CN112194478B

CN112194478B - Antibacterial magnesium porcelain

Info

Publication number: CN112194478B
Application number: CN202011097603.XA
Authority: CN
Inventors: 高秋祥; 高峰; 师全
Original assignee: Pingding Yingyu Porcelain Co ltd
Current assignee: Pingding Yingyu Porcelain Co ltd
Priority date: 2020-10-14
Filing date: 2020-10-14
Publication date: 2023-02-03
Anticipated expiration: 2040-10-14
Also published as: CN112194478A

Abstract

The invention relates to ceramic production, in particular to an antibacterial magnesium ceramic; the glaze is prepared from a blank and glaze, wherein the blank comprises the following components in parts by weight: the glaze is prepared from a blank and glaze, wherein the blank comprises the following components in parts by weight: 25 parts of wulan tea spar, 28-38 parts of raw talc, 25-40 parts of cooked talc, 3-8 parts of Pingding trilobate gangue and 1-8 parts of Pingding dry powder; the glaze comprises 94.6 parts of frit, 3 parts of Pingding dry surface, 2 parts of cellulose and 0.4 part of soda surface in parts by weight; the formula design is carried out by adopting the wulan tea crystal stone as the main raw material of the ceramic blank and glaze, no special additive is required to be added, the cost of the domestic or imported antibacterial agent in the current market is basically 40 ten thousand 120 ten thousand per ton, the cost is extremely high, the cost of the ceramic ingredients is basically not increased by the wulan tea crystal stone, and the test result shows that the antibacterial effect is excellent; the product of the invention has the advantages of fast reaction in the production process, high whiteness, fine and milky porcelain, semitransparent thin body and fat luster; good transparency, good regularity, smooth glaze surface of the porcelain, high hardness, excellent thermal stability and the like.

Description

Antibacterial magnesium porcelain

Technical Field

The invention relates to ceramic production, in particular to an antibacterial magnesium ceramic.

Background

In recent years, as consumers have been increasingly aware of daily ceramic products, higher demands have been made on the aesthetic and functional properties of the daily ceramic products. The concrete main points are as follows: 1. the lead and cadmium elution amount not only reaches the national standard, but also reaches the FDA international standard. 2. The beauty and the richness of colors are required to be pursued for practicality, and the requirements for updating products are also required. 3. The popularity of the big health concept, consumers are more concerned about health functions. This presents a new topic for our ceramic industry.

Staphylococcus aureus is an important pathogenic bacterium in humans, belonging to the genus Staphylococcus, which is also known as a mesophilic bacterium, and is a representative of gram-positive bacteria, and causes many serious infections. The american centers for disease control report that escherichia coli and staphylococcus aureus cause infections in humans in the first and second places, respectively. In recent years, researchers have conducted many exploration and research, at present, two methods are mainly used for killing surface bacterial microorganisms, one is a surface antibacterial layer technology, a layer of antibacterial material is coated on the surface of a ceramic glaze layer, the antibacterial layer is fixed through a low-temperature sintering method, an antibacterial agent is added to a glaze material technology to enable antibacterial ingredients to directly participate in the melting process of the ceramic glaze material, the first method is that the antibacterial materials are two, one is a photocatalytic titanium oxide material, and the surface microorganisms are killed through the redox reaction of trivalent titanium ions and tetravalent titanium ions under the action of light. The earliest antibacterial technology of the Japan Dongtao company is to apply a transparent titanium oxide photocatalytic antibacterial layer on a glaze layer. The other method is to thermally spray metal silver paste on the surface of the ceramic glaze layer, take the metal silver as an anode and form a very thin silver film on the surface of the glaze layer by adopting a plasma spraying method, so that the sterilization effect of the surface is achieved. This technology is still used by antibacterial sanitary wares of the company of empferia japan at present. The second method is to add antibacterial agent directly into glaze to prepare antibacterial functional glaze, and this technology was originally developed by Egyptian corporation of Japan. At present, the existing domestic antibacterial ceramics mainly adopt the technology, and at present, more antibacterial agent manufacturers exist, wherein the antibacterial agent produced by American Miaokang corporation is the best. There are many domestic products, such as Xiamen jin science and technology, shandong Boner science and technology, and Fushan Li Yuan chemical industry. The method has the problems of high metal component mixing amount, high cost, limited adding amount (generally 1-2 parts), loss of high-temperature sintering components and easy fluctuation of antibacterial performance.

