CN111718124A - Antibacterial lead-free ceramic fritted glaze and preparation method thereof - Google Patents

Abstract

The invention relates to an antibacterial lead-free ceramic fritted glaze and a preparation method thereof, belonging to the technical field of ceramic materials. The fritted glaze comprises the following components: functional material II, quartz, feldspar, dolomite, boric acid, zinc oxide and alumina. When the functional material II is prepared, specific granite porphyry at the east end of the north foot of the hillside at an ore deposit and at the south edge of the middle part of inner Mongolia is taken as a raw material, firstly, the granite porphyry collides with each other, the collision condition is controlled, different element crystals can be subjected to wall-breaking, peeling and separation layer by layer, then, parameters of a hydraulic classifier are adjusted according to the specific gravity of the different element crystals, and water separation and grading enrichment are carried out, so that the functional material II can be prepared. The functional material II is added, the density and the smoothness of the glaze surface can be improved, oil stains on the produced porcelain can be cleaned by clean water without using a cleaning agent after the produced porcelain is used, secondary pollution is avoided, and far infrared and negative oxygen ions can be released after the rare earth elements are subjected to high-temperature treatment, so that the finally prepared ceramic device has the functions of antibiosis, easy cleaning and fresh keeping.

Description

Antibacterial lead-free ceramic fritted glaze and preparation method thereof

Technical Field

The invention belongs to the technical field of ceramic materials, and particularly relates to an antibacterial lead-free ceramic fritted glaze and a preparation method thereof.

Background

At present, in the two-time firing of bone china and magnesium china, fritted glaze is generally used in China, but the prior fritted glaze cannot realize the antibacterial and easy-cleaning function, wherein if the antibacterial function is realized, an antibacterial agent must be added, so that the cost is increased, on the other hand, if the adding amount is too much, the ceramic glaze surface is defective, and if the adding amount is small, the expected antibacterial effect cannot be achieved. Therefore, there is a need for fritted glazes that can provide antibacterial and easy-to-clean functions to ceramics.

Disclosure of Invention

In view of the above, an object of the present invention is to provide an antibacterial lead-free ceramic fritted glaze; the second purpose is to provide a preparation method of the antibacterial lead-free ceramic fritted glaze.

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

1. an antibacterial lead-free ceramic fritted glaze comprises the following components in percentage by mass: functional material II: 10-30%, quartz: 15-20%, feldspar 10-20%, dolomite: 5-12%, boric acid: 2-7%, zinc oxide: 2-7%, alumina: 10 to 25 percent;

the functional material II is prepared by the following method:

coarsely crushing granite, placing the granite in a self-collision type separator for collision separation, collecting materials which are discharged by the self-collision type separator and are 5mm in thickness, placing the materials which are 5mm in thickness in a wet ball mill with a discharge port equipped with a hydraulic classifier, obtaining the materials which are 50 meshes in thickness through the hydraulic classifier, placing the materials which are 50 meshes in thickness in a magnetic separation system for magnetic separation, and removing magnetic substances, wherein the mass fraction of the magnetic substances Fe and Ti is less than or equal to 0.1%, and the materials are defined as a functional material II; the granite is granite porphyry, is at the east end of the north foot of the mountain of the yin and is at the south edge of the middle part of the inner Mongolia at an ore deposit.

Preferably, standard corundum bricks are adhered to the circumferential direction of the inner wall of the roller of the self-collision separator, convex corundum bricks are uniformly embedded in the standard corundum bricks, the height of the convex corundum bricks is 50-100mm, a high-manganese wear-resistant discharge grate plate matched with the discharge port is mounted on the discharge port, and the aperture of a discharge hole of the discharge grate plate is 5 mm.

Preferably, the length of the roller of the self-collision type separator is 4500mm, the diameter of the roller is 2400mm, and the diameter of the feeding port is 400 mm; the rotating speed of the self-collision type separator is set to be 28-32 r/min.

