阅读说明：本技术 一种具有抗菌功能的陶瓷釉及其制备方法和应用 (Ceramic glaze with antibacterial function and preparation method and application thereof ) 是由 林锦威 钟保民 徐瑜 于 2019-12-06 设计创作，主要内容包括：本发明涉及建筑陶瓷技术领域,尤其涉及一种具有抗菌功能的陶瓷釉及其制备方法和应用。一种具有抗菌功能的陶瓷釉,原料组分包括抗菌剂、含氧化硅的物质和含氧化铝的物质；所述抗菌剂的化学成分包括氧化锌、氧化铋和氧化银中的一种或多种,总原料的化学成分按照重量百分比计算为：所述氧化锌≥3％,所述氧化铋≥0.5％,所述氧化银≥0.05％；总原料的化学成分按照重量百分比计算为：氧化硅≥38％和氧化铝≤16％。本发明的目的在于提出一种具有抗菌功能的陶瓷釉,该釉料能够实现抗菌功能,有效地杀灭细菌,抗菌性能稳定,抗菌效果好。(The invention relates to the technical field of building ceramics, in particular to a ceramic glaze with an antibacterial function and a preparation method and application thereof. A ceramic glaze with antibacterial function comprises raw material components including an antibacterial agent, a substance containing silicon oxide and a substance containing aluminum oxide; the chemical components of the antibacterial agent comprise one or more of zinc oxide, bismuth oxide and silver oxide, and the chemical components of the total raw materials are calculated according to the weight percentage: the zinc oxide is more than or equal to 3 percent, the bismuth oxide is more than or equal to 0.5 percent, and the silver oxide is more than or equal to 0.05 percent; the total raw materials comprise the following chemical components in percentage by weight: more than or equal to 38 percent of silicon oxide and less than or equal to 16 percent of aluminum oxide. The invention aims to provide a ceramic glaze with an antibacterial function, which can realize the antibacterial function, effectively kill bacteria, and has stable antibacterial performance and good antibacterial effect.)

1. The ceramic glaze with the antibacterial function is characterized in that the raw material components comprise an antibacterial agent, a substance containing silicon oxide and a substance containing aluminum oxide;

the chemical components of the antibacterial agent comprise one or more of zinc oxide, bismuth oxide and silver oxide, and the chemical components of the total raw materials are calculated according to the weight percentage: the zinc oxide is more than or equal to 3 percent, the bismuth oxide is more than or equal to 0.5 percent, and the silver oxide is more than or equal to 0.05 percent;

the total raw materials comprise the following chemical components in percentage by weight: more than or equal to 38 percent of silicon oxide and less than or equal to 16 percent of aluminum oxide, wherein in the total adding amount of the silicon oxide, more than or equal to 10 percent of the silicon oxide is introduced in the form of fused quartz or high-silicon clinker, and in the total adding amount of the aluminum oxide, more than or equal to 10 percent of the aluminum oxide is introduced in the form of calcined kaolin or calcined aluminum oxide.

2. The ceramic glaze with the antibacterial function according to claim 1, wherein the chemical components of the total raw materials in the antibacterial agent are calculated according to weight percentage, the zinc oxide is more than or equal to 8%, wherein at least 1/3 content in the zinc oxide is introduced in the form of calcined zinc oxide.

3. The ceramic glaze with the antibacterial function according to claim 1, wherein the antibacterial agent comprises 0.5-3% of bismuth oxide in percentage by weight based on the chemical components of the total raw materials.

4. The ceramic glaze with the antibacterial function according to claim 1, further comprising zirconium silicate, wherein the zirconium silicate is greater than or equal to 1% in chemical composition of the total raw materials by weight percent.

5. The ceramic glaze with the antibacterial function according to claim 1, further comprising iron oxide, wherein the content of the iron oxide is less than or equal to 0.15% in terms of the chemical composition of the total raw materials in percentage by weight.

