present claims.