The magnesium porcelain belongs to a high-grade product in daily ceramics, and the whiteness is about 80 parts. The common raw materials of the magnesia porcelain comprise calcined talc and a small amount of clay, quartz, feldspar and the like, and the common raw materials generally adopt a reducing flame atmosphere and a primary or secondary firing process, wherein the secondary firing process comprises high-temperature biscuit firing (1310 ℃ -1330 ℃) and low-temperature glaze firing (1160 ℃ -1180 ℃). The temperature of the one-time firing process is 1280-1320 ℃.

The calcined talc is high in energy consumption on one hand and difficult to form on the other hand by adopting a cooked talc formula process; the reduction flame firing process is not easy to control and has high energy consumption; the low-temperature glaze firing process causes the surface hardness of the product to be low; the one-time sintering process causes the problems of poor regularity of products and the like.

The Wulan tea spar is used as a fluxed ceramic raw material, the strength and the thermal shock resistance of the ceramic material can be obviously improved after the Wulan tea spar is fired, and a ceramic product produced based on the Wulan tea spar has the functions of far infrared, antibiosis and easy cleaning; the Wulan tea spar raw material is used for ceramic production, can accelerate the porcelain forming reaction, realizes quick firing, is easy to ensure the regularity of the product under certain conditions, and is not easy to deform.

Disclosure of Invention

The invention aims to provide an antibacterial magnesium porcelain, and a new wulan tea crystalline stone material is added into a material formula. The antibacterial performance of the magnesium porcelain detected by a national fixed-point detection mechanism reaches and is superior to the national standard JC/T897-2014 antibacterial performance of antibacterial ceramic products; the product has high whiteness, good transparency, good regularity, smooth glaze surface of the porcelain, high hardness and good thermal stability.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

an antibacterial magnesium porcelain is prepared from a blank and a glaze, wherein the blank comprises the following components in parts by weight: 25 parts of wulan tea spar, 28-38 parts of raw talc, 25-40 parts of cooked talc, 3-8 parts of Pingding trilobate gangue and 1-8 parts of Pingding dry powder; 94.6 parts of fusion cake, 3 parts of Pingding dry flour, 2 parts of cellulose and 0.4 part of alkali flour.

The composition of the above-mentioned blanks and of the glaze, both having a known chemical composition (in parts), is shown in the following table:

analysis of rare earth element in Wulan tea spar trace amount (unit: mg/kg)

Element(s)	La ₂ O ₃	CeO ₂	Pr ₈ O ₁₁	Nd ₂ O ₃	Sm ₂ O ₃	Eu ₂ O ₃	Gd ₂ O ₃	Tb ₄ O ₇
									Results	61.46	129.47	12.97	40.87	6.71	0.66	7	0.89
Element(s)	Dy ₂ O ₃	Ho ₂ O ₃	Er ₂ O ₃	Tm ₂ O ₃	Yb ₂ O ₃	Lu ₂ O ₃	Y ₂ O ₃
									Results	4.68	0.83	2.47	0.33	2.12	0.62	24.60

The invention also provides a preparation method of the antibacterial magnesium porcelain, which comprises the following steps:

preparing raw materials according to the weight part ratio, ball-milling the raw materials, sieving to remove iron, filtering mud, performing vacuum mud refining and ageing of mud, performing secondary vacuum mud refining and ageing of mud, trimming blanks after blank making and forming, performing biscuit firing after the blank trimming, and polishing to obtain a smooth and fine biscuit firing product without impurities;

step two, preparing glaze materials according to the weight parts, carrying out wet ball milling on the glaze materials, preparing glaze slip, and carrying out iron removal and sieving on the glaze slip to obtain standby glaze slip;

and step three, spraying glaze on the biscuit firing product obtained in the step one by using the standby glaze slip prepared in the step two, and firing after glaze spraying to obtain the antibacterial magnesium porcelain.

Further, when the blank is ball-milled, the blank is uniformly mixed according to the formula proportion, and then is fed into a ball mill according to the following materials: ball stones: 1, water: 1.8:1, and performing wet grinding and fine crushing, and performing fineness test analysis, wherein the standard is 0.09-0.15 part of residue of a ten-thousand-hole sieve of the slurry.

Further, when the glaze slurry is ball-milled, the glaze material of the formula is filled into a wet ball mill for fine crushing, and the raw materials are as follows: ball stones: water =1:1.8: the 0.4 grind fineness criteria were: 0.01 to 0.02 portion of residue of a ten-thousand-hole sieve.

