CN112876291B

CN112876291B - Preparation method of self-cleaning antibacterial ceramic plate

Info

Publication number: CN112876291B
Application number: CN202110141929.6A
Authority: CN
Inventors: 乔栓虎; 袁国梁; 谭洪波
Original assignee: Shandong Electric Shield Polytron Technologies Inc
Current assignee: Shandong Electric Shield Polytron Technologies Inc
Priority date: 2021-02-02
Filing date: 2021-02-02
Publication date: 2023-03-24
Anticipated expiration: 2041-02-02
Also published as: CN112876291A

Abstract

The invention discloses a preparation method of a self-cleaning antibacterial ceramic plate, which comprises a high-temperature glaze firing stage, wherein a smoke extractor or/and a heat extraction fan are/is adopted to enable the pressure in a furnace to be 100-300 Pa, and glaze firing is carried out; and after glaze firing, naturally cooling to room temperature, spraying the nano titanium oxide mixed solution on the surface of the glaze by adopting an atomization method, drying, and then sintering at the temperature of 520-560 ℃, and preserving heat for 1 hour to obtain the self-cleaning antibacterial ceramic plate. The invention adopts low-pressure exhaust in the furnace and atomization spraying of the nano titanium oxide, which can promote the gas in the glaze to be discharged to the maximum extent, reduce the pinholes of the glaze surface and reduce the content and the number of the gas holes in the glaze; thus, an anatase film layer with compactness, high bonding strength and better photocatalysis is formed on the surface of the product, and the product has higher antibacterial effect.

Description

Preparation method of self-cleaning antibacterial ceramic plate

Technical Field

The invention relates to a preparation method of a self-cleaning antibacterial ceramic plate, and belongs to the technical field of building materials.

Background

The first origin of the antibacterial ceramic is a Kilamic ceramic plate developed by INAX corporation in Japan in the last 90 th century, and in recent years, the antibacterial ceramic plate with a self-cleaning function is developed along with the continuous deep development of the industry under the background of the large-scale rise of the domestic ceramic industry. The key point of the self-cleaning antibacterial ceramic plate is the addition of an inorganic antibacterial agent in the glaze, and the titanium oxide is the most widely researched and applied in China at present. Titanium oxide is used in two ways, one is to add the titanium oxide into glaze to prepare split-phase liquid drop self-cleaning glaze, and the other is to form a film on the surface of a ceramic plate and utilize the film to carry out self-cleaning and photocatalysis. Deng Zhihua, etc. show that when the titanium oxide addition in the glaze is 5wt%, it has high surface hardness and good hydrophilic self-cleaning property. The Chinese invention patent application CN 101417892A discloses a technology for preparing nano phase-splitting self-cleaning glaze for ceramic external wall tiles by using high-titanium waste residues as main raw materials, and the nano phase-splitting self-cleaning glaze is high in photocatalytic efficiency, good in antifouling effect of glaze surfaces and self-cleaning. The disadvantages of adding titanium oxide to glazes are: 1. the titanium oxide is converted into rutile type with poor photocatalytic activity in a high-temperature heat treatment process, the content and the quantity of titanium oxide distributed on the surface are small, the titanium oxide is easy to agglomerate, and a large number of pinholes are easy to form on the surface; 2. the normal temperature glaze system can form a porous system along with the temperature rise and water loss, and the existence of a large number of internal pores is also the main reason for the uneven surface of the glaze and more pores and needle holes in the later period. Chinese patent application CN 111792670A discloses a manufacturing process of low-porosity ceramic, which adds an anatase type titanium oxide photocatalyst into wax water, and attaches the photocatalyst to the surface of a ceramic tile in a waxing way; but such methods are not very versatile.

Disclosure of Invention

Aiming at the prior art, the invention provides a preparation method of a self-cleaning antibacterial ceramic plate in order to improve the self-cleaning effect and the antibacterial effect of the ceramic.