Preferably, the mass ratio of the fine material with the diameter of 5mm to the water in the wet ball mill is 50-65:35-50, the installed capacity of a motor in the wet ball mill is 500kw, the electricity consumption in actual normal operation is 300 kw/h, and the rotating speed is 19-20 r/min.

Preferably, the mixing flow rate of water and materials in the hydraulic classifier is adjusted to be 75-100m³/h。

Preferably, the magnetic separation is completed in three stages, namely, firstly, the magnetic separation is carried out in a flat-plate magnetic separator with the magnetic field strength of 5500-.

Preferably, in the functional material II:

oxides of conventional elements: al (Al)₂O₃：13-14％，SiO₂：75-77，Fe₂O₃：0.06-0.08％，CaO：0.5-0.7％，MgO：0.05-0.07％，K₂O：5-5.5％，Na₂O：3.5-3.7％，TiO₂: 0.01 to 0.02 percent; vector burning: 0.38-0.4%;

oxide containing fifteen rare earth elements: la₂O₃：15-18mg/kg，CeO₂：35-40mg/kg，Pr₈O₁₁：3.0-3.5mg/kg，Nd₂O₃：10-12mg/kg，Sm₂O₃：1.5-2.0mg/kg，Eu₂O₃：0.5-1.0mg/kg，Gd₂O₃：1.5-2.0mg/kg，Tb₄O₇：0.2-1.0mg/kg，Dy₂O₃：1.2-1.5mg/kg，Ho₂O₃：0.2-0.4mg/kg，Er₂O₃：0.5-0.8mg/kg，Tm₂O₃：0.09-0.12mg/kg，Yb₂O₃：0.5-0.9mg/kg，Lu₂O₃：0.1-0.5mg/kg，Y₂O₃：7-9mg/kg。

Preferably, in the granite:

oxides of conventional elements: al (Al)₂O₃：13-15％，SiO₂：72-77％，Fe₂O₃：1.7-2.2％，CaO：0.9-1.5％，MgO：0.15-0.4％，K₂O：5.0-6.0％，Na₂O：3.2-4.0％，TiO₂: 0.12-0.2%, burning vector: 0.4 to 0.8 percent;

macroelements: n: 1000-1200mg/kg, P: 170-200mg/kg, K: 40000-50000 mg/kg;

medium elements: ca: 5500-6000Mg/kg, Mg: 800-900mg/kg, S: 70-80 mg/kg;

trace elements: cu: 2-5mg/kg, Fe: 13000-15000mg/kg, Mn: 180-250mg/kg, Zn: 40-80mg/kg, B: 6-8mg/kg, Se: 3.0-7.0mg/kg, Mo: 3.5-6.5 mg/kg;

oxide containing fifteen rare earth elements: la₂O₃：60-70mg/kg，CeO₂：130-150mg/kg，Pr₈O₁₁：15-20mg/kg，Nd₂O₃：65-80mg/kg，Sm₂O₃：12-20mg/kg，Eu₂O₃：0.3-1.0mg/kg，Gd₂O₃：14-20mg/kg，Tb₄O₇：2.5-5mg/kg，Dy₂O₃：14-20mg/kg，Ho₂O₃：2.5-3.0mg/kg，Er₂O₃：7.0-10.0mg/kg，Tm₂O₃：1.1-1.5mg/kg，Yb₂O₃：7-10mg/kg，Lu₂O₃：1.0-1.5mg/kg，Y₂O₃：80-120mg/kg；

Rare light metalOxide of the element: sc (Sc)₂O₃：30-50mg/kg，RbO₂：1300-1500mg/kg。

2. The preparation method of the antibacterial lead-free ceramic fritted glaze comprises the following steps:

uniformly mixing the functional material II, quartz, feldspar, dolomite, boric acid, zinc oxide and alumina, putting the mixture into a melting furnace, heating to 1450-.

Preferably, the particle sizes of the quartz, the feldspar, the dolomite, the boric acid, the zinc oxide and the alumina are all 80 meshes.

