阅读说明：本技术 一种具有乳白色面釉的金属塘瓷釉料及其制备方法 (Metal enamel glaze with milky glaze and preparation method thereof ) 是由 陈一丕 陈一川 陈一寸 于 2021-10-13 设计创作，主要内容包括：本发明涉及陶瓷制备技术领域,具体为一种具有乳白色面釉的金属塘瓷釉料及其制备方法,所述釉料包括面釉和底釉,所述面釉包括以下按照重量份的材料：石英16-24份、钠长石22-28份、萤石12-18份、重晶石6-12份、方解石5-15份、石灰石15-20份、硼砂5-8份、纯碱6-10份、硝酸钠4-8份、氟硅酸钠2-6份、氧化钛4-10份、氧化钴2-5份、氧化镍4-8份、氧化铜2-4份、氧化铬3-8份、二氧化锆8-12份、刚玉颗粒12-15份、助熔剂16-18份、磨料10-20份；其中,所述磨料包括碳化硅和氮化硼。本发明制备的金属搪瓷釉料具有良好的机械性能,且能耐磨耐高温和耐腐蚀。(The invention relates to the technical field of ceramic preparation, in particular to a metal enamel glaze with milky overglaze and a preparation method thereof, wherein the glaze comprises overglaze and ground glaze, and the overglaze comprises the following materials in parts by weight: 16-24 parts of quartz, 22-28 parts of albite, 12-18 parts of fluorite, 6-12 parts of barite, 5-15 parts of calcite, 15-20 parts of limestone, 5-8 parts of borax, 6-10 parts of soda ash, 4-8 parts of sodium nitrate, 2-6 parts of sodium fluosilicate, 4-10 parts of titanium oxide, 2-5 parts of cobalt oxide, 4-8 parts of nickel oxide, 2-4 parts of copper oxide, 3-8 parts of chromium oxide, 8-12 parts of zirconium dioxide, 12-15 parts of corundum particles, 16-18 parts of fluxing agent and 10-20 parts of grinding material; wherein the abrasive comprises silicon carbide and boron nitride. The metal enamel glaze prepared by the invention has good mechanical properties, and can resist abrasion, high temperature and corrosion.)

1. The metal enamel glaze with the milky glaze comprises a glaze layer and a ground glaze, and is characterized in that the glaze layer comprises the following materials in parts by weight: 16-24 parts of quartz, 22-28 parts of albite, 12-18 parts of fluorite, 6-12 parts of barite, 5-15 parts of calcite, 15-20 parts of limestone, 5-8 parts of borax, 6-10 parts of soda ash, 4-8 parts of sodium nitrate, 2-6 parts of sodium fluosilicate, 4-10 parts of titanium oxide, 2-5 parts of cobalt oxide, 4-8 parts of nickel oxide, 2-4 parts of copper oxide, 3-8 parts of chromium oxide, 8-12 parts of zirconium dioxide, 12-15 parts of corundum particles, 16-18 parts of fluxing agent and 10-20 parts of grinding material; wherein the abrasive comprises silicon carbide and boron nitride.

2. The metal enamel glaze with milky glaze according to claim 1, wherein the glaze comprises the following materials in parts by weight: 18 parts of quartz, 26 parts of albite, 15 parts of fluorite, 10 parts of barite, 12 parts of calcite, 18 parts of limestone, 6 parts of borax, 8 parts of soda ash, 6 parts of sodium nitrate, 5 parts of sodium fluosilicate, 7 parts of titanium oxide, 3 parts of cobalt oxide, 6 parts of nickel oxide, 3 parts of copper oxide, 6 parts of chromium oxide, 10 parts of zirconium dioxide, 14 parts of corundum particles, 17 parts of fluxing agent and 15 parts of grinding material.

3. The metal enamel glaze with milky overglaze according to claim 1 or 2, wherein the abrasive consists of silicon carbide and boron nitride in a weight ratio of 4: 1.

4. The metal enamel glaze with opalescent overglaze according to claim 1, wherein the flux is composed of calcium carbonate, talc and silica.