Preferably, the first ageing process of the pug in the first step is to store the pug strips subjected to vacuum pugging in a clean pug storehouse with the ambient temperature of 15-25 ℃ and the relative humidity of 50 parts HR for ageing, wherein the ageing period is about 3-7 days, the environment must be clean and tidy, the pug strips cannot fall to the ground and can not be stained, and the pug strips can not be mixed with impurities.

Preferably, biscuiting is completed in a natural gas tunnel kiln, a gas tunnel kiln or an electric shuttle kiln, wherein the firing temperature ranges from 1230 ℃ to 1250 ℃, and the firing curve is as follows: room temperature-200 deg.C, 60 min; at 200-400 deg.c for 90 min; 400-600 ℃ for 100 minutes; (ii) a 600-900 ℃ for 120 minutes; 900-1000 ℃ for 30 minutes; 75 minutes at 1000-1200 ℃; 1200-1250 ℃ for 30 minutes; keeping the temperature for 1 hour, and cooling to 700 ℃ for two hours.

Preferably, the method is characterized in that the firing after the glaze spraying in the three steps is finished in a natural gas tunnel kiln, a gas tunnel kiln or an electric-firing shuttle kiln, and qualified products are obtained at the firing temperature of 1130-1150 ℃; the firing curve is as follows: room temperature-200 deg.C for 60 min; at 200-400 deg.c for 90 min; 400-600 ℃ for 100 minutes; 600-900 ℃ for 120 minutes; 900-1000 ℃ for 45 minutes; 1000-1150 ℃ for 80 minutes; keeping the temperature for 1 hour, and cooling to 700 ℃ for two hours.

Functional experiments and tests

1) Research and test of far infrared function

First we tested the far infrared function of wulan theophyllite raw ore, see table 1.

TABLE 1 far-infrared test of wulan tea-crystal stone raw ore

From the above far infrared test results of the wulan tea spar raw material, we can see that wulan tea spar and raw ore can emit far infrared rays with a wavelength of 220m and a relative energy of more than 0.7 at normal temperature, wherein the highest intensity can reach 0.87 at a wave band of 3-5m, and can reach about 0.8 at a wave band of 5-20 μm, and the processed and purified wulan tea spar is not much different from the raw ore, the wave band performance is approximately the same, and the relative energy value is slightly reduced.

Specifically, in the ceramic proportion, according to the experimental result, the adding proportion of the wulan tea crystal stones is basically 20-50% (for daily ceramics, building ceramics and sanitary wares, not including later-stage physical therapy porcelain products), and if the adding amount is below 50%, the far infrared function is lower than that of the raw materials (or raw ores)? In practice, the formula consisting of different types in various proportions is tested, and the basic conclusion is as follows: the far infrared emission intensity is increased along with the increase of the adding amount of the glaucous tea kyanite; the components in the B composition are different, and the far infrared emission intensity of the material is obviously different. But the overall band is narrowed. The relative energy values of far infrared emissions for different proportions of the wulan tawnite are listed in table 2.

TABLE 2 relative energy of far infrared emission of wulan tea spar in different ceramic materials (wavelength maximum between 2-22 μm)

Therefore, the conclusion can be drawn that the ceramic product made from the wulan tea spar is a ceramic product with the function of emitting infrared rays, the wavelength of the ceramic product is within the range of 2-20 microns, the far infrared emission intensity is increased along with the increase of the adding amount of wulan tea spar, and simultaneously, the phase composition of the wulan tea spar formed in ceramics made of different materials is different due to the difference of reactant formulas. The different phases show the difference of internal energy (enthalpy) of the ceramic material, and also show that a plurality of rare earth elements contained in the wulan tea boulder enter the crystal phase of the material to generate anomer allotrope, a part of rare earth oxide or (certain mineral) in the crystal boundary hinders the migration of liquid phase components to the crystal phase so as to inhibit the growth and growth of the crystal, so that the phase internal energy is increased, and therefore, the vibration energy, the motion kinetic energy, the rotation kinetic energy and the like of the irregular motion of ions in the material are also increased, and a part of the rare earth oxide is melted in the glass phase to play a toughening role. Based on this analysis, we judged that ceramic materials incorporating wulan tea crystals can exhibit strong blackbody properties at high temperatures. In practice, when the daily-used ceramic is prepared by secondary sintering, the same frit glaze is used in the secondary glaze sintering process, when the ceramic is subjected to glaze sintering in the same kiln, the plain body glaze surface without the wulan tea spar has good quality, and the ceramic plain body glaze surface containing the wulan tea spar is overfire, and is expressed as orange glaze and even bubbles. The sintering temperature of the same product is reduced, the glaze sintering temperature is reduced from 1140 ℃ to 1130 ℃, 1120 ℃, 1110 ℃, 1090 ℃ and 1080 ℃ through multiple times of trial sintering, and compared with the glaze effect, the glaze sintered in the range of 1090-1110 ℃ has the best quality, and is reduced by 30-50 ℃ compared with the glaze sintering temperature of the original product. In the same daily-use porcelain once fired, the glaze surface is generally better than that of the original product after the same raw glaze is used and the blank of the Wulan tea spar is added and fired, and the glaze surface defects are obviously reduced (see application test parts and object samples). This shows that in the high temperature stage, the temperature of the product is higher than the temperature of the kiln due to the fact that the green body shows strong black body property, so that the integral melting process of the glaze is prolonged, and the temperature is increased. In addition, the porcelain forming speed of all the daily porcelain varieties is greatly increased, the pushing speed is 22 cars/shift originally, the highest pushing speed is increased to 27 cars/shift, and the water absorption rate of the product is very low. The analysis reason is that a plurality of rare earth trace elements contained in the A. Play a good role in mineralization and accelerate the reaction speed of porcelain formation. B. The black body properties exhibited by the green body result in a reduction in firing time.

