CN102515533A - Alkali silicate glass frit, zirconium frit opaque glaze, zirconium raw material opaque glaze and preparation methods of the zirconium frit opaque glaze and the zirconium raw material opaque glaze - Google Patents

Abstract

The invention discloses an alkali silicate glass frit, a zirconium frit opaque glaze, a zirconium raw material opaque glaze and a ceramic glazing method, wherein the main raw material of the frit glaze is a frit formed of waste silica gel and soda ash , wherein the amount of waste silica gel and soda ash meets the molar ratio of SiO ₂ and Na ₂ O introduced at 2-3:1, and the raw material glaze is directly pulped and fired with waste silica gel and other raw materials. The opacifying glaze of the present invention uses zirconium-containing waste silica gel (abbreviated as waste silica gel, the same below) as raw materials, and uses the residual zirconium as an opacifying agent, which not only solves the problems of waste silica gel storage and environmental pollution, but also reduces the types of raw materials used , reduces the production cost of the opacity glaze, the waste silica gel in the preparation process can be used directly without physical and chemical treatment, which is convenient for industrial application, and the performance of the obtained opacity glaze can meet the general requirements.

Description

A kind of alkali silicate glass frit, zirconium opacity glaze and preparation method thereof

technical field

The invention relates to an alkali silicate glass frit, an opaque glaze and a preparation method thereof, in particular to an alkali silicate glass frit, a zirconium opaque glaze and a preparation method thereof, and belongs to the technical field of inorganic non-metallic materials.

Background technique

Glass frits can be used to produce opacified glazes, and alkali silicate glass frits with sodium oxide and silicon dioxide as the main components are also raw materials for the production of water glass (common name: sodium silicate). Opaque glazes are widely used in the decoration of ceramics and enamel. The root of opacification is that the glassy glaze produces a second phase with a different refractive index from the matrix glass due to phase separation or crystallization, which causes light to pass through the glaze. It is caused by multiple refractions. Zirconium opacity glaze is one of the widely used opacity glazes, and its research has a history of nearly a hundred years. Zirconium opaque glaze has the advantages of high whiteness, good opacification effect, strong covering ability, can reduce the requirements for blank raw materials and process control, stable opacification effect, insensitive to atmosphere, and low cost, and can be used for sanitary porcelain , Production of glazed tiles and enamel products.

Usually, zircon sand, zirconium silicate or zirconium oxide is used as opacifying agent to prepare zircon opaque glaze. The opacification mechanism is caused by residual or recrystallized zirconium compound particles in the glaze. In the preparation process of zirconium glaze, the opacifying effect is achieved by grinding zirconium opacifying agent into the frit, or directly mixing zirconium opacifying agent with other raw materials, melting at high temperature, and then precipitating zirconium-containing crystals. The zirconium opacifier has a high melting point, and the firing temperature of the glaze is relatively high. No matter what kind of zirconium opacifier is used, there are only two crystal phases of zircon and baddeleyite that work in the end. Zircon sand or zirconia as an opacifying agent occupies a large proportion in the cost of zirconium opacifying glaze. In addition, the composition of zirconium opacity glaze is complex, and more raw materials containing lithium or boron are used. For example, in the patent CN200710139659.5 (medium temperature high white zirconium lithium raw material opacity glaze and its production method), in addition to using 10-15% zirconium In addition to British powder, 12-15% lithium porcelain stones need to be added; in addition to using 13-18% zirconium silicate in the patent CN201010559507.2 (a white opaque glaze for piezoelectric ceramic atomizer and its preparation method), Also need to add 15 to 25% boric acid. There are many types of raw materials, which not only increase the cost of raw materials, but also increase the cost of raw material handling, storage and process links.

Zirconium-containing waste silica gel (hereinafter referred to as "waste silica gel") is derived from the solid waste produced after mineral extraction of zirconium oxide or zirconium oxychloride and other zirconium products, and its main components are silica and zirconium dioxide (5-12% ), the former is one of the main components of alkali silicate glass frit and zirconium opaque glaze, and the latter can be used as an opacifying agent for opaque glaze. In addition, waste silica gel also contains a small amount of calcium and aluminum, which are also beneficial components of zirconium opaque glaze. At present, there are few reports of opacifying glazes made from zirconium-containing waste silica gel. If it is used as an opacifying agent to formulate opacifying glazes, the cost can be greatly reduced, which is very meaningful for the industrial application of zirconium opacifying agents.

