CN115490426A - Ceramic glaze and preparation process thereof - Google Patents

Abstract

The invention discloses a ceramic glaze and a preparation process thereof, relates to the field of ceramic glaze, and aims to solve the problem of poor zinc oxide dispersibility in the prior art; industrial alumina and Suzhou kaolin are used as base materials, the glaze has high whiteness, the whitening effect can be further achieved by adding titanium dioxide, the glaze has an antibacterial and bacteriostatic effect by adding an antibacterial agent, the surface characteristic of nano zinc oxide can be improved by adding sodium hexametaphosphate, and the rheological behavior of the nano zinc oxide glaze is greatly influenced. The glaze with low viscosity, high stability and good uniformity can be obtained by adding the dispersing agent; the glaze prepared by the formula has good antibacterial effect, good glaze surface adaptability, no pinhole and bright white color.

Description

Ceramic glaze and preparation process thereof

Technical Field

The invention relates to the field of ceramic glaze, in particular to ceramic glaze and a preparation process thereof.

Background

The building sanitary ceramic industry pays great attention to the adoption of advanced glaze technology, and a large number of companies with ceramic glaze, ceramic frit and pigment with strong speciality appear in China. The glaze used in the building sanitary ceramic products is more and more abundant, and most of the glaze products used in Tao Qi can be classified into the following categories and uses:

1. lead glaze and lead-free glaze; 2. raw glaze and fritted glaze; 3. glaze for primary firing or secondary firing; 4. glaze for ceramic tiles, tableware, sanitary ceramics and electroceramics; 5. dipping, spraying and pouring glaze according to the glaze application method; 6. high-temperature glaze and low-temperature glaze; 7. high expansion glaze and low expansion glaze; 8. firing atmosphere oxidizing flame, neutral flame and reducing flame; 9. colored glaze and colorless glaze; 10. transparent glaze and opaque glaze; 11. glossy glaze, matte glaze, semi-matte glaze or fancy glaze, and the like.

Chinese patent CN202011488519.0 discloses a low-color-difference ceramic glaze, which adopts the technical scheme that the low-color-difference ceramic glaze comprises the following components: 20 to 40 percent of quartz stone, 25 to 45 percent of potassium feldspar, 5 to 10 percent of kaolin, 1 to 5 percent of borax, 1 to 3 percent of zinc oxide, 1 to 3 percent of zirconium silicate, 7 to 15 percent of calcium carbonate, 1 to 5 percent of magnesium carbonate, 1 to 5 percent of strontium carbonate,

0.5-2% of phosphorus pentoxide, 1-3% of lithium carbonate and 0.5-2% of modified graphene;

the preparation method of the low-color-difference ceramic glaze comprises the following steps:

step 1, crushing quartz stone and potash feldspar, and ball-milling the crushed quartz stone and potash feldspar through a 300-mesh screen to obtain mixed powder;

step 2, mixing the mixed powder with kaolin, borax, zinc oxide, zirconium silicate, calcium carbonate, magnesium carbonate, strontium carbonate, phosphorus pentoxide and lithium carbonate, and then carrying out ball milling to obtain a basic glaze;

step 3, mixing the basic glaze with 40-50% of modified graphene to obtain a first glaze;

and 4, dispersing the residual modified graphene into water, and adding amine chloride to obtain a second glaze.

Chinese patent CN202110351771.5 discloses a cloth grain ceramic glaze, which adopts the technical scheme that the cloth grain ceramic glaze comprises the following components:

2-5 parts of zinc oxide, 4-8 parts of zirconium silicate, 7-10 parts of potassium feldspar, 10-30 parts of albite, 10-15 parts of aluminum powder, 5-10 parts of calcite, 5-10 parts of dolomite, 4-10 parts of medium aluminum powder, 1-5 parts of quartz, 10-15 parts of kaolin and 1-5 parts of yttrium silicate; the yttrium silicate comprises 0.5-2.5 parts by mass of yttrium silicate whiskers and 0.5-2.5 parts by mass of flaky yttrium silicate; the preparation method of the flaky yttrium silicate comprises the following steps:

taking 6-10 parts by mass of yttrium nitrate hexahydrate, 1-4 parts by mass of ethyl orthosilicate and 10-30 parts by mass of absolute ethyl alcohol;

uniformly mixing yttrium nitrate hexahydrate and ethyl orthosilicate, adding absolute ethyl alcohol, stirring in a closed container, simultaneously heating the closed container in a water bath, heating to 35-45 ℃, and uniformly stirring to obtain a precursor solution; carrying out solvothermal reaction on the precursor solution at 100-120 ℃ for 12-24 h to obtain gel, and drying the gel to obtain intermediate powder;

uniformly mixing the intermediate powder and the mixed double salt according to the mass ratio of 1:1-3, carrying out heat treatment at 800-1000 ℃, washing and pickling the obtained product, and drying to obtain the flaky yttrium silicate.

The preparation method of the cloth-textured ceramic glaze comprises the following steps:

mixing zinc oxide, zirconium silicate, potassium feldspar, albite, aluminum powder, calcite, dolomite, medium aluminum powder, quartz, kaolin and yttrium silicate, ball-milling, and sieving to obtain the cloth grain ceramic glaze.

The technical scheme uses zinc oxide, but because the force fields of atoms inside and outside the particles are different, the particles are easy to agglomerate, so that the dispersibility is poor, and after the zinc oxide is added into a glaze, the viscosity of the glaze is increased rapidly, so that the glazed surface is cracked or cannot be glazed.

Disclosure of Invention

In view of the problems in the prior art, the invention discloses a ceramic glaze, which adopts the technical scheme that the ceramic glaze comprises the following components:

industrial alumina, kaolin, titanium dioxide, carboxymethyl cellulose, an antibacterial agent, zinc oxide and sodium hexametaphosphate.

The main component of the industrial alumina is alpha-Al ₂ O ₃ The mineral of (1). Removing impurities such as Si, fe, ti and the like from the high bauxite ore by a chemical method. Calcining at 1300-1400 ℃ to become alpha-Al ₂ O ₃ And has volume shrinkage; the industrial alumina is mainly used for producing sintered mullite, sintered alumina, fused corundum refractory materials, artificial ruby and the like.

Kaolin is a non-metallic mineral, a clay and claystone based on clay minerals of the kaolinite group. It is also called dolomitic soil because it is white and fine. The name is obtained from Kaolin village in Jingdezhen of Jiangxi province. The pure kaolin is in a white, fine and soft soil shape and has good physical and chemical properties such as plasticity, fire resistance and the like. The mineral components of the mineral composition mainly comprise kaolinite, halloysite, hydromica, illite, montmorillonite, quartz, feldspar and other minerals. Kaolin has wide application, is mainly used for paper making, ceramics and refractory materials, is used for coating, rubber filler, enamel glaze and white cement raw materials, and is used for industrial departments such as plastics, paint, pigment, grinding wheels, pencils, daily cosmetics, soap, pesticide, medicine, textile, petroleum, chemical industry, building materials, national defense and the like in a small amount.

Titanium dioxide is an inorganic substance with a chemical formula of TiO ₂ White solid or powdery amphoteric oxides, with a molecular weight of 79.9, having non-toxicity, optimal opacity, optimal whiteness and brightness, are considered to be the best performing white pigments in the world today. The titanium white has strong adhesive force, is not easy to chemically change and is snow white forever. It can be widely used in the industries of paint, plastics, paper making, printing ink, chemical fiber, rubber, cosmetics, etc. It has high melting point, and can be used for making refractory glass, glaze, enamel, pottery clay, high-temperature-resistant experimental ware, etc. Titanium dioxide can be extracted from rutile by acid decomposition or from titanium tetrachloride decomposition. Titanium dioxide is stable in nature, is used in large quantities as a white pigment in paints, has good hiding power, is similar to white lead, but does not turn black like white lead; it has the same persistence as zinc white. Titanium dioxide is also used as a matting agent for enamels and produces a very bright, hard and acid-resistant enamel finish.