2) Research and test of antibacterial function

The results of the antibacterial tests of various developed products are shown in table 3.

TABLE 3 antibacterial Rate% of different ceramic materials (see test report)

According to different proportions of the wulan tea spar contained in various porcelain varieties, different antibacterial rates are shown. The basic rule is that along with the increase of the proportion of the glaucophyll theophyllite, the antibacterial rate is also continuously increased. For staphylococcus aureus and escherichia coli, it is believed that the enamel layer plays a dominant role and the body plays an auxiliary role for the former. In the latter case, the body plays a dominant role and the glaze layer plays an auxiliary role. Therefore, in order to increase the sterilization rate of staphylococcus aureus, the proportion of wulan theophyllite in the glaze layer needs to be increased, and in order to increase the sterilization rate of escherichia coli, the content of wulan theophyllite in the blank needs to be increased. Of course, different materials show different sterilization rates under the condition of the same proportion of the bird-lan tea spar. Generally, the higher the energy of the formed porcelain (high energy state structure), the higher the sterilization rate. When the water absorption of the green body is high, the contribution of the green body to the sterilization rate is rapidly reduced once the sample green body absorbs water. This is because electrons escaping from the green body are trapped by water and impair the ability of the surface to form radicals. It should be emphasized that the antibacterial property of the material is reduced when the surface of the material is coated with some organic silicon or non-polar substances because the material structure of the surface weakens the formation of free radicals and the strength is different, the sterilization rate is increased along with the increase of the proportion of wulan tea stones, and the sterilization rate is rapidly reduced when the proportion of wulan tea stones exceeds a certain value in the aspect of the strength. But the antibacterial performance is related to the proportion of wulan tea spar and different system basic components, and is similar to the far infrared function in the aspect of antibacterial performance of materials, namely wulan tea spar is the main factor for exciting the antibacterial performance in the formula, but the expression result is different due to different excited substances, and the infrared emission function is basically the same as the infrared emission function.

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

the Wulan tea stone contains a large amount of rare elements, the Wulan tea stone is used as a main raw material of a ceramic blank and a glaze for formula design, no special additive is required to be added, the cost of the current domestic or imported antibacterial agent in the market is basically 40 ten thousand to 120 ten thousand per ton, the cost is extremely high, the Wulan tea stone basically does not greatly improve the cost of ceramic ingredients, and the test result shows that the antibacterial effect is excellent. When the proportion of the wulan theophyllite in the formula of the blank glaze is more than 30 parts, the antibacterial rate can reach more than 95 parts, and when the proportion is between 20 and 30 parts, the antibacterial rate also exceeds more than 90 parts specified by the national standard, so that the ceramic product can be said to come out a brand-new way of the ceramic with the antibacterial function in the future.

In addition, the invention provides a magnesia porcelain, which is prepared by adding raw talc into a blank, correspondingly reduces the using amount of cooked talc, saves the energy for calcining the raw talc and simultaneously improves the forming performance of pug. The method has the advantages of high whiteness, fine and milky porcelain, semitransparent thin body, fat luster, good transparency, good regularity, smooth glaze surface of the porcelain, high hardness and good thermal stability.

The addition of the glaucophyll crystalline stone raw material can produce a color-changeable ceramic product, and the prepared magnesia ceramic product has excellent heat conduction and heat resistance. The adding of the glaucophyllite raw material accelerates the porcelain forming reaction, realizes quick firing, easily ensures the regularity of the product under certain conditions and is not easy to deform.