Contents of the invention

The invention provides an alkali silicate glass frit using waste silica gel as a raw material. Compared with the alkali silicate glass frit traditionally used in the production of water glass, the frit is easy to melt, and the melting temperature is reduced by about 20-150°C. In addition, the resulting glass frit will contribute to improved viscosity and strength due to the introduction of zirconium.

In addition, aiming at the shortcomings of the existing zirconium opacity glazes, which have many raw materials and high production costs, the present invention also provides two kinds of zirconium opacity glazes, both of which use zirconium-containing waste silica gel (abbreviated as waste silica gel, the same below) The remaining zirconium is an opacifying agent, which not only solves the problems of waste silica gel storage and environmental pollution, but also reduces the types of raw materials used and reduces the production cost of opacifying glazes.

Further, the present invention also provides a method for preparing zirconium opaque glaze, which requires less raw materials, waste silica gel can be used directly without physical and chemical treatment, and is convenient for industrial application.

The main purpose of the present invention is to study the industrial solid waste produced in the production process of zirconia or zirconium oxychloride—the application of zirconium-containing waste silica gel in actual industrial production. The research shows that waste silica gel can be used as raw material to produce Alkali silicate glass frit and zirconium opaque glaze are turned into treasure, which not only protects the environment but also reduces production costs.

Its specific technical scheme is as follows:

An alkali silicate glass frit is characterized in that: raw materials include waste silica gel and soda ash, wherein the amount of waste silica gel and soda ash satisfies the molar ratio of introduced SiO ₂ to Na ₂ O of 2-3:1.

The frit obtained above can also be directly used as a raw material for producing water glass (commonly known as sodium silicate). Generally, the melting temperature of the frit is between 1250-1280°C.

The invention provides a zirconium frit opacifying glaze, which uses waste silica gel to replace traditional zirconium silicate, zircon sand or zirconia opacifying agent to prepare zirconium opacifying glaze. The raw materials include: a) frit, b) clay , c) At least one of albite, limestone and fluorite, wherein the frit is formed from waste silica gel and soda ash, and the amount of waste silica gel and soda ash meets the molar ratio of introduced SiO ₂ and Na ₂ O of 2-3 : 1, the consumption of clay is 1% of clinker quality, and the consumption of c raw material is 5% of clinker quality.

In the zirconium frit opaque glaze, the waste silica gel is mainly composed of silica and zirconia, wherein the content of zirconia is 5-12wt% of the waste silica gel.

The above-mentioned preparation method of zirconium frit opacity glaze is characterized in that it comprises the following steps:

(1) Take waste silica gel and soda ash in proportion, mix them evenly, and heat them to 1250~1280°C to melt them;

(2) Quenching, filtering and drying the molten glass to obtain a frit;

(3) Mix the clinker with other raw materials (referring to at least one of the above-mentioned raw material b clay and raw material c albite, limestone and fluorite), and perform ball milling;

(4) Adjust the obtained slurry to a suitable concentration, and glaze the ceramic body by dipping, glazing or spraying;

(5) The glazed ceramic body is fired at 1000°C, kept for 1 hour, and cooled with the furnace to obtain the finished product.

During ball milling, the mass ratio of the amount of balls, water and raw materials used can be the general ratio in the field, and those skilled in the art can choose from the prior art.

The above-mentioned frit glaze uses waste silica gel as an opacifying agent, and waste silica gel also contains a large amount of silicon dioxide, which provides raw materials for the opacifying glaze. In the formula of the present invention, there are few types of raw materials and low cost, and the performance of the obtained glaze meets the requirements of general sanitary porcelain and glazed tiles. In addition, since the waste silica gel containing zirconium is in an amorphous form, and the distribution of zirconium in it is relatively uniform, it is used as Zirconium opacifier can make the glaze fusible and uniform in composition.

The present invention also provides a zirconium raw material opacity glaze, which is characterized in that it comprises the following raw materials in weight percentage:

Waste silica gel 32-56%

Silica sand 0-23%

Feldspar 16-41%

Limestone 2-12%

Alumina 0-8.4%

Zinc Oxide 0-4.3%

Fluorite 2.9-4.8%

Kaolin 0-17.5%

Magnesium Oxide 0-1%.

In the aforementioned zirconium raw material opaque glaze, the waste silica gel is mainly composed of silica and zirconia, wherein the content of silica is 5-12wt% of the waste silica gel.

The present invention also provides a method for glazing ceramics with this raw opaque glaze, which is characterized in that it comprises the following steps:

(1) Mix the raw materials and perform ball milling;

(2) Adjust the obtained slurry to a suitable concentration, and glaze the ceramic body by dipping, coating or spraying;

(3) Dry the glazed green body, then fire it at 1200~1280°C, keep it warm for 0.5-1h, and cool it with the furnace to get the finished product.