The invention has the beneficial effects that: the invention provides an antibacterial lead-free ceramic fritted glaze and a preparation method thereof, wherein a functional material II is added into the fritted glaze, so that the density of a glaze surface can be effectively improved, the smoothness of the glaze is improved, oil stains on the produced porcelain can be cleaned by clear water without using a cleaning agent after the porcelain is used, secondary pollution is avoided, and far infrared and negative oxygen ions can be released after rare earth elements are subjected to high-temperature treatment, so that a finally prepared ceramic device has the functions of antibiosis, easy cleaning and fresh keeping. The method comprises the following steps of preparing a functional material II, wherein the specific granite porphyry at the east end of the north foot of the mountain at an ore deposit and at the south edge of the middle part of inner Mongolia is used as a raw material, the granite porphyry ore deposit forms magma crystals in the magma forming process, multiple metal elements form a multiphase inclusion under the action of differentiation, assimilation and the like in the forming process, and more than 40 kinds of mineral elements are formed, wherein different metal elements have different densities, specific gravities and hardnesses. The lead-free fritted glaze has the advantages of simple preparation method and low cost, and is suitable for expanded production.

Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.

Drawings

For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:

FIG. 1 is a topographical view of granite used in example 1;

FIG. 2 is a topographical view of a functional material II prepared in example 1;

FIG. 3 is a microscopic view of the functional material II prepared in example 1;

FIG. 4 is a graph showing the results of an infrared radiation test of the functional material II prepared in example 1;

FIG. 5 is a topographical view of the antibacterial lead-free ceramic fritted glaze prepared in example 2;

FIG. 6 is a topographical view of the ceramic article prepared in example 3 in the sun;

FIG. 7 is a graph of light transmission test results for the ceramic articles prepared in example 3;

fig. 8 is a graph of the infrared radiation test results for the ceramic articles prepared in example 3.

Detailed Description

The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.

Granite used in the invention is granite porphyry, the ore deposit is located at east end of northern foot of the yin mountain and south edge of middle part of inner Mongolia, belongs to transition area of mountain region of yin mountain and plateau of Wulanchou city, the area of the ore deposit reaches 16 square kilometers, and the granite comprises:

oxides of conventional elements: al (Al)₂O₃：13-15％，SiO₂：72-77％，Fe₂O₃：1.7-2.2％，CaO：0.9-1.5％，MgO：0.15-0.4％，K₂O：5.0-6.0％，Na₂O：3.2-4.0％，TiO₂: 0.12-0.2%, burning vector: 0.4 to 0.8 percent;

macroelements: n: 1000-1200mg/kg, P: 170-200mg/kg, K: 40000-50000 mg/kg;

medium elements: ca: 5500-6000Mg/kg, Mg: 800-900mg/kg, S: 70-80 mg/kg;

trace elements: cu: 2-5mg/kg, Fe: 13000-15000mg/kg, Mn: 180-250mg/kg, Zn: 40-80mg/kg, B: 6-8mg/kg, Se: 3.0-7.0mg/kg, Mo: 3.5-6.5 mg/kg;

oxide containing fifteen rare earth elements: la₂O₃：60-70mg/kg，CeO₂：130-150mg/kg，Pr₈O₁₁：15-20mg/kg，Nd₂O₃：65-80mg/kg，Sm₂O₃：12-20mg/kg，Eu₂O₃：0.3-1.0mg/kg，Gd₂O₃：14-20mg/kg，Tb₄O₇：2.5-5mg/kg，Dy₂O₃：14-20mg/kg，Ho₂O₃：2.5-3.0mg/kg，Er₂O₃：7.0-10.0mg/kg，Tm₂O₃：1.1-1.5mg/kg，Yb₂O₃：7-10mg/kg，Lu₂O₃：1.0-1.5mg/kg，Y₂O₃：80-120mg/kg；

Oxides of rare light metal elements: sc (Sc)₂O₃：30-50mg/kg，RbO₂：1300-1500mg/kg。

The equipment parameters used in the examples are as follows:

the length of a roller of the self-collision type separator is 4500mm, the diameter of the roller is 2400mm, the diameter of a feeding hole is 400mm, standard corundum bricks are pasted in the circumferential direction of the inner wall of the roller, convex corundum bricks are uniformly embedded in the standard corundum bricks, the height of a protrusion of the convex corundum bricks is 50mm, a high-manganese wear-resistant discharge grate plate matched with a discharge hole is installed on the discharge hole of the separator, and the aperture of a discharge hole of the discharge grate plate is 5 mm;

the installed capacity of the motor in the wet ball mill is 500 kw.

