CN112110651B - Preparation method of ultra-smooth sanitary ceramic antibacterial glaze - Google Patents

Abstract

The invention discloses an ultra-smooth sanitary ceramic antibacterial glaze and a preparation method thereof, wherein the sanitary ceramic antibacterial glaze comprises the following raw materials in parts by weight: 50-80 parts of ceramic frit, 2-21 parts of quartz, 1-8 parts of potassium feldspar, 1-6 parts of albite, 2-5 parts of calcined talc, 1-4 parts of calcined zinc oxide, 2-5 parts of calcite, 0.5-2 parts of nano zirconium and 2-9 parts of nano tourmaline; 1-3 parts of rare earth antibacterial material; 1-3 parts of rare earth antibacterial material, wherein the rare earth antibacterial material is prepared from nano tourmaline and nano rare earth oxide according to the weight percentage of 5-9: 1-5. The antibacterial glaze has good antibacterial effect and smooth glaze surface.

Description

Preparation method of ultra-smooth sanitary ceramic antibacterial glaze

Technical Field

The invention relates to a preparation method of an ultra-smooth sanitary ceramic antibacterial glaze.

Background

The new coronavirus, hepatitis A, hepatitis E, typhoid, cholera, hand-foot-and-mouth disease and some parasitic diseases can be transmitted through the fecal oral route. Therefore, the antibacterial and bactericidal function of the toilet environment, especially the toilet bowl, is particularly important in the human plague resisting germ infection. Chinese patent CN101218091A is an antibacterial glaze and enamel published by international company of american standards that achieves antibacterial effect by adding 8 wt.% to 35 wt.% zinc oxide to the top glaze. The invention can achieve sufficient antibacterial effect by adding at least 10 wt.% of ZnO, and the zinc oxide has high cost, and can cause glaze crystallization, increase of firing temperature, influence on color difference, smoothness, porosity and the like when being used in large amount. Chinese patent CN105272377A discloses a preparation method of antibacterial ceramic. The patent adopts a sol-gel method to attach antibacterial ions on a white carbon black carrier to obtain an antibacterial material, and then the antibacterial material is mixed with a common glaze to prepare the antibacterial glaze. The effective antibacterial material is metal ion liquid and rare earth ion salt. The invention can reach the antibacterial rate of more than 90 percent required by JC/T897-2014 by adding at least 10 wt.% of antibacterial material, and the antibacterial active ingredients of the antibacterial material are mainly Ag and Ag-Zn. And excessive antibacterial materials are added, so that the color difference, smoothness, porosity and other properties of the ceramic glaze surface are influenced.

Chinese patent CN101218091A is an antibacterial glaze and enamel published by international company of american standards that achieves antibacterial effect by adding 8 wt.% to 35 wt.% zinc oxide to the top glaze. The invention can achieve sufficient antibacterial effect by adding at least 10 wt.% of ZnO, and the zinc oxide has high cost, and can cause glaze crystallization, increase of firing temperature, influence on color difference, smoothness, porosity and the like when being used in large amount. Chinese patent CN105272377A discloses a preparation method of antibacterial ceramic. The patent adopts a sol-gel method to attach antibacterial ions on a white carbon black carrier to obtain an antibacterial material, and then the antibacterial material is mixed with a common glaze to prepare the antibacterial glaze. The effective antibacterial material is metal ion liquid and rare earth ion salt. The invention can reach the antibacterial rate of more than 90 percent required by JC/T897-2014 by adding at least 10 wt.% of antibacterial material, and the antibacterial active ingredients of the antibacterial material are mainly Ag and Ag-Zn. And excessive antibacterial materials are added, so that the color difference, smoothness, porosity and other properties of the ceramic glaze surface are influenced.

Disclosure of Invention

The invention mainly aims to provide a preparation method of an ultra-smooth sanitary ceramic antibacterial glaze.