The invention is realized by the following technical scheme:

a preparation method of a self-cleaning antibacterial ceramic plate comprises a high-temperature glaze firing stage, wherein in the glaze firing stage, a smoke extractor or/and a heat extraction fan are/is adopted to enable the pressure in a furnace to be 100-300 Pa, and glaze firing is carried out; after glaze firing, naturally cooling to room temperature, spraying the nano titanium oxide mixed solution on the surface of the glaze by adopting an atomization method, drying, and then sintering at the temperature of 520-560 ℃, and preserving heat for 1 hour to obtain the self-cleaning antibacterial ceramic plate.

Further, when the glaze is fired, the adopted glaze is conventional glaze, and when the glaze is used, the glaze is ground into slurry, coated on the green body and then enters a roller kiln for firing. Specifically, the raw materials may be: 30% of potassium feldspar, 16% of albite, 8% of calcite, 6% of calcined talc, 5% of barium carbonate, 5% of alumina, 17% of clinker, 8% of calcined soil and 5% of kaolinite in percentage by weight.

Further, in the glaze firing, the firing set temperature is 1150 ℃, and the firing period is 72min.

The nano titanium oxide mixed solution is prepared by the following method: taking 1L of deionized water, adding 10g of sodium polyacrylate as a dispersing agent, adding 1.5g of nano titanium oxide powder (the particle size of the nano titanium oxide powder is 5-7 nm), and carrying out nano ball milling for 5min (the particle size is less than 100nm after the nano ball mill mixes the materials) for later use.

Further, the specific way of spraying the nano titanium oxide mixed solution on the surface of the glaze by adopting an atomization method is as follows: and (3) coating a nano functional layer on the surface of the sample by using an ultrasonic atomizer, wherein the size of atomized particles is 1-5 microns, and the atomization time is 3s (the 3s time is based on that continuous functional layers with the thickness less than 10 microns are sequentially paved on the surface of glaze).

The core process of the invention is the low-pressure exhaust in the furnace and the atomization spraying of the nano titanium oxide, and the low-pressure is adopted: promoting the gas in the glaze to be discharged to the maximum extent, reducing the pinholes of the glaze and reducing the content and the number of the air holes in the glaze; the low-temperature sintering has the following functions: an anatase film layer with compactness, high bonding strength and better photocatalysis is formed on the surface of the product. After the porosity of the glaze is reduced and the pinhole of the glaze is reduced, an anatase film layer with better combination effect and catalytic effect is formed on the surface of the glaze, so that the product has self-cleaning and antibacterial functions.

The preparation method of the self-cleaning antibacterial ceramic plate has the following advantages:

(1) In the glaze firing stage, micro-size air holes in the glaze are eliminated to the maximum extent under low pressure in the furnace, and the phenomena of pinholes, bubbles, rough glaze surface, unevenness and the like caused by the bubbles and the like are reduced, so that the product achieves the self-cleaning purpose;

(2) The nano ball milling process reduces the particle size of the aggregate to the maximum extent, and the low-temperature sintering exerts the photocatalysis effect of anatase titanium oxide to the maximum extent, so that the product has higher antibacterial effect.

All documents cited herein are incorporated by reference in their entirety and to the extent such documents do not conform to the meaning of the present invention, the present invention shall control. Further, the various terms and phrases used herein have the ordinary meaning as is well known to those skilled in the art.

Drawings

FIG. 1: photos of the ceramic plate prepared by the original process.

FIG. 2: photographs of the ceramic plates prepared according to the present invention.

Detailed Description

The present invention will be further described with reference to the following examples. However, the scope of the present invention is not limited to the following examples. It will be understood by those skilled in the art that various changes and modifications may be made to the invention without departing from the spirit and scope of the invention.

Unless otherwise specified, the instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like known in the art and are commercially available. Unless otherwise specified, the experimental methods, detection methods, and the like described in the following examples are conventional experimental methods, detection methods, and the like in the prior art.