Example 1

Production of functional materials based on granite II

Coarsely crushing granite to the particle size of less than 400mm, placing the granite in a self-collision type separator for collision separation, wherein the rotation speed of the separator is 28r/min, collecting fine materials of 5mm discharged by the self-collision type separator, adding the fine materials of 5mm and water into a wet ball mill with a hydraulic classifier at a discharge port according to the mass ratio of 60:40, wherein the power consumption of the ball mill in the ball milling process is 320kw/h, the rotation speed is 20r/min, and the mixing flow of the water and the materials in the hydraulic classifier is adjusted to be 90m³And h, obtaining fine materials of 50 meshes, carrying out magnetic separation on the fine materials of 50 meshes in a flat magnetic separator with the magnetic field strength of 8500 gauss, then carrying out magnetic separation in a flat magnetic separator with the magnetic field strength of 11000 gauss, and finally carrying out magnetic separation under a vertical ring pulsating high gradient magnetic separator with the magnetic field strength of 13000 gauss to remove magnetic substances, wherein the materials with the mass fraction of the magnetic substances Fe and Ti being less than 0.1 percent are defined as functional materials II, and the materials with the mass fraction of the magnetic substances Fe and Ti being more than or equal to 0.1 percent and less than or equal to 0.13 percent are defined as functional materials III.

The granite used in the above method has a morphology as shown in fig. 1, and comprises:

conventional elements: al (Al)₂O₃：14.04％、SiO₂：72.55％、Fe₂O₃：1.79％、CaO：0.98％、MgO：0.18％、K₂O：5.8％、Na₂O：3.7％、TiO₂: 0.19%, burning vector: 0.77 percent;

macroelements: n: 1005mg/kg, P: 178mg/kg, K: 44392 mg/kg;

medium elements: ca: 5922Mg/kg, Mg: 845mg/kg, S: 74.8 mg/kg;

trace elements: cu: 2.0mg/kg, Fe: 13689mg/kg, Mn: 197mg/kg, Zn: 42.4mg/kg, B: 6.8mg/kg, Se: 3.1mg/kg, Mo: 3.5 mg/kg;

fifteen rare earth elements: la₂O₃：62.77mg/kg、CeO₂：134.19mg/kg、Pr₈O₁₁：18.40mg/kg、Nd₂O₃：66.58mg/kg、Sm₂O₃：12.93mg/kg、Eu₂O₃：0.32mg/kg、Gd₂O₃：14.79mg/kg、Tb₄O₇：2.52mg/kg、Dy₂O₃：14.86mg/kg、Ho₂O₃：2.69mg/kg、Er₂O₃：7.55mg/kg、Tm₂O₃：1.12mg/kg、Yb₂O₃：7.13mg/kg、Lu₂O₃：1.07mg/kg、Y₂O₃：80.83mg/kg。

The morphology of the functional material II prepared by the method is shown in FIG. 2, and the microscopic image is shown in FIG. 3, and the functional material II comprises:

oxides of conventional elements: al (Al)₂O₃：13.01％，SiO₂：76.15％，Fe₂O₃：0.08％，CaO：0.7％，MgO：0.05％，K₂O：5.33％，Na₂O：3.54％，TiO₂: 0.02 percent; loss on ignition: 0.4 percent;

oxide containing fifteen rare earth elements: la₂O₃：16.07mg/kg，CeO₂：38.53mg/kg，Pr₈O₁₁：3.33mg/kg，Nd₂O₃：10.47mg/kg，Sm₂O₃：1.71mg/kg，Eu₂O₃：0.53mg/kg，Gd₂O₃：1.68mg/kg，Tb₄O₇：0.22mg/kg，Dy₂O₃：1.27mg/kg，Ho₂O₃：0.21mg/kg，Er₂O₃：0.66mg/kg，Tm₂O₃：0.09mg/kg，Yb₂O₃：0.59mg/kg，Lu₂O₃：0.10mg/kg，Y₂O₃：7.14mg/kg。