5. The metal enamel glaze with milky overglaze according to claim 4, wherein the flux is composed of calcium carbonate, talc and silica in a weight ratio of 3:5: 2.

6. The metal enamel frit with an opalescent glaze according to claim 1, wherein the corundum particles have a particle size of 10 to 18 μm.

7. The metal enamel glaze with the milky overglaze according to claim 1, wherein the ground glaze comprises the following raw materials in parts by weight: 14-20 parts of silicon dioxide, 19-24 parts of quartz, 6-10 parts of barium molybdate and 4-8 parts of boron oxide.

8. A process for preparing the metal enamel frit with opalescent overglaze according to claim 1, characterized in that it comprises the steps of: weighing the raw materials in parts by weight, grinding the raw materials uniformly in a mortar at the temperature of 1100-1200 ℃, sieving the ground raw materials with a 60-mesh sieve, putting the ground raw materials into a small crucible, preserving the heat for 1.2-1.5h to obtain uniform fused porcelain glaze, immediately pouring the fused porcelain glaze into cold water for quenching, finally taking out the porcelain glaze from the water, putting the porcelain glaze into a 100 ℃ drying box for drying for 1h, putting the dried porcelain glaze into a ball milling tank, adding the grinding material, adding 50% of water, grinding for 14min, and pouring the ground slurry out of the 40-mesh sieve.

Technical Field

The invention relates to the technical field of ceramic preparation, in particular to a metal enamel glaze with milky overglaze and a preparation method thereof.

Background

Enamels originate from decorations, also known as enamels. Due to the limitation of the materials used, the method is limited to the manufacture of artware for a long time. Until the 18 th century, cast iron enamels appeared, and then rapid development of such commodities was achieved. The main components and structure of the enamel are consistent with those of glass, the disordered silicon-oxygen network structure of the enamel determines that the strain tolerance and fracture toughness of the enamel are low, the enamel is highly sensitive to cracks, and the enamel is easy to crack and peel due to the accumulation of thermal stress in the thermal cycle process, which is one of the main restriction factors of the enamel coating applied under the condition of high-temperature thermal shock. In addition, the glass phase in the enamel does not have a fixed melting point, when the temperature is higher than the glass transition point, the coating slowly changes from a solid state (glass state) to a liquid state (high elastic state or even molten state), and the barrier effect of the softened enamel coating on corrosive media (such as oxygen, sulfur, chlorine, molten metal, deposited salt and the like) is obviously reduced, so that the protection effect is lost, and the quality and the service life of the product are seriously reduced.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a metal enamel glaze with milky overglaze and a preparation method thereof.

The purpose of the invention is realized by the following technical scheme:

a metal enamel glaze with a milky glaze comprises a glaze and a ground glaze, wherein the glaze comprises the following materials in parts by weight: 16-24 parts of quartz, 22-28 parts of albite, 12-18 parts of fluorite, 6-12 parts of barite, 5-15 parts of calcite, 15-20 parts of limestone, 5-8 parts of borax, 6-10 parts of soda ash, 4-8 parts of sodium nitrate, 2-6 parts of sodium fluosilicate, 4-10 parts of titanium oxide, 2-5 parts of cobalt oxide, 4-8 parts of nickel oxide, 2-4 parts of copper oxide, 3-8 parts of chromium oxide, 8-12 parts of zirconium dioxide, 12-15 parts of corundum particles, 16-18 parts of fluxing agent and 10-20 parts of grinding material; wherein the abrasive comprises silicon carbide and boron nitride.

Further, the overglaze comprises the following materials in parts by weight: 18 parts of quartz, 26 parts of albite, 15 parts of fluorite, 10 parts of barite, 12 parts of calcite, 18 parts of limestone, 6 parts of borax, 8 parts of soda ash, 6 parts of sodium nitrate, 5 parts of sodium fluosilicate, 7 parts of titanium oxide, 3 parts of cobalt oxide, 6 parts of nickel oxide, 3 parts of copper oxide, 6 parts of chromium oxide, 10 parts of zirconium dioxide, 14 parts of corundum particles, 17 parts of fluxing agent and 15 parts of grinding material.

