阅读说明：本技术 一种抗菌釉料及其制备方法和应用 (Antibacterial glaze and preparation method and application thereof ) 是由 梁健 江伟辉 劳新斌 洪翔 戚芳 于 2020-12-07 设计创作，主要内容包括：本发明公开了一种抗菌釉料,由底釉和面釉构成；所述底釉的组成为硅酸锆7～12wt％、二氧化钛1～2wt％、余量为基础底釉料；所述面釉的组成为稀土无机化合物0.5～2wt％、余量为基础面釉料,所述稀土无机化合物中含有含量≥16wt％的二氧化钛和含量≥15wt％的二氧化钍。此外,还公开了上述抗菌釉料的制备方法和应用。本发明通过配方设计以获得可辐射远红外线的釉层,使得卫生陶瓷制品具有除菌抗菌作用,从而有效提高了抗菌卫生陶瓷的抗菌效果,更好地解决了环境优化及净化的问题。(The invention discloses an antibacterial glaze material, which consists of a ground glaze and a surface glaze; the base glaze comprises 7-12 wt% of zirconium silicate, 1-2 wt% of titanium dioxide and the balance of base glaze; the overglaze comprises 0.5-2 wt% of rare earth inorganic compound and the balance of basic overglaze, wherein the rare earth inorganic compound contains titanium dioxide with the content of more than or equal to 16 wt% and thorium dioxide with the content of more than or equal to 15 wt%. In addition, a preparation method and application of the antibacterial glaze are also disclosed. The glaze layer capable of radiating far infrared rays is obtained through the formula design, so that the sanitary ceramic product has the antibacterial and antibacterial effects, the antibacterial effect of the antibacterial sanitary ceramic is effectively improved, and the problems of environment optimization and purification are better solved.)

1. An antibacterial glaze material comprises a ground glaze and a surface glaze; the method is characterized in that: the base glaze comprises 7-12 wt% of zirconium silicate, 1-2 wt% of titanium dioxide and the balance of base glaze; the overglaze comprises 0.5-2 wt% of rare earth inorganic compound and the balance of basic overglaze, wherein the rare earth inorganic compound contains titanium dioxide with the content of more than or equal to 16 wt% and thorium dioxide with the content of more than or equal to 15 wt%.

2. The antibacterial glaze according to claim 1, wherein: the chemical composition of the rare earth inorganic compound is 35-43 wt% of silicon dioxide, 16-25 wt% of titanium dioxide, 15-20 wt% of thorium dioxide, 1-4 wt% of calcium oxide, 2-3 wt% of cerium dioxide, 1-2 wt% of phosphorus pentoxide, 1-1.5 wt% of aluminum oxide, 0.5-1 wt% of polonium, 0.4-1.2 wt% of barium oxide, 0.5-0.9 wt% of lanthanum oxide, 0.5-0.6 wt% of sulfur trioxide, 0.3-0.4 wt% of sodium oxide, 0.2-0.3 wt% of neodymium oxide, 0.2-0.3 wt% of potassium oxide, 0.2-0.3 wt% of zinc oxide, 0.1-0.2 wt% of yttrium oxide, 0.1-0.2 wt% of silver oxide, 0.1-0.2 wt% of iron oxide, 0-0.1 wt% of chlorine, 0-0.1 wt% of germanium oxide, 0.1 wt% of lead oxide, and 10-12 wt% of burnt lead.

3. The antibacterial glaze according to claim 1, wherein: according to the proportion of the basic ground glaze in the ground glaze, the basic ground glaze comprises 25-35 wt% of quartz, 20-28 wt% of terrazzo albite, 8-12 wt% of calcined kaolin, 1.5-4 wt% of calcined zinc oxide, 1-4 wt% of calcined alpha alumina, 6-10 wt% of wollastonite, 8-12 wt% of limestone, 2-6 wt% of strontium carbonate, 3-6 wt% of high-temperature frit and 1-3 wt% of calcined talc.