Grinding the functional material II to be 200 meshes and pressing the fine powder into a cake, obtaining a ceramic cake sample after the high temperature of 1250 ℃, placing the sample in a testing area of an infrared radiation measuring instrument, testing the radiation energy of the sample in the wavelength range of 0.76-300 mu m, and obtaining the testing result shown in figure 4, wherein the infrared radiation energy of the sample is obviously increased, and the infrared radiation range of the sample is 5-18 mu m.

Detecting the release amount of negative oxygen ions of the sample, wherein the release amount of the negative oxygen ions is 2746/cm³。

Example 2

Preparation of antibacterial lead-free ceramic fritted glaze from functional material II prepared in example 1

The frit glaze comprises the following components in percentage by mass: functional material II: 30%, quartz: 15%, feldspar: 10%, dolomite: 12%, boric acid: 3%, zinc oxide: 5%, alumina: 25 percent.

Uniformly mixing the functional material II, quartz, feldspar, dolomite, boric acid, zinc oxide and alumina, putting the mixture into a melting furnace, heating to 1480 ℃, keeping the temperature for 2 hours, discharging, and quenching the flowing glass liquid with water to obtain the functional material II, wherein the particle sizes of the quartz, the feldspar, the dolomite, the boric acid, the zinc oxide and the alumina are all 80 meshes. The morphology of the antibacterial lead-free ceramic fritted glaze is shown in fig. 5.

Example 3

Preparation of ceramics from the functional materials II and III prepared in example 1

(1) Preparation of a ceramic body from the functional Material III prepared in example 1

The ceramic blank comprises the following components in percentage by mass: functional material III: 30 percent of coal-series kaolin, 60 percent of calcium bentonite, 7 percent of calcium bentonite and 3 percent of serpentine.

Wherein, the coal-series kaolin has the following physical and chemical indexes: al (Al)₂O₃：38-40％，SiO₂：45-50％，Fe₂O₃：0.1-0.12％，CaO：0.05-0.07％，MgO：0.05-0.08％，K₂O：0.05-0.07％，Na₂O：0.03-0.05％，TiO₂：0.1-0.3％；

The physicochemical indexes of the calcium bentonite are as follows: al (Al)₂O₃：13-18％，SiO₂：65-68％，Fe₂O₃：1.0-1.2％，CaO：0.55-0.6％，MgO：1.3-1.5％，K₂O：0.05-0.06％，Na₂O：0.4-0.6％，TiO₂：0.04-0.06％；

Physical and chemical indexes of serpentine: al (Al)₂O₃：0.3-0.45％，SiO₂：40-42％，Fe₂O₃₊TiO₂：0.5-0.8％，CaO：1.2-1.6％，MgO：40-43％。

Respectively dry-grinding coal-series kaolin, calcium-based bentonite and serpentine to 120 meshes or less, removing worn mechanical iron by magnetic separation, adding the obtained mixture and functional material III into a wet ball mill, adding water, grinding and homogenizing for 12h, sieving the ground slurry with a sieve of 250 meshes to obtain a slurry with a sieve residue of not more than 0.5%, stirring the slurry in a tank, sequentially feeding the slurry into a primary slurry electromagnetic separator and a secondary slurry electromagnetic separator, and mixing with Fe₂O₃+TiO₂Controlling the content at 0.12-0.15% to obtain ceramic blank, press-filtering the ceramic blank, ageing at 28 deg.C for 5 days, vacuum-pugging to make it meet the blank-making requirements, and preparing ceramic blank body.