6. The preparation method of the ceramic glaze with the antibacterial function according to claim 1, wherein the antibacterial agent is added into the raw materials of the ceramic glaze according to the weight percentage, water is added into the raw materials, and the ceramic glaze with the antibacterial function is prepared by ball milling for 5-12 hours, wherein the fineness of ball milling slurry is a ten-thousand-hole sieve, the screen residue is 0.7-1.2%, and the granularity D of the slurry is ₅₀＝10±3μm，D ₉₀＝32±5μm。

7. The method for preparing ceramic tiles using ceramic glaze with antibacterial function according to claim 6, characterized by comprising the following steps:

(1) ball milling powder and granulating by a spray tower;

(2) pressing and drying the green bricks;

(3) spraying a cover glaze, and performing ink-jet printing treatment;

(4) pouring the antibacterial glaze: spraying the ceramic glaze with the antibacterial function on the surface of the ink-jet printing layer;

(5) and putting into a kiln for sintering to obtain the ceramic tile with the antibacterial function.

8. The method for preparing ceramic tiles using ceramic glaze with antibacterial function according to claim 7, wherein the thickness of the antibacterial glaze layer sprayed in the step (4) is not less than 0.1 mm.

9. The ceramic tile using the ceramic glaze with the antibacterial function according to claim 7, wherein the firing temperature in the step (5) is 1150-1250 ℃ and the firing time is 50-90 min.

10. The method for preparing ceramic tiles using ceramic glaze with antibacterial function according to claim 7, wherein the kiln firing is further followed by one or more steps of edging, polishing, grading or antifouling treatment.

Technical Field

The invention relates to the technical field of building ceramics, in particular to a ceramic glaze with an antibacterial function and a preparation method and application thereof.

Background

The most common bacteria in the living room are colibacillus and staphylococcus aureus which have the greatest threat to human health. In particular to Escherichia coli called as 'human health first killer', which can cause gastrointestinal tract infection of human body or animal when invading some parts of human body or animal, mainly caused by infection of specific pilus antigen, pathogenic toxin, etc. Staphylococcus aureus has its trace in air, water and dust. In recent years, when a body is infected with staphylococcus aureus, leukocytes in the body are reduced, so that the resistance of the body is reduced, and the risk of disease is increased. For home decoration, dead corners of pollution and bacteria breeding always exist, bacteria are easy to breed particularly in places such as family kitchens, toilets and the like, fine pinholes which cannot be seen by naked eyes exist on the surfaces of ceramic tiles, the service life of the ceramic tiles is long, bacteria are easy to accumulate and breed and even infect, and the health of people is seriously affected. Therefore, how to impart excellent antibacterial performance to ceramic tiles is a key issue in the field of architectural ceramics.

Disclosure of Invention

Aiming at the problems in the background art, the invention aims to provide a ceramic glaze with an antibacterial function, which can realize the antibacterial function and effectively kill bacteria under the condition of not influencing the chromaticity and the appearance of the original product, and has stable antibacterial performance and good antibacterial effect.

The invention also aims to provide a preparation method of the ceramic glaze with the antibacterial function, and the prepared glaze has high-efficiency bactericidal and bacteriostatic effects and stable sustainable bactericidal effects, and solves the problem that the conventional glaze does not have antibacterial performance or has poor antibacterial performance.

The invention also aims to provide a preparation method of the ceramic tile with the ceramic glaze with the antibacterial function, the ceramic tile prepared by the ceramic glaze with the antibacterial function can reach the indexes of JC/T897-2014 antibacterial ceramic product antibacterial performance, the antibacterial rate is more than or equal to 90 percent, the antibacterial durability is more than or equal to 85 percent, and the ceramic tile has high-efficiency antibacterial capability and strong antifouling capability.