Further, the abrasive is composed of silicon carbide and boron nitride in a weight ratio of 4: 1.

Further, the fluxing agent is composed of calcium carbonate, talcum powder and silicon dioxide.

Further, the fluxing agent is composed of calcium carbonate, talcum powder and silicon dioxide according to the weight ratio of 3:5: 2.

Further, the particle size of the corundum particles is 10-18 μm.

Further, the ground glaze comprises the following raw materials in parts by weight: 14-20 parts of silicon dioxide, 19-24 parts of quartz, 6-10 parts of barium molybdate and 4-8 parts of boron oxide.

Further, the preparation method comprises the following steps: weighing the raw materials in parts by weight, grinding the raw materials uniformly in a mortar at the temperature of 1100-1200 ℃, sieving the ground raw materials with a 60-mesh sieve, putting the ground raw materials into a small crucible, preserving the heat for 1.2-1.5h to obtain uniform fused porcelain glaze, immediately pouring the fused porcelain glaze into cold water for quenching, finally taking out the porcelain glaze from the water, putting the porcelain glaze into a 100 ℃ drying box for drying for 1h, putting the dried porcelain glaze into a ball milling tank, adding the grinding material, adding 50% of water, grinding for 14min, and pouring the ground slurry out of the 40-mesh sieve.

The invention has the beneficial effects that:

(1) the corundum particles are added, the corundum particles can enhance the network structure and physical impedance capability of the glaze to improve the high-temperature protection capability of the enamel glaze, and can control the type and size of crystals and adjust the thermal physical performance of the glaze by changing the crystallization behavior of enamel.

(2) The added chromium oxide and zirconium dioxide can remarkably improve the acid and alkali resistance of the glaze, and the excellent high-temperature performance of the zirconium dioxide can also improve the thermal shock resistance of the glaze; the cobalt oxide and the nickel oxide are used as the adhesive in the glaze, so that the adhesive force of the glaze on the metal surface can be effectively improved, and the high-temperature resistance of the glaze can be improved; titanium oxide, fluorite and sodium fluosilicate are used as coloring agents in the glaze, the milky color of the glaze is improved, and the function of beautifying the appearance is achieved.

Detailed Description

The technical solution of the present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited to the following.

Example 1

A method for preparing the metal enamel glaze with milky overglaze, comprising the steps of: weighing 16 parts of quartz, 22 parts of albite, 12 parts of fluorite, 6 parts of barite, 5 parts of calcite, 15 parts of limestone, 5 parts of borax, 6 parts of soda ash, 4 parts of sodium nitrate, 2 parts of sodium fluosilicate, 4 parts of titanium oxide, 2 parts of cobalt oxide, 4 parts of nickel oxide, 2 parts of copper oxide, 3 parts of chromium oxide, 8 parts of zirconium dioxide, 12 parts of corundum particles, 4 parts of calcium carbonate, 9 parts of talcum powder, 3 parts of silicon dioxide, 8 parts of silicon carbide and 2 parts of boron nitride according to parts by weight, putting the mixture into a mortar at the temperature of 1100 ℃, grinding the mixture uniformly, sieving the mixture through a 60-mesh sieve, putting the mixture into a small crucible, preserving the temperature for 1.2 to obtain uniform fused porcelain glaze, immediately pouring the fused porcelain glaze into cold water for quenching, finally taking out the porcelain glaze from the water, putting the porcelain glaze into a drying oven at the temperature of 100 ℃, putting into a ball milling tank, adding the grinding materials, adding 50% of water, grinding for 14min, pouring the ground slurry out of 40 meshes, obtaining the metal enamel glaze with the milky overglaze.