(2) Preparation of ceramics

The antibacterial lead-free ceramic fritted glaze prepared in example 2 was applied to the ceramic body prepared in step (1), and fired to obtain a porcelain article. The appearance diagram of the porcelain product in the sun is shown in fig. 6, and in the sun, the porcelain shows different colors, because the electronic layers of rare earth elements in the lead-free frit glaze are more and complicated, so that the spectrum lines of the rare earth elements are more than those of other elements, and the rare earth elements can absorb and emit electromagnetic radiation with various wavelengths in ultraviolet and visible infrared light regions, so that the finally fired porcelain has changeable colors, is bright and soft and bright in color, and is difficult to compare with shoulders by manually adding any color base. The porcelain also had high transmittance under light, as shown in fig. 7.

The ceramic chip is placed in a testing area of an infrared radiation measuring instrument to test the radiation energy of the ceramic chip in the wavelength range of 0.76-300 mu m, the test result is shown in figure 8, as can be seen from figure 8, the infrared radiation energy of the ceramic chip is obviously increased, and the infrared radiation range of the ceramic chip is 9-13 mu m.

Testing the negative oxygen ion release amount of the porcelain ceramic chip, wherein the oxygen ion release amount is 3200-³。

The above porcelain was tested for strength and its impact strength was 1.69J/cm²Water absorption of 0.8% and glaze hardness of 513.4kg/mm²Putting the porcelain into an electric furnaceAfter the porcelain is burnt to 180 ℃, the porcelain is put into water with the temperature of about 20 ℃, and the porcelain does not crack and has good thermal shock resistance.

The antibacterial performance of the porcelain is tested according to JC/T897-2014, the antibacterial rate to Staphylococcus aureus ATCC6538 is more than or equal to 99.94 percent, and the antibacterial rate to Escherichia coli ATCC25922 is more than or equal to 99.99 percent.

Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.

Claims (10)

1. An antibacterial lead-free ceramic fritted glaze is characterized in that the fritted glaze comprises the following components in percentage by mass: functional material II: 10-30%, quartz: 15-20%, feldspar 10-20%, dolomite: 5-12%, boric acid: 2-7%, zinc oxide: 2-7%, alumina: 10 to 25 percent;

the functional material II is prepared by the following method:

coarsely crushing granite, placing the granite in a self-collision type separator for collision separation, collecting materials which are discharged by the self-collision type separator and are 5mm in thickness, placing the materials which are 5mm in thickness in a wet ball mill with a discharge port equipped with a hydraulic classifier, obtaining the materials which are 50 meshes in thickness through the hydraulic classifier, placing the materials which are 50 meshes in thickness in a magnetic separation system for magnetic separation, and removing magnetic substances, wherein the mass fraction of the magnetic substances Fe and Ti is less than or equal to 0.1%, and the materials are defined as a functional material II; the granite is granite porphyry, is at the east end of the north foot of the mountain of the yin and is at the south edge of the middle part of the inner Mongolia at an ore deposit.

2. The antibacterial lead-free ceramic fritted glaze of claim 1, wherein standard corundum bricks are adhered to the circumferential direction of the inner wall of the roller of the self-collision separator, convex corundum bricks are uniformly embedded in the standard corundum bricks, the convex corundum bricks have a projection height of 50-100mm, the discharge port is provided with a high-manganese wear-resistant discharge grate matched with the discharge port, and the aperture of the discharge hole of the discharge grate is 5 mm.

3. The antibacterial lead-free ceramic fritted glaze of claim 2, wherein the length of the roller of the self-impact separator is 4500mm, the diameter of the roller is 2400mm, and the diameter of the feeding port is 400 mm; the rotating speed of the self-collision type separator is set to be 28-32 r/min.

4. The antibacterial lead-free ceramic fritted glaze of claim 1, wherein the mass ratio of the fine material with a diameter of 5mm to water in the wet ball mill is 50-65:35-50, the installed capacity of a motor in the wet ball mill is 500kw, the power consumption in actual normal operation is 300-350kw/h, and the rotating speed is 19-20 r/min.