In order to achieve the purpose, the invention adopts the following technical scheme:

a ceramic glaze with antibacterial function comprises raw material components including an antibacterial agent, a substance containing silicon oxide and a substance containing aluminum oxide;

the chemical components of the antibacterial agent comprise one or more of zinc oxide, bismuth oxide and silver oxide, and the chemical components of the total raw materials are calculated according to the weight percentage: the zinc oxide is more than or equal to 3 percent, the bismuth oxide is more than or equal to 0.5 percent, and the silver oxide is more than or equal to 0.05 percent;

the total raw materials comprise the following chemical components in percentage by weight: more than or equal to 38 percent of silicon oxide and less than or equal to 16 percent of aluminum oxide, wherein in the total adding amount of the silicon oxide, more than or equal to 10 percent of the silicon oxide is introduced in the form of fused quartz or high-silicon clinker, and in the total adding amount of the aluminum oxide, more than or equal to 10 percent of the aluminum oxide is introduced in the form of calcined kaolin or calcined aluminum oxide.

Zn ²⁺The plasma acts directly with the bacteria because of Zn ²⁺The plasma can destroy the activity of active enzyme of cell membrane or cell plasma of bacteria at very low concentration, damage the three-dimensional structure (denaturation), and cause dysfunction in a short time, so that Zn is added ²⁺(Ag ⁺、Bi ²⁺) Are toxic to microorganisms (bacteria, molds, viruses also broadly including algae and protozoa). Zn ²⁺Can strongly attract enzyme protein in the bacterial body, and can be quickly combined to make the enzyme using said enzyme as essential group lose activity, so that the bacterial can be dead, and when the bacterial body is killed, Zn can be added ²⁺And the bacterial colonies dissociate and contact with other bacterial colonies to play a new round of antibacterial action, and the process is repeated. The antibacterial agent contained in the ceramic glaze with antibacterial function comprises one or more of zinc oxide, bismuth oxide and silver oxide, and the three antibacterial agents can be freely combined or exist independently and can enable the three antibacterial agents to be combined freelyThe ceramic glaze has an antibacterial effect.

In addition, the content of the silicon oxide in the ceramic glaze with the antibacterial function is more than or equal to 38 percent, wherein more than or equal to 10 percent of the total amount of the silicon oxide is required to be introduced in the form of fused quartz or high-silicon clinker, the content of the aluminum oxide is less than or equal to 16 percent, wherein more than or equal to 10 percent of the total amount of the aluminum oxide is required to be introduced in the form of calcined kaolin or calcined aluminum oxide, and the antibacterial ion (Zn) in the glaze is favorably formed by limiting the content of the silicon oxide and the aluminum oxide in the ceramic glaze with the antibacterial function and limiting the component sources of the silicon oxide and the aluminum oxide ²⁺、Ag ⁺And Bi ²⁺) The antibacterial glaze plays a role of a carrier, can stabilize the existence of antibacterial ions in the glaze and prevent the antibacterial ions from easily separating from the glaze layer, can slowly release the antibacterial ions, stabilizes the concentration of the antibacterial ions and stabilizes the antibacterial performance.

The antibacterial ceramic glaze provided by the present application contains the raw materials in a total weight percentage of 100%.

Preferably, in the antibacterial agent, the chemical components of the total raw materials are calculated according to weight percentage, the zinc oxide is more than or equal to 8 percent, wherein the content of at least 1/3 in the zinc oxide is introduced in the form of calcined zinc oxide.

When the content of zinc oxide in the ceramic glaze with the antibacterial function is more than or equal to 8%, the antibacterial effect is more obvious, and as the calcined zinc oxide has more effective activity than other zinc sources, the particle size is small, the specific surface area is large, and the replacement performance and the adsorbability of the ceramic glaze with the antibacterial function are higher, wherein at least 1/3 content in the zinc oxide is introduced in the form of calcined zinc oxide, and the residual zinc oxide is added in the form of raw zinc oxide, so that the antibacterial effect of the ceramic glaze with the antibacterial function is more favorably improved.

Preferably, in the antibacterial agent, the addition amount of the bismuth oxide is 0.5-3% by weight of the chemical components of the total raw materials.