During ball milling, the mass ratio of the amount of balls, water and raw materials used can be the general ratio in the field, and those skilled in the art can choose from the prior art.

The above-mentioned raw material glaze uses untreated zirconium-containing silicon dioxide waste silica gel as raw material, which reduces the types of raw materials, especially the use of expensive raw materials, and reduces the post-processing burden of waste silica gel, which not only utilizes industrial waste but also reduces zirconium emulsion. The production cost of cloudy glaze has good environmental and social economic benefits. In addition, because the waste silica gel containing zirconium is amorphous and zirconium is evenly distributed in it, it can be used as a zirconium opacifying agent to make the glaze fusible and uniform in composition. The performance of the obtained opacifying glaze can meet the general requirements and can be used For the decoration of general glazed tiles, wine bottles, sanitary porcelain, enamel, etc.

Detailed ways

The present invention will be further described below through specific examples. It should be understood that the following descriptions are only for explaining the present invention and not limiting its content. Unless otherwise stated, the following raw material compositions are all percentages by weight.

Example 1

The frit is made from waste silica gel and soda ash, wherein the waste silica gel contains 5-12wt% zirconia and the rest is silica. In the raw materials, the amount of waste silica gel and soda ash is such that the molar ratio of SiO ₂ and Na ₂ O introduced is 75:25, that is, 3:1. The frit is prepared as follows:

1. Take waste silica gel and soda ash in proportion, mix them evenly, and heat them to 1280°C in an electric furnace or kiln to melt them;

2. Quench the molten glass with water, filter it dry, and dry it at 120°C to obtain a frit. The resulting frit can be directly used as a raw material for producing water glass (commonly known as sodium silicate), and can also be used as a raw material for opacified glaze.

Example 2

The frit is made from waste silica gel and soda ash, wherein the waste silica gel contains 5-12wt% zirconia and the rest is silica. In the raw materials, the amount of waste silica gel and soda ash is such that the molar ratio of SiO ₂ and Na ₂ O is 67:33. Except that the waste silica gel and soda ash are heated to 1250°C for melting, other steps for preparing frits are as in Example 1 .

Example 3

The opaque glaze is made from waste silica gel, soda ash, clay and albite, wherein the waste silica gel contains 5-12wt% zirconia and the rest is silica. In the raw material, the consumption of waste silica gel and soda ash meets the molar ratio of introducing SiO ₂ and Na ₂ O, which is 75:25, that is, 3:1, and the consumption of clay is 1% of the total amount of frit, and the consumption of albite feldspar is 5% of the total amount of waste silica gel and soda ash. Waste silica gel and soda ash are added in the form of frit, and the method for preparing frit glaze is as follows:

1. Take waste silica gel and soda ash in proportion, mix them evenly, and heat them to 1280°C in an electric furnace or kiln to melt them;

2. Quench the molten glass with water, filter it dry, and dry it at 120°C to obtain a frit;

3. Mix the frit with clay and albite for ball milling (material: water: ball mass ratio is 1:0.7:1.5);

4. Glaze the ceramic body by dipping, glazing or spraying;

5. The glazed ceramic body is fired at 1000°C for 1 hour, and then cooled with the furnace to obtain the finished product. The appearance quality of the obtained glaze can meet the general requirements of ordinary opacified ceramic products such as glazed tiles.

Example 4

Except that albite is replaced by light limestone, others are as in Example 3. The appearance quality of the obtained glaze can meet the general requirements of ordinary opacified ceramic products such as glazed tiles.

Example 5

Except that albite was replaced by fluorite, others were as in Example 3. The appearance quality of the obtained glaze can meet the general requirements of ordinary opacified ceramic products such as glazed tiles.

Example 6

The opaque glaze is made from waste silica gel, soda ash, clay, albite, light limestone and fluorite, wherein the waste silica gel contains 5-12wt% zirconia and the rest is silica. In the raw material, the consumption of waste silica gel and soda ash meets the molar ratio of introducing SiO ₂ and Na ₂ O, which is 75:25, that is, 3:1, and the consumption of clay is 1% of the total amount of frit, and the consumption of albite feldspar is 1.5% of the frit, the amount of light limestone is 3.0% of the frit, and the amount of fluorite is 0.5% of the frit. Waste silica gel and soda ash are added in the form of frit, and the preparation method is as in Example 3. The appearance quality of the obtained glaze can meet the general requirements of ordinary opacified ceramic products such as glazed tiles.