5. The antibacterial lead-free ceramic fritted glaze of claim 1, wherein the mixing flow rate of water and materials in the hydraulic classifier is adjusted to 75-100m³/h。

6. The antibacterial lead-free ceramic fritted glaze of claim 1, wherein the magnetic separation is completed in three stages, firstly, the magnetic separation is performed in a flat magnetic separator with the magnetic field strength of 5500-.

7. The antibacterial lead-free ceramic fritted glaze of any one of claims 1 to 6, wherein in the functional material II:

oxides of conventional elements: al (Al)₂O₃：13-14％，SiO₂：75-77，Fe₂O₃：0.06-0.08％，CaO：0.5-0.7％，MgO：0.05-0.07％，K₂O：5-5.5％，Na₂O：3.5-3.7％，TiO₂: 0.01 to 0.02 percent; vector burning: 038-0.4%; oxide containing fifteen rare earth elements: la₂O₃：15-18mg/kg，CeO₂：35-40mg/kg，Pr₈O₁₁：3.0-3.5mg/kg，Nd₂O₃：10-12mg/kg，Sm₂O₃：1.5-2.0mg/kg，Eu₂O₃：0.5-1.0mg/kg，Gd₂O₃：1.5-2.0mg/kg，Tb₄O₇：0.2-1.0mg/kg，Dy₂O₃：1.2-1.5mg/kg，Ho₂O₃：0.2-0.4mg/kg，Er₂O₃：0.5-0.8mg/kg，Tm₂O₃：0.09-0.12mg/kg，Yb₂O₃：0.5-0.9mg/kg，Lu₂O₃：0.1-0.5mg/kg，Y₂O₃：7-9mg/kg。

8. The antimicrobial lead-free ceramic fritted glaze of any one of claims 1-6, wherein the granite has:

oxides of conventional elements: al (Al)₂O₃：13-15％，SiO₂：72-77％，Fe₂O₃：1.7-2.2％，CaO：0.9-1.5％，MgO：0.15-0.4％，K₂O：5.0-6.0％，Na₂O：3.2-4.0％，TiO₂: 0.12-0.2%, burning vector: 0.4 to 0.8 percent;

macroelements: n: 1000-1200mg/kg, P: 170-200mg/kg, K: 40000-50000 mg/kg;

medium elements: ca: 5500-6000Mg/kg, Mg: 800-900mg/kg, S: 70-80 mg/kg;

trace elements: cu: 2-5mg/kg, Fe: 13000-15000mg/kg, Mn: 180-250mg/kg, Zn: 40-80mg/kg, B: 6-8mg/kg, Se: 3.0-7.0mg/kg, Mo: 3.5-6.5 mg/kg;

oxide containing fifteen rare earth elements: la₂O₃：60-70mg/kg，CeO₂：130-150mg/kg，Pr₈O₁₁：15-20mg/kg，Nd₂O₃：65-80mg/kg，Sm₂O₃：12-20mg/kg，Eu₂O₃：0.3-1.0mg/kg，Gd₂O₃：14-20mg/kg，Tb₄O₇：2.5-5mg/kg，Dy₂O₃：14-20mg/kg，Ho₂O₃：2.5-3.0mg/kg，Er₂O₃：7.0-10.0mg/kg，Tm₂O₃：1.1-1.5mg/kg，Yb₂O₃：7-10mg/kg，Lu₂O₃：1.0-1.5mg/kg，Y₂O₃：80-120mg/kg；

Oxides of rare light metal elements: sc (Sc)₂O₃：30-50mg/kg，RbO₂：1300-1500mg/kg。

9. The method for preparing an antibacterial lead-free ceramic fritted glaze according to any one of claims 1 to 8, wherein the method comprises the following steps:

uniformly mixing the functional material II, quartz, feldspar, dolomite, boric acid, zinc oxide and alumina, putting the mixture into a melting furnace, heating to 1450-.

10. The method of claim 9, wherein the particle sizes of the quartz, feldspar, dolomite, boric acid, zinc oxide and alumina are all 80 mesh fine.

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