The technical scheme adopted by the invention for solving the technical problem is as follows:

An ultra-smooth sanitary ceramic antibacterial glaze comprises the following raw materials in percentage by weight:

50-80 parts of ceramic frit, 2-21 parts of quartz, 1-8 parts of potassium feldspar, 1-6 parts of albite, 2-5 parts of calcined talc, 1-4 parts of calcined zinc oxide, 2-5 parts of calcite, 0.5-2 parts of nano zirconium and 2-9 parts of nano tourmaline; 1-3 parts of rare earth antibacterial material; 1-3 parts of rare earth antibacterial material, wherein the rare earth antibacterial material is prepared from nano tourmaline and nano rare earth oxide according to the weight percentage of 5-9: 1-5.

Preferably, the content of the ceramic frit is controlled to be 60-75% of the total weight of the raw materials.

In a preferred embodiment, in the rare earth antibacterial material, the nano tourmaline and the nano rare earth oxide are mixed according to the weight percentage of 7: 3.

In a preferred embodiment, the rare earth oxide comprises Dy₂ O₂ 、Sm₂ O₃ 、Pr₆ O₁₁ One or more rare earth oxides.

In a preferred embodiment, the fabric further comprises 0.1-0.3 part of organic fibers.

In a preferred embodiment, the ultra-smooth roughness average is less than 0.052 um.

The invention also provides a preparation method of the ultra-smooth sanitary ceramic antibacterial glaze, which comprises the following steps of: ceramic frit, quartz, potash feldspar, albite, calcined talc, calcined zinc oxide, calcite, nano zirconium and nano tourmaline; putting the raw materials into a ball mill, adding sodium carboxymethylcellulose, adding water for ball milling, finishing ball milling until the size of slurry is less than 10 mu m and accounts for 80-90%, adding a rare earth antibacterial material, continuously ball milling and uniformly mixing to obtain a milled product, controlling the abrasive grain degree to be 90-99%, sieving with a 180-mesh sieve, removing iron, adjusting the performance of the glaze slurry to enable the concentration of the glaze slurry to reach 1.65 +/-0.05 g/cm3, and obtaining the uniform ultra-smooth antibacterial sanitary ceramic overglaze.

In a preferred embodiment, after the rare earth antibacterial material is prepared from nano tourmaline and nano rare earth oxide according to the weight percentage, a proper amount of water, a dispersing agent and a debonding agent are added, the mixture is placed into a ball mill for intermittent ball milling at 400r/min for 100-.

In a preferred embodiment, the method further comprises: and spraying the obtained uniform ultra-smooth antibacterial sanitary ceramic overglaze on the surface of the sanitary ceramic white blank.

In a preferred embodiment, the thickness of the glaze layer in the green state is 0.15-0.5mm, and the thickness of the porcelain-forming overglaze is controlled to be 0.1-0.3 mm.

In a preferred embodiment, the glazed ceramic green body is sent into a drying kiln to be dried until the water content is less than 1 percent, and is put into the kiln to be fired for one time, wherein the firing temperature is 1200-1250 ℃.

Compared with the background technology, the technical scheme has the following advantages:

1. the ceramic frit is introduced, and due to the high content of silicon dioxide and aluminum oxide, the fired glaze surface not only has high hardness, but also has high strength. The high hardness can ensure that the glaze is not easy to scratch and has better stain resistance effect. And the high strength can ensure that the glaze is not easy to break.

2. Tourmaline powder has permanent spontaneous polarization effect, so that the tourmaline powder has negative ion release property. The negative ions released by the antibacterial agent can wrap the bacteria with positive charges, so that the bacteria lose the proliferation condition, and the antibacterial effect is generated. Under the action of an electrostatic field of tourmaline particles, the added rare earth elements with valence-change characteristics can increase the electron transfer capacity and enhance the electrolytic capacity of the tourmaline on air water molecules, thereby enhancing the anion release function of the tourmaline and enhancing the antibacterial performance of a glaze surface. The rare earth antibacterial sanitary ceramic glaze provided by the invention meets the requirements of JC/T8972014 antibacterial ceramic product antibacterial performance that the antibacterial rate is more than or equal to 90 percent and the antibacterial durability is more than or equal to 85 percent.