Carboxymethyl cellulose, natural cellulose is the polysaccharide which is distributed most widely and has the most content in nature, and the source is very rich. Current cellulose modification technologies focus primarily on both etherification and esterification. Carboxymethylation is one of the etherification techniques. Carboxymethyl cellulose (CMC) is obtained after carboxymethylation of cellulose, and an aqueous solution of the carboxymethyl cellulose has the effects of thickening, film forming, adhesion, water retention, colloid protection, emulsification, suspension and the like, is widely applied to industries such as petroleum, food, medicine, textile, paper making and the like, and is one of the most important cellulose ethers. The carboxymethyl cellulose is used as adhesive, plasticizer, glaze suspending agent, color fixing agent, etc. for ceramic industry.

The antibacterial agent is an inorganic antibacterial agent, and the metals (or ions thereof) such as silver, copper, zinc and the like are fixed on the surface of porous materials such as fluorite, silica gel and the like by utilizing the antibacterial capability of the metals such as silver, copper, zinc and the like through methods such as physical adsorption ion exchange and the like to prepare the antibacterial agent, and then the antibacterial agent is added into corresponding products to obtain the material with the antibacterial capability. Metals such as mercury, cadmium, lead and the like also have antibacterial capacity, but are harmful to human bodies; ions such as copper, nickel, lead and the like have colors and affect the appearance of products, and zinc has certain antibacterial property, but the antibacterial strength of the zinc is only 1/1000 of that of silver ions. Therefore, silver ion antibacterial agents dominate inorganic antibacterial agents.

The silver ion antibacterial agent is the most commonly used antibacterial agent, is white fine powder and has the heat-resistant temperature of over 1300 ℃. The carrier of the silver ion antibacterial agent includes glass, zirconium phosphate, zeolite, ceramic, activated carbon, and the like. Sometimes, some copper ions and zinc ions are added to improve the synergistic effect. The long-acting biochar antibacterial material prepared by the biochar loaded silver particles overcomes the characteristics of instability and uneven distribution of other carriers (such as glass, zirconium phosphate, zeolite, ceramic and activated carbon). In addition, inorganic antibacterial agents such as zinc oxide, copper oxide, ammonium dihydrogen phosphate, and lithium carbonate are also included.

Zinc oxide, here used is nano zinc oxide, nano zinc oxide (ZnO), white hexagonal crystal or spherical particle with particle size less than 100nm, average particle size of 50nm, specific surface area greater than 4m ² (ii) in terms of/g. Has extremely high chemical activity, excellent catalytic activity and photocatalytic activity, infrared ray and ultraviolet ray radiation resisting and sterilizing functions and high flowability.

As a novel functional material, the nano ZnO has surface effect, small-size effect and quantum effect, shows various special functions in the aspects of catalysis, optics, magnetism, mechanics and the like, and has important application value in the fields of ceramics, chemical engineering, electronics and the like. The nano ZnO is added into the ceramic glaze, and can endow a ceramic finished product with a plurality of new functions due to the particularity of the nano ZnO. The fine grain size of nano ZnO can increase the surface free energy and enhance the surface activity.

Sodium hexametaphosphate, an inorganic compound, has the chemical formula of (NaPO 3) 6, is white crystalline powder, is easily soluble in water and insoluble in organic solvents, and is mainly used as a quality modifier, a pH regulator, a metal ion chelating agent, a binder and an expanding agent in the food industry.

The influence of solid particles on the fluidity in the ceramic glaze is very complex, and the influencing factors mainly comprise solid content, the size and the shape of the solid particles, the agglomeration degree of the solid particles, the solvation degree of charged quantity, the interaction among the particles and the like. Due to the high dispersibility, large specific surface area and high surface energy of nano ZnO, there is a tendency to self-agglomerate and coalesce with other solid particles in the glaze to reduce the surface energy of the system, thereby affecting the stability and uniformity of the glaze. The addition of the dispersing agent can not only improve the surface characteristics of the nano ZnO, but also greatly influence the rheological behavior of the nano ZnO glaze. The glaze with low viscosity, high stability and good uniformity can be obtained by adding the dispersing agent.