EXAMPLES preparation of self-cleaning antibacterial ceramic plate

The preparation method comprises the following steps: comprises a high-temperature glaze firing stage, wherein in the glaze firing stage, a heat extraction fan is adopted to enable the pressure in the furnace to be 100-300 Pa, and glaze firing is carried out (the firing setting temperature is 1150 ℃, the firing period is 72 min); and after glaze firing, naturally cooling to room temperature, spraying the nano titanium oxide mixed solution on the surface of the glaze by adopting an atomization method, drying, and then sintering at the temperature of 520-560 ℃, and preserving heat for 1 hour to obtain the self-cleaning antibacterial ceramic plate.

When glaze firing is carried out, the adopted glaze comprises the following components: 30% of potassium feldspar, 16% of albite, 8% of calcite, 6% of calcined talc, 5% of barium carbonate, 5% of alumina, 17% of clinker, 8% of calcined soil and 5% of kaolinite in percentage by weight.

The nano titanium oxide mixed solution is prepared by the following method: taking 1L of deionized water, adding 10g of sodium polyacrylate serving as a dispersing agent, adding 1.5g of nano titanium oxide powder (the particle size of the nano titanium oxide powder is 5-7 nm), and carrying out nano ball milling for 5min (the particle size is less than 100nm after the nano ball mill mixes the materials) for later use.

The specific way of spraying the nano titanium oxide mixed solution on the glaze surface by adopting an atomization method is as follows: and (3) coating a nano functional layer on the surface of the sample by adopting an ultrasonic atomizer, wherein the size of atomized particles is 1-5 microns, and the atomization time is 3s.

The invention has carried out 9 groups of experiments, except that glaze burns the pressure, sintering temperature (as shown in table 1), other steps, parameter, etc. are homogeneous. After the self-cleaning antibacterial ceramic plate was prepared, antibacterial performance test tests (test was performed using JIS Z2801.

TABLE 1

Conventional process (TiO is added into glaze) ₂ And then high-temperature glaze firing) is shown in fig. 1 (the surface of the traditional ceramic glaze layer is uneven under a magnifier, the surface is easy to store dirt and dirt, and bacteria are easy to propagate), and the photo of the ceramic plate prepared by the invention is shown in fig. 2.

The above examples are provided to enable those skilled in the art to fully disclose and describe how to make and use the claimed embodiments, and are not intended to limit the scope of the disclosure. Modifications apparent to those skilled in the art are intended to be within the scope of the appended claims.

Claims

1. A preparation method of a self-cleaning antibacterial ceramic plate comprises a high-temperature glaze firing stage, and is characterized in that: in the glaze firing stage, a smoke extractor or/and a heat extraction fan are/is adopted to enable the pressure of 100-300 Pa to be formed in the furnace, glaze firing is carried out, the firing set temperature is 1150 ℃, the firing period is 72min, gas in the glaze is promoted to be discharged to the maximum extent, glaze surface pinholes are reduced, and the content and the number of the gas holes in the glaze are reduced; after glaze firing, cooling to room temperature, spraying a nano titanium oxide mixed solution on the surface of the glaze by adopting an atomization method, drying and sintering, wherein the sintering temperature is 520-560 ℃, and preserving heat for 1 hour to form an anatase film layer on the surface of the glaze, thereby obtaining the self-cleaning antibacterial ceramic plate;

the glaze firing adopts glaze materials which comprise the following components: 30% of potassium feldspar, 16% of albite, 8% of calcite, 6% of calcined talc, 5% of barium carbonate, 5% of alumina, 17% of clinker, 8% of calcined soil and 5% of kaolinite in percentage by weight;

the nano titanium oxide mixed solution is prepared by the following method: taking 1L water, adding 10g sodium polyacrylate as a dispersing agent, adding 1.5g nanometer titanium oxide powder, and performing nanometer ball milling for later use.

2. The preparation method of the self-cleaning antibacterial ceramic plate according to claim 1, wherein the specific way of spraying the nano titanium oxide mixed solution on the surface of the glaze by adopting the atomization method is as follows: and (3) coating a nano functional layer on the surface of the sample by using an ultrasonic atomizer, wherein the size of atomized particles is 1-5 microns, and the atomization time is 3s.

3. A self-cleaning antibacterial ceramic plate prepared by the method for preparing a self-cleaning antibacterial ceramic plate according to claim 1 or 2.