Example 7

The opaque glaze is made from waste silica gel, soda ash, clay, light limestone and fluorite, wherein the waste silica gel contains 5-12wt% zirconia and the rest is silica. In the raw materials, the amount of waste silica gel and soda ash meets the molar ratio of introducing _SiO2 and _Na2O , which is 67:33, and the amount of clay is 1% of the total amount of waste silica gel and soda ash, and the amount of light limestone is 1% of the frit. 1%, the amount of fluorite is 4% of the frit, waste silica gel and soda ash are added in the form of frit. Example 3 of the method for preparing frit glaze except that the waste silica gel and soda ash are heated to 1250°C for melting. The appearance quality of the obtained glaze can meet the general requirements of ordinary opacified ceramic products such as glazed tiles.

Example 8

Except that the consumption of light limestone is 4% of clinker, the consumption of fluorite is 1% of clinker, others are as embodiment 7. The appearance quality of the obtained glaze can meet the general requirements of ordinary opacified ceramic products such as glazed tiles.

Example 9

The opaque glaze is made from waste silica gel, soda ash, clay, albite and light limestone, wherein the waste silica gel contains 5-12wt% zirconia and the rest is silica. In the raw material, the consumption of waste silica gel and soda ash satisfies the molar ratio of introducing SiO ₂ and Na ₂ O and is 67:33, and the consumption of clay is 1% of waste silica gel and soda ash total amount, and the consumption of albite is waste silica gel and 2.5% of the total amount of soda ash, and the amount of light limestone is 2.5% of the total amount of waste silica gel and soda ash. Waste silica gel and soda ash are added in the form of frit, and the method for preparing frit glaze is as follows:

1. Take waste silica gel and soda ash in proportion, mix them evenly, and heat them to 1250°C in an electric furnace or kiln to melt them;

2. Quench the molten glass with water, filter it dry, and dry it at 120°C to obtain a frit;

3. Mix the clinker with clay, albite, and light limestone, and perform ball milling (material: water: ball mass ratio is 1:0.7:1.5);

4. Glaze the ceramic body by dipping, glazing or spraying;

5. The glazed ceramic body is fired at 1000°C for 1 hour, and then cooled with the furnace to obtain the finished product. The appearance quality of the obtained glaze can meet the general requirements of ordinary opacified ceramic products such as glazed tiles.

Example 10

The opaque glaze is made from waste silica gel, soda ash, clay, fluorite and light limestone, wherein the waste silica gel contains 5-12wt% zirconia and the rest is silica. In the raw materials, the amount of waste silica gel and soda ash meets the requirement that the molar ratio of _SiO2 and _Na2O introduced is 75:25, that is, 3:1, while the amount of clay is 1% of the total amount of waste silica gel and soda ash, and the amount of fluorite is The amount of light limestone is 2.5% of the total amount of waste silica gel and soda ash, and the amount of light limestone is 2.5% of the total amount of waste silica gel and soda ash. The waste silica gel and soda ash are added in the form of frit. Except that waste silica gel and soda ash are heated to 1280°C for melting, the method of preparing frit glaze is as in Example 6, and the appearance quality of the obtained glaze can meet the general requirements of ordinary opaque ceramic products such as glazed tiles.

Example 11

The opaque glaze is made from waste silica gel, soda ash, clay, fluorite and albite, wherein the waste silica gel contains 5-12wt% zirconia and the rest is silica. In the raw materials, the amount of waste silica gel and soda ash meets the requirement that the molar ratio of _SiO2 and _Na2O introduced is 75:25, that is, 3:1, while the amount of clay is 1% of the total amount of waste silica gel and soda ash, and the amount of fluorite is The amount of albite is 2.5% of the total amount of waste silica gel and soda ash, and the amount of albite is 2.5% of the total amount of waste silica gel and soda ash. The waste silica gel and soda ash are added in the form of frit. Except that waste silica gel and soda ash are heated to 1280°C for melting, the method of preparing frit glaze is as in Example 6, and the appearance quality of the obtained glaze can meet the general requirements of ordinary opaque ceramic products such as glazed tiles.

Example 12

With 32.2% of waste silica gel, 22.3% of silica sand, 16% of feldspar, 12.2% of limestone, 8.4% of aluminum oxide, 4.2% of zinc oxide, and 4.7% of fluorite as raw materials, the sum of each raw material is 100%, and the glaze of the present invention does not need to be melted. Blocks can be directly made into raw material glaze, and its preparation method is as follows:

1. Mix the raw materials and make pulp by ball milling (the mass ratio of material: water: ball is 1: 1.2: 2);

2. Glaze the ceramic body by dipping, glazing or spraying;

3. Dry the body after glazing, then fire it at 1200~1280℃ for 0.5-1h, and cool it with the furnace to get the finished product.