As a preferred technical scheme of the invention, the weight ratio of each component is as follows: 71 percent of industrial alumina, 20 percent of kaolin, 2 percent of titanium dioxide, 1 percent of carboxymethyl cellulose, 1.5 percent of antibacterial agent, 4 percent of zinc oxide and 0.5 percent of sodium hexametaphosphate.

As a preferred technical solution of the present invention, the kaolin is suzhou kaolin.

Suzhou kaolin is a medium to low temperature hydrothermally altered residual type kaolin. It is produced in the Suzhou Yangshan area of Jiangsu province in China, thus being named. The quality is fine and smooth, and the whiteness can reach more than 90 percent after the baking, so the product is also named Suzhou carclazyte. The high-quality Suzhou clay is obtained by manual selection, the impurities are few, and the main minerals are tubular halloysite and flaky kaolinite, which are rare natural high-quality raw materials in special ceramics. 37-39% of alumina, 46-48% of silicon dioxide, 1730 ℃ of refractoriness and low plasticity. Mainly used for manufacturing ceramics. Can also be used as a bonding agent of refractory materials.

In a preferred embodiment of the present invention, the antibacterial agent is a silver-based nano antibacterial agent.

As a preferable technical scheme of the invention, the silver-based nano antibacterial agent is Micro-KF107.

The invention also discloses a preparation method of the ceramic glaze, which adopts the technical scheme that the preparation method comprises the following steps:

step 1, weighing each raw material in proportion;

step 2, adding industrial alumina into a phase transfer agent for calcination to obtain alpha-Al ₂ O ₃ ；

Step 3, calcining kaolin into calcined kaolin;

step 4, mixing alpha-Al ₂ O ₃ Mixing the calcined kaolin and other raw materials to obtain a blank ingredient;

step 5, adding water and a diluent into the blank ingredients in the step 4, and then performing ball milling to obtain powder;

step 6, drying, granulating, staling and molding the powder obtained in the step 5 to obtain an intermediate product; and 7, drying, bisque firing, glazing and glaze firing the intermediate product obtained in the step 6.

As a preferred embodiment of the present invention, in the step 7, the glaze firing system is as follows:

firstly heating to 100 ℃ and 200 ℃, and keeping the temperature for 0.5 hour respectively;

then gradually heating to 300 deg.C, 400 deg.C, 500 deg.C, 600 deg.C, 700 deg.C, 800 deg.C, 900 deg.C and 1000 deg.C, and keeping the temperature for 20min at each stage.

As a preferred technical scheme of the invention, in the glaze firing system, the heating rate is 8-10 ℃/min.

The invention has the beneficial effects that: according to the invention, industrial alumina and Suzhou kaolin are used as base materials, so that the glaze has higher whiteness, and the whitening effect can be further achieved by adding titanium dioxide, carboxymethyl cellulose is added to crosslink all materials together, the antibacterial agent is added to enable the glaze to have antibacterial and bacteriostatic effects, and sodium hexametaphosphate is added to improve the surface characteristics of nano zinc oxide and have greater influence on the rheological behavior of the nano zinc oxide glaze. The glaze with low viscosity, high stability and good uniformity can be obtained by adding the dispersing agent; the glaze prepared by the formula has good antibacterial effect, good glaze surface adaptability, no pinhole and bright white color.

Detailed Description

Example 1

The embodiment discloses a first implementation mode of the invention, and adopts the technical scheme that the invention comprises the following components:

industrial alumina, suzhou kaolin, titanium dioxide, carboxymethyl cellulose, micro-KF107, nano zinc oxide and sodium hexametaphosphate.