Bismuth oxide as fluxing agent can reduce the melting temperature of glaze and simultaneously lead Bi to ²⁺More easily dissolved in silicon-oxygen tetrahedron, and excessive addition of bismuth oxide easily leads toThe melting temperature of the glaze is too low, the reaction such as decomposition, oxidation and the like in the blank is not completed, so that the bubbles of the blank are difficult to discharge, the condition of large-area pinholes on the glaze surface is caused, and meanwhile, most Bi is ²⁺The glass phase directly dissolved in the ceramic glaze can not be dissolved in the silicon-oxygen tetrahedron, thereby reducing the antibacterial performance.

Preferably, when the ceramic glaze is a non-transparent glaze, the ceramic glaze further comprises zirconium silicate, and the zirconium silicate is more than or equal to 1% of the total raw materials in percentage by weight.

Zirconium silicate is added into the ceramic glaze with the antibacterial function, so that the antibacterial performance is favorable, and the addition of the zirconium silicate can promote Zn ²⁺、Ag ⁺And Bi ²⁺The antibacterial ions can be better dissociated from the cellular protoplasm enzymes and contact with other bacterial colonies to play a new round of antibacterial action, and further the antibacterial performance of the ceramic glaze with the antibacterial function is improved.

Preferably, the iron oxide-containing composite material also comprises iron oxide, and the content of the iron oxide is less than or equal to 0.15 percent in terms of the chemical components of the total raw materials in percentage by weight.

Since some enzyme proteins can loosely bind small molecular weight organic substances (enzyme cofactors), such as metal ions and some organic compounds with low molecular weight, if the content of iron oxide in the ceramic glaze with antibacterial function is too high, iron ions Fe released by the enzyme proteins are too high ²⁺Is easy to be combined with enzyme protein, thereby affecting Zn ²⁺、Ag ⁺And Bi ²⁺Binding to enzymes affects the antimicrobial effect.

Preferably, the antibacterial agent is added into the raw materials of the ceramic glaze according to the weight percentage, water is added into the raw materials, and the ceramic glaze with the antibacterial function is prepared by ball milling for 5-12 hours, wherein the fineness of ball milling slurry is ten thousand-hole sieve, the screen residue is 0.7-1.2%, and the particle size D of the slurry is ₅₀＝10±3μm，D ₉₀＝32±5μm。

The final antibacterial performance is affected by the excessively fine or coarse slurry, for example, when the slurry is excessively coarse, slurry particles are agglomerated and coarse, the stability and uniformity are poor, the performance of the slurry is reduced, and the antibacterial performance is correspondingly reduced.

Preferably, the ceramic glaze with the antibacterial function comprises the following chemical components in percentage by weight:

3-10% (1.5-4%) of zinc oxide (wherein the content is introduced in the form of calcined zinc oxide), 0.5-3% of bismuth oxide, 0.05-0.5% of silver oxide, 1-2% of zirconium silicate, 0.05-0.15% of iron oxide, 38-48% (5-10%) of silicon oxide (wherein the content is introduced in the form of fused silica), 10-16% (3-5%) of aluminum oxide (wherein the content is introduced in the form of calcined kaolin), 3-6% of potassium oxide, 3-6% of sodium oxide, 6-14% of calcium oxide, 3-8% of magnesium oxide and 10-13% of loss on ignition.

Preferably, the preparation method of the ceramic tile using the ceramic glaze with the antibacterial function comprises the following steps:

(1) ball milling powder and granulating by a spray tower;

(2) pressing and drying the green bricks;

(3) spraying a cover glaze, and performing ink-jet printing treatment;

(4) pouring the antibacterial glaze: spraying the ceramic glaze with the antibacterial function on the surface of the ink-jet printing layer;

(5) and putting into a kiln for sintering to obtain the ceramic tile with the antibacterial function.

The ceramic glaze with the antibacterial function is sprayed on the surface of the ceramic tile overglaze, so that the ceramic glaze can be in direct contact with air, and when bacteria in the air are adsorbed on the surface of the ceramic tile, the antibacterial agent in the ceramic glaze with the antibacterial function can play a role in destroying cell membranes of the bacteria or the activity of cell protoplasm active enzyme, and playing a role in antibacterial sterilization.