Example 2

A method for preparing the metal enamel glaze with milky overglaze, comprising the steps of: weighing 18 parts of quartz, 26 parts of albite, 15 parts of fluorite, 10 parts of barite, 12 parts of calcite, 18 parts of limestone, 6 parts of borax, 8 parts of soda ash, 6 parts of sodium nitrate, 5 parts of sodium fluosilicate, 7 parts of titanium oxide, 3 parts of cobalt oxide, 6 parts of nickel oxide, 3 parts of copper oxide, 6 parts of chromium oxide, 10 parts of zirconium dioxide, 14 parts of corundum particles, 4 parts of calcium carbonate, 10 parts of talcum powder, 3 parts of silicon dioxide, 12 parts of silicon carbide and 3 parts of boron nitride according to parts by weight, putting the mixture into a mortar at the temperature of 1150 ℃, grinding the mixture uniformly, sieving the mixture through a 60-mesh sieve, putting the mixture into a small crucible, preserving the temperature for 1.3 hours to obtain uniform fused porcelain glaze, immediately pouring the fused porcelain glaze into cold quenching water for crushing, finally taking out the porcelain glaze from the water, putting the porcelain glaze into a drying box at the temperature of 100 ℃, drying the mixture for 1 hour, putting the mixture into a ball milling tank, adding the grinding materials, adding 50 percent of water, grinding for 14 minutes, pouring the ground slurry out of 40-mesh sieve, obtaining the metal enamel glaze with the milky overglaze.

Example 3

A method for preparing the metal enamel glaze with milky overglaze, comprising the steps of: weighing 24 parts of quartz, 28 parts of albite, 18 parts of fluorite, 12 parts of barite, 15 parts of calcite, 20 parts of limestone, 8 parts of borax, 10 parts of soda ash, 8 parts of sodium nitrate, 6 parts of sodium fluosilicate, 10 parts of titanium oxide, 5 parts of cobalt oxide, 8 parts of nickel oxide, 4 parts of copper oxide, 8 parts of chromium oxide, 12 parts of zirconium dioxide, 15 parts of corundum particles, 5 parts of calcium carbonate, 11 parts of talcum powder, 2 parts of silicon dioxide, 16 parts of silicon carbide and 4 parts of boron nitride according to parts by weight, putting the mixture into a mortar at 1200 ℃, grinding the mixture uniformly, sieving the mixture through a 60-mesh sieve, putting the mixture into a small crucible, preserving the temperature for 1.5 hours to obtain uniform fused porcelain glaze, immediately pouring the fused porcelain glaze into cold water for quenching, finally taking out the porcelain glaze from the water, putting the porcelain glaze into a drying oven at 100 ℃ for drying for 1 hour, putting into a ball milling tank, adding the grinding materials, adding 50% of water, grinding for 14 minutes, pouring the ground slurry out of 40 meshes, obtaining the metal enamel glaze with the milky overglaze.

Comparative example

The raw materials and preparation methods of this comparative example and example 2 are substantially the same, except that this comparative example does not contain corundum particles.

The metal enamel frits manufactured in examples 1 to 3 and comparative example were tested for heat resistance and acid resistance, and the results are shown in the following table 1:

test results

TABLE 1

The heat resistance test method comprises the following steps: GB11418-89 test method for enamel heat resistance;

the test method of the acid resistance comprises the following steps: the method comprises the steps of adding 10g of citric acid into 100mL of distilled water to prepare a 10% citric acid solution, overlapping three pieces of filter paper on a test board, dripping the citric acid solution by using a dropper to moisten the filter paper, standing for 15min at normal temperature, removing the filter paper, cleaning the glaze surface on the filter paper by using water, wiping the glaze surface with dry cloth, and then drawing three lines at the position by using a 3B pencil, wherein the dry cloth can wipe off the trace of the pencil and has the acid resistance AA; the dry cloth cannot be used, but the wet cloth can wipe off the pencil marks and resist the acid A level; the pencil marks can not be wiped off by dry and wet cloth, and the reagent is resistant to the acid B (AA: the best acid resistance; A: the moderate acid resistance; B: the poor acid resistance).

From table 1 above, it can be seen that the data of example 2 is better and is the most preferred example, and that the addition of rigid particles has a greater effect on both the heat resistance and the acid resistance of the glaze.

The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.