The weight ratio of each component is as follows: 71% industrial alumina, 20% Suzhou kaolin, 2% titanium dioxide, 1% carboxymethylcellulose, 1.5% micro-KF107, 4% nano-zinc oxide, 0.5% sodium hexametaphosphate.

The invention also discloses a preparation method of the ceramic glaze, which adopts the technical scheme that the preparation method comprises the following steps:

step 1, weighing 142g of industrial alumina, 40g of Suzhou kaolin, 4g of titanium dioxide, 2g of carboxymethyl cellulose, 3g of micro-KF107, 8g of nano zinc oxide and 1g of sodium hexametaphosphate.

Step 2, adding the industrial alumina into a phase transfer agent, and calcining at 1200 ℃ to obtain alpha-Al ₂ O ₃ ；

Step 3, calcining kaolin into calcined kaolin;

step 4, mixing alpha-Al ₂ O ₃ Mixing the calcined kaolin and other raw materials to obtain a blank ingredient;

step 5, adding water and a diluent into the blank ingredient in the step 4, and then performing ball milling to obtain powder;

step 6, drying, granulating, staling and molding the powder obtained in the step 5 to obtain an intermediate product;

and 7, drying, bisque firing, glazing and glaze firing the intermediate product obtained in the step 6. The temperature, the holding time and the heating speed in the glaze firing process are shown as follows:

example 2

This example is different from example 1 in that the glaze firing temperature rise rate was 10 ℃/min.

Example 3

This example is different from example 1 in that the glaze firing temperature rise rate was 10 ℃/min.

Although the present invention has been described in detail with reference to the specific embodiments, the present invention is not limited to the above embodiments, and various changes and modifications without inventive changes may be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.

Claims (8)

1. A ceramic glaze is characterized by comprising the following components:

industrial alumina, kaolin, titanium dioxide, carboxymethyl cellulose, an antibacterial agent, zinc oxide and sodium hexametaphosphate.

2. The ceramic glaze material as claimed in claim 1, wherein the weight ratio of each component is as follows:

71 percent of industrial alumina, 20 percent of kaolin, 2 percent of titanium dioxide, 1 percent of carboxymethyl cellulose, 1.5 percent of antibacterial agent, 4 percent of zinc oxide and 0.5 percent of sodium hexametaphosphate.

3. The ceramic glaze according to claim 1, wherein: the kaolin is Suzhou kaolin.

4. The ceramic glaze according to claim 1, wherein: the antibacterial agent is a silver-based nano antibacterial agent.

5. A ceramic glaze according to claim 3, wherein: the silver-based nano antibacterial agent is Micro-KF107.

6. A method of preparing the ceramic enamel of claim 1 comprising the steps of:

step 1, weighing each raw material in proportion;

step 2, adding industrial alumina into a phase inversion agent for calcination to obtain alpha-Al ₂ O ₃ ；

Step 3, calcining kaolin into calcined kaolin;

step 4, mixing alpha-Al ₂ O ₃ Mixing the calcined kaolin and other raw materials to obtain a blank ingredient;

step 5, adding water and a diluent into the blank ingredient in the step 4, and then performing ball milling to obtain powder;

step 6, drying, granulating, staling and molding the powder obtained in the step 5 to obtain an intermediate product;

and 7, drying, biscuit firing and glazing the intermediate product obtained in the step 6, and then firing the intermediate product in a glaze manner.

7. The method for preparing ceramic glaze according to claim 6, wherein: in the step 7, the glaze firing system is as follows:

firstly heating to 100 ℃ and 200 ℃, and preserving heat for 0.5 hour respectively;

then gradually heating to 300 deg.C, 400 deg.C, 500 deg.C, 600 deg.C, 700 deg.C, 800 deg.C, 900 deg.C and 1000 deg.C, and keeping the temperature for 20min at each stage.

8. The method for preparing ceramic glaze according to claim 7, wherein: in the glaze firing system, the heating rate is 8-10 ℃/min.