3. The antibacterial glaze provided by the invention is proved to have a certain mildew-proof effect. The rice treated under the same high-temperature condition is placed on the antibacterial glaze surface and the common glaze surface treated under the same sterilization condition, then the rice is respectively placed in glass culture dishes treated under the same sterilization condition, the glass culture dishes are sealed by a preservative film and a glass cover, and only part of the antibacterial glaze surface is obviously observed to be yellow after the rice is placed for 72 hours or more, while the common ceramic is completely yellow and grows black mold. Experiments prove that the antibacterial ceramic glaze has a mildew-proof effect obviously superior to that of common sanitary ceramics, and the mildew-proof glaze has a high application value for relatively humid and closed toilet environments.

4. The slurry with the granularity of less than 10 mu m accounts for 90-99 percent, so that the roughness of the glaze surface can be reduced, the glaze surface is smoother, and is not easy to hang dirt and easy to clean. The test shows that the lowest point of the roughness of the glaze surface can be reduced to 0.021um, and the average value of the roughness can be reduced to 0.025 um. On the other hand, tourmaline has permanent electrodes, and each crystal in the powder has positive and negative electrodes. To a certain extent, the finer the tourmaline powder, the stronger the anion releasing function. Therefore, after the superfine ball milling, the release function of tourmaline negative ions uniformly dispersed in the glaze slip is also enhanced, thereby improving the antibacterial performance of the glaze surface.

5. According to the ultra-smooth antibacterial glaze provided by the invention, the antibacterial material is directly added into the glaze, and the generated antibacterial negative ions exist in the glaze surface and the vicinity of the glaze surface, so that the effect of inhibiting bacteria is achieved without directly contacting antibacterial silver ions.

Drawings

The invention is further illustrated by the following figures and examples.

FIG. 1 is a diagram of the results of the anti-mildew experiment according to the preferred embodiment.

Detailed Description

The sanitary ceramic glaze of the invention consists of two layers of glaze: the ground glaze is common sanitary ceramic white glaze, and the overglaze is an antibacterial glaze containing rare earth antibacterial material, and the rare earth antibacterial material consists of nano tourmaline and rare earth oxide. The ground glaze is directly sprayed on the surface of the sanitary ceramic blank to obtain the sanitary ceramic white blank. The preparation method of the ultra-smooth sanitary ceramic antibacterial glaze provided by the invention is realized by the following steps:

1) preparing a white blank:

the ground glaze is common sanitary ceramic opaque glaze, and the ground glaze is directly sprayed on the surface of a sanitary ceramic blank to obtain a sanitary ceramic white blank.

2) Preparing a cover glaze:

the materials are prepared according to the following weight percentage: 50-80% of ceramic frit (Tangshan Zhuang Xin science and technology Co., Ltd.), 2-21% of quartz, 1-8% of potassium feldspar, 1-6% of albite, 2-5% of calcined talc, 1-4% of calcined zinc oxide, 2-5% of calcite, 0.5-2% of nano zirconium and 2-9% of nano tourmaline; putting the raw materials into a ball mill, adding sodium carboxymethylcellulose which is not more than 0.3 percent of the total weight of the raw materials, adding water for ball milling, finishing ball milling until the granularity of slurry is less than 10 mu m and accounts for 80-90 percent, adding 1-3 percent of rare earth antibacterial material, continuously carrying out ball milling and uniformly mixing to obtain a mixture, controlling the granularity of the obtained mixture to be 90-99 percent, sieving the obtained mixture with a 180-mesh sieve, removing iron, adjusting the performance of glaze slurry to enable the concentration of the glaze slurry to reach 1.65 +/-0.05 g/cm3, and obtaining the uniform ultra-smooth antibacterial sanitary ceramic overglaze;

The rare earth antibacterial material consists of nano tourmaline and nano rare earth oxide (including Dy)₂ O₂ 、Sm₂ O₃ 、Pr₆ O₁₁ One or more of rare earth oxides). The materials are mixed according to the weight percentage of 7:3, a proper amount of water, a dispersing agent and a debonding agent are added, and the mixture is placed into a ball mill to be milled for 120min in an intermittent ball milling mode at 350r/min, so that the mixture can be milled. And putting the milled slurry into a drying box, drying and crushing to obtain the rare earth antibacterial material.