4. The antibacterial glaze according to claim 1, wherein: according to the proportion of the basic overglaze, the basic overglaze comprises 8-12 wt% of quartz, 11-15 wt% of terrazzo albite, 1-6 wt% of wollastonite, 1-7 wt% of limestone, 1-5 wt% of kaolin, 1-6 wt% of calcined zinc oxide, 2-8 wt% of calcined talc and 40-60 wt% of high-temperature frit.

5. The antibacterial glaze according to claim 3 or 4, wherein: the melting temperature of the high-temperature frit is 1050-1150 ℃.

6. The method for preparing an antibacterial glaze according to any one of claims 1 to 5, characterized in that:

(1) preparation of the ground glaze

Proportioning the components of the ground glaze, and performing ball milling and mixing to obtain the ground glaze with the average fineness of 6-13 mu m;

(2) preparation of overglaze

And (3) proportioning the components of the overglaze, and performing ball milling and mixing to obtain the overglaze with the average fineness of 6-10 mu m.

7. Use of an antibacterial enamel according to one of claims 1 to 5, characterized in that: firstly applying base glaze and then applying surface glaze on the surface of the ceramic body; the thickness of the ground glaze is 0.6-1 mm, and the thickness of the cover glaze is 0.05-0.15 mm; and drying the glazed ceramic blank, and sintering to obtain the ceramic product with the antibacterial glaze layer.

8. The use of an antibacterial glaze according to claim 7, characterized in that: sintering at 1170-1250 ℃ for 0.5-2 h with a sintering period of 14-25 h.

Technical Field

The invention relates to the technical field of ceramic glaze, in particular to an antibacterial glaze as well as a preparation method and application thereof.

Background

With the improvement of living standard and living quality of people, people pay more and more attention to environment optimization and purification of public places, living spaces, daily life and hospital facilities. The antibacterial sanitary ceramic products are more and more widely applied in the life of people, and some antibacterial sanitary ceramic manufacturers try to add silver ions into antibacterial sanitary ceramic glaze for antibiosis in order to make up for the vacancy of the antibacterial sanitary ceramic products on the market in the aspects of healthy and environment-friendly home furnishing, but the antibacterial rate of a common silver ion antibacterial material is only about 95%, the durability of a silver ion antibacterial agent is not good, the antibacterial effect is lower than 85% after half a year, and the antibacterial effect of the antibacterial sanitary ceramic products using the antibacterial sanitary ceramic products is poor. In order to better solve the problems of environmental optimization and purification, a ceramic glaze with higher antibacterial rate needs to be produced and applied to the antibacterial sanitary ceramic products.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide an antibacterial glaze material, wherein a glaze layer capable of radiating far infrared rays is obtained through formula design, so that a ceramic product has a sterilization and antibacterial effect, the antibacterial effect of the antibacterial sanitary ceramic is effectively improved, and the problems of environment optimization and purification are better solved. The invention also aims to provide a preparation method and application of the antibacterial glaze.

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

the antibacterial glaze provided by the invention is composed of a ground glaze and a surface glaze; the base glaze comprises 7-12 wt% of zirconium silicate, 1-2 wt% of titanium dioxide and the balance of base glaze; the overglaze comprises 0.5-2 wt% of rare earth inorganic compound and the balance of basic overglaze, wherein the rare earth inorganic compound contains titanium dioxide with the content of more than or equal to 16 wt% and thorium dioxide with the content of more than or equal to 15 wt%.

Zirconium is a transition element, which readily absorbs hydrogen, nitrogen and oxygen, and has a very strong affinity for oxygen in particular; titanium is a silvery white transition element, and the chemical and physical properties of titanium are similar to those of zirconium; thorium is a radioactive metal element, which is extremely reactive in its chemical nature. According to the invention, three elements of zirconium, titanium and thorium are introduced into the glaze, so that the glaze layer obtained by firing the glaze can radiate far infrared rays, thereby playing a role in sterilization and antibiosis.