Example 13

Using 32.6% of waste silica gel, 7.1% of silica sand, 24.3% of feldspar, 8.5% of limestone, 17.5% of kaolin, 4.2% of zinc oxide, 4.8% of fluorite, and 1% of light MgO as raw materials, the sum of all raw materials is 100%. The method is as in Example 12.

Example 14

Using waste silica gel 49%, feldspar 24.5%, limestone 8.4%, kaolin 4.2%, zinc oxide 4.3%, fluorite 4.8%, aluminum oxide 3.8%, MgO 1% as raw materials, the sum of each raw material is 100%, the preparation method for:

1. Mix the raw materials and make pulp by ball milling (the mass ratio of material: water: ball is 1: 1.2: 2);

2. Glaze the ceramic body by dipping, glazing or spraying;

3. Dry the body after glazing, then fire it at 1250°C for 0.5h, and cool it with the furnace to get the finished product.

Example 15

Using 56% waste silica gel, 22.9% feldspar, 2% limestone, 10.5% kaolin, 2.9% fluorite, 5.2% alumina, and 0.5% MgO as raw materials, the sum of each raw material is 100%. The preparation method is as in Example 14.

Example 16

32% of waste silica gel, 17% of silica sand, 41% of feldspar, 5% of limestone, 4% of fluorite, and 1% of light MgO are used as raw materials, and the sum of each raw material is 100%. The preparation method is as in Example 12.

In the above examples, the whiteness, gloss and density of the three glaze samples obtained in Examples 12-14 are shown in Table 1 below, and the performance of the glaze samples in Examples 15 and 16 is similar to that of Example 14. The properties of the glazes prepared in Examples 12-16 meet the general requirements, and can be used on wine bottles, sanitary porcelain and other utensils.

Claims (8)

1. An alkali silicate glass frit, characterized in that: raw materials include waste silica gel and soda ash, wherein the consumption of waste silica gel and soda ash meets _SiO2 and _Na2O 's mol ratio of introduction is 2-3:1. 2. The alkali silicate glass frit according to claim 1, characterized in that: the waste silica gel is mainly composed of silica and zirconia, wherein the content of zirconia is 5-12wt% of the waste silica gel. 3. A zirconium frit opacity glaze, characterized in that the raw materials include: a) frit, b) clay, c) at least one of albite, limestone and fluorite, wherein the frit is made of waste silica gel and Soda ash is formed, the amount of waste silica gel and soda ash meets the molar ratio of introduced SiO ₂ and Na ₂ O is 2-3:1, the amount of clay is 1% of the mass of the frit, and the amount of c raw material is 5% of the mass of the frit . 4. The zirconium frit opaque glaze according to claim 3, characterized in that: the waste silica gel is mainly composed of silica and zirconia, wherein the content of zirconia is 5-12wt% of the waste silica gel. 5. a preparation method of the zirconium frit opaque glaze as claimed in claim 3, is characterized in that, comprises the following steps: (1) Take waste silica gel and soda ash in proportion, mix them evenly, and heat them to 1250-1280°C to melt them; (2) Quenching, filtering and drying the molten glass to obtain frit; (3) Mix the frit with other raw materials for ball milling; (4) Adjust the obtained slurry to a suitable concentration, and glaze the ceramic body by dipping, coating or spraying; (5) The glazed ceramic body is fired at 1000°C, kept for 1 hour, and cooled with the furnace to obtain the finished product. 6. A zirconium raw material opacity glaze is characterized in that it comprises the following raw materials in weight percentage: Waste silica gel 32-56% Silica sand 0-23% Feldspar 16-41% Limestone 2-12% Alumina 0-8.4% Zinc Oxide 0-4.3% Fluorite 2.9-4.8% Kaolin 0-17.5% Magnesium Oxide 0-1%. 7. The zirconium raw material opaque glaze according to claim 6, characterized in that: the waste silica gel is mainly composed of silica and zirconia, wherein the content of zirconia is 5-12wt% of the waste silica gel. 8. A method for preparing the zirconium raw material opaque glaze according to claim 6, characterized in that, comprising the following steps: (1) Mix the raw materials and perform ball milling; (2) Adjust the obtained slurry to a suitable concentration, and glaze the ceramic body by dipping, coating or spraying; (3) Dry the glazed green body, then fire it at 1200-1280°C, keep it warm for 0.5-1h, and cool it with the furnace to get the finished product.