3) Spraying a surface glaze: virtually spraying the ultra-smooth antibacterial glaze obtained in the step 2) on the surface of a sanitary ceramic white blank, wherein the thickness of a glaze layer in a green state is 0.15-0.5 mm, and the thickness of a finished porcelain surface glaze is controlled to be 0.1-0.3 mm;

4) and (3) firing: and (3) feeding the glazed sanitary ceramic green body into a drying kiln for drying until the water content is less than 1%, and feeding the sanitary ceramic green body into the kiln for one-time firing at the firing temperature of 1200-1250 ℃.

5) And (3) performance testing: and (3) testing the antibacterial property and antibacterial durability of the glaze according to JC/T8972014 antibacterial property of the antibacterial ceramic product. And (3) detecting the surface roughness Ra of the sample according to the 7.2 requirement of GB/T10610-2009, measuring each sample for 5 times, and averaging the measurement results to obtain the roughness of the single sample. The final detection result is the roughness average value of 5 samples, and the numerical value is accurate to 3 bits after the decimal point.

6) Examples 1-7 are ultra-smooth sanitary ceramic antibacterial glazes prepared by the above method according to the components and parameters of table 1 below.

TABLE 1

7) Comparative examples 1-8 show that the roughness of the enamel surface is lower regardless of the difference between the ceramic frit and the formulation components. The method shows that the abrasive grain size is controlled to be 90-99% and is beneficial to preparing the ultra-smooth glaze surface. When the content of the ceramic frit is less than 60% or more than 75%, pores are easily formed on the glaze, the roughness is relatively high, and the formation of an ultra-smooth glaze is not favorable. The ceramic frit belongs to a calcined raw material, does not generate violent physical and chemical reactions in the sintering process, and is favorable for preparing an ultra-smooth glaze surface by introducing a proper amount of ceramic frit. The content of the ceramic frit is controlled to be 60-75%, and the roughness of the ceramic glaze surface can be reduced to be below 0.04 microns. In comparative examples 6 to 8, it was found that increasing the content of nano tourmaline to a certain extent results in an increase in roughness, which is not favorable for the smoothness of the glaze.

TABLE 2-examples 3 to 4 tests for antibacterial Properties

The antibacterial test results of comparative examples 1 to 4 show that the antibacterial performance of the glaze surface can be greatly improved by independently adding a certain content of nano tourmaline or rare earth antibacterial material. The antibacterial rate and the antibacterial durability can be obviously improved by adding the nano tourmaline and the rare earth antibacterial material in a composite way, and when 3 percent of nano tourmaline and 1.5 percent of rare earth antibacterial material are added (example 4), the antibacterial performance of the glaze surface meets the requirement that the antibacterial rate is more than or equal to that required by JC/T8972014 antibacterial ceramic product antibacterial performance. The content of the nano tourmaline and the rare earth antibacterial material is continuously increased (examples 5-8), so that the antibacterial rate of the sample can be increased to more than 99%. This is because tourmaline has permanent electrodes, and each crystal in the powder has positive and negative electrodes. The negative ions released by the antibacterial agent can wrap the bacteria with positive charges, so that the bacteria lose the proliferation condition, and the antibacterial effect is generated. To a certain extent, the finer the tourmaline powder, the stronger the anion release function. Therefore, the release function of tourmaline negative ions uniformly dispersed in the glaze slip is enhanced after the superfine ball milling. The rare earth element has large atomic radius, the electronic structures of the outer layer and the secondary outer layer are basically the same, and the third layer 4f orbit has unpaired electrons, so that the material has valence-changing property. Under the action of an electrostatic field of tourmaline particles, the addition of rare earth elements can increase the electron transfer capacity and enhance the electrolytic capacity of tourmaline on air water molecules, thereby strengthening the negative ion release function of tourmaline again and further enhancing the antibacterial function of ceramic glaze. When the content of the fusion cake is controlled to be 60-75%, and the nano tourmaline and rare earth antibacterial material are added in a compounding manner, the glaze surface prepared by the process method disclosed by the invention not only has an ultralow roughness value, but also has excellent antibacterial property and antibacterial durability, and meets the requirements of antibacterial ceramic products JC/T8972014 antibacterial property.