The invention can take the following further measures:

the chemical composition of the rare earth inorganic compound is 35-43 wt% of silicon dioxide, 16-25 wt% of titanium dioxide, 15-20 wt% of thorium dioxide, 1-4 wt% of calcium oxide, 2-3 wt% of cerium dioxide, 1-2 wt% of phosphorus pentoxide, 1-1.5 wt% of aluminum oxide, 0.5-1 wt% of polonium, 0.4-1.2 wt% of barium oxide, 0.5-0.9 wt% of lanthanum oxide, 0.5-0.6 wt% of sulfur trioxide, 0.3-0.4 wt% of sodium oxide, 0.2-0.3 wt% of neodymium oxide, 0.2-0.3 wt% of potassium oxide, 0.2-0.3 wt% of zinc oxide, 0.1-0.2 wt% of yttrium oxide, 0.1-0.2 wt% of silver oxide, 0.1-0.2 wt% of iron oxide, 0-0.1 wt% of chlorine, 0.1-0.1 wt% of germanium oxide, 0.1 wt% of lead oxide, and 10-10 wt% of burnt lead.

Furthermore, according to the proportion of the basic ground glaze in the ground glaze, the basic ground glaze comprises, by weight, 25-35% of quartz, 20-28% of terrazzo albite, 8-12% of calcined kaolin, 1.5-4% of calcined zinc oxide, 1-4% of calcined alpha alumina, 6-10% of wollastonite, 8-12% of limestone, 2-6% of strontium carbonate, 3-6% of high-temperature frit and 1-3% of calcined talc.

Furthermore, according to the proportion of the basic overglaze, the basic overglaze comprises 8-12 wt% of quartz, 11-15 wt% of terrazzo albite, 1-6 wt% of wollastonite, 1-7 wt% of limestone, 1-5 wt% of kaolin, 1-6 wt% of calcined zinc oxide, 2-8 wt% of calcined talc and 40-60 wt% of high-temperature frit.

In the scheme, the melting temperature of the high-temperature frit is 1050-1150 ℃.

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

the preparation method of the antibacterial glaze provided by the invention comprises the following steps:

(1) preparation of the ground glaze

Proportioning the components of the ground glaze, and performing ball milling and mixing to obtain the ground glaze with the average fineness of 6-13 mu m;

(2) preparation of overglaze

And (3) proportioning the components of the overglaze, and performing ball milling and mixing to obtain the overglaze with the average fineness of 6-10 mu m.

The application of the antibacterial glaze material provided by the invention is that firstly, the ground coat is applied on the surface of the ceramic body, and then the surface glaze is applied; the thickness of the ground glaze is 0.6-1 mm, and the thickness of the cover glaze is 0.05-0.15 mm; and drying the glazed ceramic blank, and sintering to obtain the ceramic product with the antibacterial glaze layer.

Further, in the application of the antibacterial glaze, the antibacterial glaze is sintered at 1170-1250 ℃, the high-temperature heat preservation time is 0.5-2 hours, and the sintering period is 14-25 hours.

The invention has the following beneficial effects:

(1) according to the invention, three elements of zirconium, titanium and thorium are introduced into the glaze, the transition elements of zirconium and titanium are subjected to surface water activation, so that hydroxyl for capturing free holes is generated on the surface of the glaze, hydroxyl free radicals are formed, free electrons of the transition elements are quickly combined with absorbed oxygen to form superoxide free radicals, and finally, through the combination of the hydroxyl free radicals, the superoxide free radicals and the thorium, the glaze layer obtained by sintering the glaze is promoted to radiate far infrared rays (the far infrared emissivity is more than 0.83), so that the functions of resisting bacteria, removing ammonia, removing formaldehyde and the like are achieved.

(2) According to the invention, the high-temperature frit is added into the formula of the overglaze and the ground glaze, so that the glossiness of the glaze surface is improved, and the quality of the glaze surface can be effectively improved; on the other hand, the catalyst can provide a good environment for the combined catalysis of the three elements of zirconium, titanium and thorium, and is beneficial to the exertion of the effects of antibiosis, ammonia removal and formaldehyde removal.

The present invention will be described in further detail with reference to examples.