Preferably, the thickness of the antibacterial glaze layer sprayed in the step (4) is more than or equal to 0.1 mm.

The glaze layer of the ceramic glaze with the antibacterial function is too thin, and the antibacterial effect is influenced by few antibacterial ions in the glaze layer, so that the antibacterial effect on the surface of the ceramic tile is weakened.

Preferably, the firing temperature in the step (5) is 1150-1250 ℃, and the firing time is 50-90 min.

After high-temperature firing, the ceramic tile of the obtained ceramic glaze with the antibacterial function has good antibacterial performance, and can reach the antibacterial performance index of JC/T897-2014 antibacterial ceramic products.

Preferably, the kiln firing process further comprises one or more steps of edging, polishing, grading or antifouling treatment.

Preferably, the antifouling treatment is surface waxing or surface treatment with a surface antifouling treatment agent for polished glazed tiles.

The ceramic tile using the ceramic glaze with the antibacterial function is subjected to edging, polishing, grading and antifouling treatment to obtain the antifouling glazed brick with the antibacterial function, so that the antibacterial performance and antifouling performance of the glazed brick are effectively improved, and a strong practical effect is achieved while an attractive effect is achieved.

Compared with the prior art, the invention has the following beneficial effects:

1. a ceramic glaze with antibacterial agent is disclosed, the antibacterial agent includes one or more of zinc oxide, bismuth oxide and silver oxide, the three antibacterial agents can be freely combined or exist independently, and antibacterial ion (Zn) in the antibacterial agent ²⁺、Ag ⁺And Bi ²⁺) The activity of cell membrane or cell protoplasm active enzyme of bacteria can be destroyed under very low concentration, thereby killing bacteria, and a new round of antibacterial action is exerted through ion dissociation and contact with other bacterial colonies, and the antibacterial action is strong and the antibacterial effect is good.

2. By limiting the content of silicon oxide and aluminum oxide in the ceramic glaze with antibacterial function and limiting the component sources of the silicon oxide and the aluminum oxide, the formation of silicon-oxygen tetrahedron in the glaze is facilitated, and antibacterial ions (Zn) in the glaze are resisted ²⁺、Ag ⁺And Bi ^{2 +}) The antibacterial glaze plays a role of a carrier, can stabilize the existence of antibacterial ions in the glaze and prevent the antibacterial ions from easily separating from the glaze layer, so that the antibacterial ions are slowly released, the concentration of the antibacterial ions is stabilized, and the prepared glaze has stable antibacterial performance.

3. By controlling the preparation process parameters of the ceramic glaze with the antibacterial function, such as the ball milling fineness and the slurry granularity, and controlling the preparation process of a product using the glaze, such as the glaze coating thickness, the obtained glaze has a stable structure and excellent antibacterial performance, the prepared ceramic tile can reach the indexes of JC/T897-2014 antibacterial ceramic product antibacterial performance, the antibacterial rate is more than or equal to 90 percent, and the antibacterial durability is more than or equal to 85 percent.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments.

And (3) performance testing:

1. and (3) determination of antibacterial rate: the antibacterial rate is determined according to the test method of JC/T897-2014 antibacterial ceramic product antibacterial performance.

2. And (3) antibacterial durability measurement: the antibacterial durability is determined according to the test method of JC/T897-2014 antibacterial ceramic product antibacterial performance.

3. And (3) antifouling rating measurement: the pollution agent for testing the pollution resistance of the ceramic tile comprises a paste pollution agent, a pollution agent capable of generating an oxidation reaction, a pollution agent capable of generating a film, olive oil and the like, wherein the pollution resistance is classified into 1-5 grades according to the difficulty of cleaning, and the higher the grade is, the better the pollution resistance is.

The conventional ceramic glaze raw material can be kaolin, calcined kaolin, Guangdong black mud, talc, calcined talc, potash albite, potash feldspar, albite, bentonite, dolomite, calcium carbonate, zinc oxide, calcined zinc oxide, silver sulfide, silver iodide, bismuth oxide and bismuth sulfate.