8) The rice treated under the same high-temperature condition is placed on the antibacterial glaze surface and the common glaze surface treated under the same sterilization condition, then the rice is respectively placed in glass culture dishes treated under the same sterilization condition, the glass culture dishes are sealed by preservative films and glass covers, and only part of the antibacterial glaze surface is obviously observed to be yellow after being placed for 72 hours or more, while the common ceramic is completely yellow and grows black mold (figure 1). Experiments prove that the antibacterial ceramic glaze has a mildew-proof effect obviously superior to that of common sanitary ceramics, and the mildew-proof glaze has a high application value for relatively humid and closed toilet environments.

The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.

Claims (9)

1. An ultra-smooth sanitary ceramic antibacterial glaze is characterized in that: the raw materials comprise the following components in percentage by weight:

50-80 parts of ceramic frit, 2-21 parts of quartz, 1-8 parts of potassium feldspar, 1-6 parts of albite, 2-5 parts of calcined talc, 1-4 parts of calcined zinc oxide, 2-5 parts of calcite, 0.5-2 parts of nano zirconium and 2-9 parts of nano tourmaline; 1-3 parts of rare earth antibacterial material, wherein the rare earth antibacterial material is prepared from nano tourmaline and nano rare earth oxide according to the weight percentage of 5-9: 1-5; controlling the content of the fusion cake to be 60-75%, and controlling the roughness of the ceramic glaze surface to be below 0.04 microns; the ceramic frit has a high silica and alumina content.

2. The ultra-smooth sanitary ceramic antibacterial glaze according to claim 1, characterized in that: in the rare earth antibacterial material, the nano tourmaline and the nano rare earth oxide are mixed according to the weight percentage of 7: 3.

3. The ultra-smooth sanitary ceramic antibacterial glaze according to claim 1, characterized in that: the rare earth oxide comprises Dy₂ O₂ 、Sm₂ O₃ 、Pr₆ O₁₁ At least one of rare earth oxides.

4. The ultra-smooth sanitary ceramic antibacterial glaze according to claim 1, characterized in that: also comprises 0.1 to 0.3 portion of organic fiber.

5. The preparation method of the ultra-smooth sanitary ceramic antibacterial glaze according to any one of claims 1 to 3, characterized in that: firstly, mixing the following raw materials in percentage by weight: ceramic frit, quartz, potash feldspar, albite, calcined talc, calcined zinc oxide, calcite, nano zirconium and nano tourmaline; putting the raw materials into a ball mill, adding sodium carboxymethylcellulose, adding water for ball milling, finishing ball milling until the slurry granularity is less than 10 mu m and accounts for 80-90%, adding a rare earth antibacterial material, continuously ball milling and uniformly mixing to obtain a product, controlling the abrasive grain size to be 90-99%, sieving with a 180-mesh sieve, removing iron, adjusting the glaze slurry performance to enable the glaze slurry concentration to reach 1.65 +/-0.05 g/cm³ To obtain the uniform ultra-smooth antibacterial sanitary ceramic overglaze.

6. The preparation method of the ultra-smooth sanitary ceramic antibacterial glaze according to claim 5, characterized in that: the rare earth antibacterial material is prepared by mixing nano tourmaline and nano rare earth oxide according to the weight percentage, adding a proper amount of water, a dispersing agent and a debonding agent, putting the mixture into a ball mill, performing intermittent ball milling at 400 r/min for 100-.

7. The method for applying the ultra-smooth antibacterial sanitary ceramic glaze according to any one of claims 1 to 4, which is characterized by comprising the step of spraying the uniform ultra-smooth antibacterial sanitary ceramic overglaze on the surface of a sanitary ceramic blank.

8. The method for applying the ultra-smooth sanitary ceramic antibacterial glaze according to claim 7,

the thickness of the glaze layer in the green state is 0.15-0.5mm, and the thickness of the ceramic surface glaze is controlled to be 0.1-0.3 mm.

9. The application method of the ultra-smooth sanitary ceramic antibacterial glaze according to claim 7, characterized in that: and (3) feeding the glazed sanitary ceramic green body into a drying kiln for drying until the water content is less than 1%, and feeding the sanitary ceramic green body into the kiln for one-time firing at the firing temperature of 1200-1250 ℃.

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