Detailed Description

1. The antibacterial glaze material provided by the embodiment of the invention is composed of a ground glaze and a surface glaze; wherein the content of the first and second substances,

the ground glaze comprises, by weight, 25-35% of quartz, 20-28% of water-milled albite, 8-12% of calcined kaolin, 1.5-4% of calcined zinc oxide, 1-4% of calcined alpha alumina, 6-10% of wollastonite, 8-12% of limestone, 2-6% of strontium carbonate, 3-6% of high-temperature frit, 1-3% of calcined talc, 7-12% of zirconium silicate and 1-2% of titanium dioxide.

The overglaze comprises 8-12 wt% of quartz, 11-15 wt% of water-milled albite, 1-6 wt% of wollastonite, 1-7 wt% of limestone, 1-5 wt% of kaolin, 1-6 wt% of calcined zinc oxide, 2-8 wt% of calcined talc, 40-60 wt% of high-temperature frit and 0.5-2 wt% of rare earth inorganic compound.

The raw material compositions of the ground glaze and the overglaze used in the examples of the present invention are shown in tables 1 and 2.

TABLE 1 composition of raw materials for base coat of examples of the present invention

TABLE 2 composition of the raw materials for overglaze of the examples of the present invention

Tables 1 and 2 the underglaze and overglaze used a conventional high temperature frit with a melting temperature of 1100 ℃, which was chemically composed of: 54.74 wt% of silicon oxide, 11.21 wt% of aluminum oxide, 0.14 wt% of iron oxide, 0.06 wt% of titanium oxide, 19.22 wt% of calcium oxide, 1.52 wt% of magnesium oxide, 1.2 wt% of zirconium oxide, 0.8 wt% of boron oxide, 0.5 wt% of zinc oxide, 1.96 wt% of barium oxide, 6.48 wt% of potassium oxide, 1.69 wt% of sodium oxide and 0.48 wt% of ignition loss.

The chemical composition of the rare earth inorganic compound in the overglaze is shown in table 3.

TABLE 3 chemical composition of rare earth inorganic compound of examples of the present invention

2. The preparation method of the antibacterial glaze material provided by the embodiment of the invention comprises the following steps:

(1) preparation of the ground glaze

Proportioning raw materials of the ground glaze shown in the table 1, and performing ball milling and mixing to obtain the ground glaze with the average fineness of 6-13 mu m;

(2) preparation of overglaze

The overglaze with the average fineness of 6-10 mu m is obtained after the raw materials of the overglaze are proportioned and mixed by ball milling as shown in Table 2.

The composition of the raw materials of the glaze of each embodiment of the invention is shown in table 4.

3. The application of the antibacterial glaze material of the embodiment of the invention is as follows: firstly applying base glaze and then applying surface glaze on the surface of the ceramic body; the thickness of the ground glaze is 0.6-1 mm, and the thickness of the surface glaze is 0.05-0.15 mm; and drying the glazed ceramic blank, and firing at 1170-1250 ℃ for 0.5-2 h at a high-temperature heat preservation time for 20h to obtain the ceramic product with the glaze layer.

The application process parameters of the examples of the present invention are shown in table 4.

Table 4 raw material composition and applied process parameters for various examples of the present invention

Numbering in glaze compositions corresponds to tables 1, 2, 3

4. Performance testing

The ceramic product prepared by the embodiments of the invention is subjected to Escherichia coli and Staphylococcus aureus antibacterial rate test according to the detection method of JC/T897-2014; and (3) testing the removal rate of ammonia gas and formaldehyde according to a detection method of QB/T2761-2006, and testing the far infrared emissivity according to a detection method of LY/T3203-2020/4.4. The results are shown in Table 5.

TABLE 5 results of performance testing of ceramic articles prepared according to examples of the present invention

The results in table 5 show that the glaze layer formed by the antibacterial glaze material provided by the embodiment of the invention effectively plays an antibacterial role, the antibacterial rates of escherichia coli and staphylococcus aureus are both more than 95% (the highest can be more than 99%), and the antibacterial rate is still more than 95% after one year; the ammonia removal rate and the formaldehyde removal rate both reach more than 80 percent (the highest removal rate can reach more than 90 percent).