Detailed Description

The present invention is further illustrated by the following specific examples.

Example 1

1. Preparation of the pug

(1) Ingredients (taking the following weight portions)

25 parts of wulan tea spar, 29 parts of raw talc, 36 parts of cooked talc, 5 parts of Pingding trilobate gangue and 5 parts of Pingding dry powder.

The raw materials are uniformly mixed according to the formula proportion, and are put into a ball mill (according to the proportion of material: ball stone: water 1.8.

(2) Iron removal sieving

The slurry passes through 4 sets of iron removal screening systems, each set of system comprises two wet magnetic separators, and one three-layer vibrating screen (180 meshes, 200 meshes and 250 meshes respectively) obtains purified, uniform and qualified slurry with certain particle size distribution, and the slurry is put into a slurry pool for later use.

(3) Filter-pressing mud

The mechanical equipment used in the working procedure is a plunger pump and a mud filter, the plunger pump is used for pumping the qualified mud which is reserved in a mud pool into the mud filter, and the mud slices with water content of 20-25 parts are formed through the dehydration of filter cloth.

(4) Vacuum pugging and staleness of mud

A. And (3) carrying out vacuum pugging on the dewatered mud slices once by using a vacuum pugging machine with the vacuum degree of not less than 0.09 MPa.

B. And (3) neatly storing the mud strips subjected to vacuum pugging in a clean mud warehouse with the ambient temperature of 15-25 ℃ and the relative humidity of 50 parts HR for ageing for about 3-7 days. The environment must be clean and tidy, and the mud bar can not fall to the ground and can not be dirty, guarantees that the mud bar can not sneak into impurity.

(5) Secondary vacuum pugging

A. And performing secondary vacuum pugging on the mud strips aged for 3-7 days, wherein the vacuum is controlled to be-0.09 MPa to-0.095 MPa, so that the water content of the mud strips is kept consistent and uniformly diffused in the process, and hard mud blocks and dry mud residues cannot appear. The prepared mud strip is aged for more than 24 hours, so that the moisture in the mud strip is fully and uniformly diffused for forming.

B. When the mud strip is used for forming, the vacuum pugging is carried out again, the vacuum degree is not lower than 0.092PMa in the process, and the purpose is to divide the mud strip into mud strips with various diameters and thicknesses meeting the requirements of various varieties.

2. Blank making

(1) The process adopts the forming equipment such as a rolling forming machine, a cold-pressing forming machine, pressure grouting, high-pressure grouting and the like to produce ceramic mud blanks with various shapes. In the process, the product is designed reasonably, the sizes of all parts are accurate, the gravity analysis is fully considered, the bottom weight and the mouth weight are light, the process is a key point, and the deformation defect can be caused in the firing process due to slight error in design.

(2) Drying various products after forming to automatic demoulding, drying the demoulded products in a drying room with the ambient temperature of about 60 ℃, and controlling the water content to be below 2 parts to obtain qualified blanks.

(3) Repairing and testing blank

The working procedure adopts a trimmer, sand paper, iron sand and a sea brocade grading tool to polish the edge of the blank smoothly and polish the front and back of the product smoothly. The blank is carefully inspected by clear water to achieve round product mouth, smooth whole body, no defects of rolling marks, mud dragging, mud residue, blank missing and pimples exist, so that the product is attractive and elegant, and then the product is dried in a blank warehouse at the ambient temperature of about 30 ℃ to obtain qualified green blanks.

3. Biscuit firing

The working procedure can be completed in a natural gas tunnel kiln, a gas tunnel kiln and an electric burning shuttle kiln, and the burning temperature is 1230-1250 ℃.

The firing curve is as follows:

4. grinding and polishing

This procedure was accomplished in a manual grinding and polishing machine. So that the biscuit firing product is smooth, fine and free of impurities.

5. Preparation of glaze

(1) Glaze material

The following percentage contents are taken to form the mixture ratio.

94.6 parts of fusion cake, 3 parts of Pingding dry flour, 2 parts of cellulose and 0.4 part of alkali flour.

(2) Formation of glaze slip

The glaze according to the formula is put into a wet ball mill for fine crushing (according to the standard of the grinding fineness of the glaze: ball stone: water = 1.8: 0.01 to 0.02 portion of residue of a ten-thousand-hole sieve.

(3) Iron removal and sieving

And (3) after the ground glaze slip reaches the standard through chemical analysis, passing through a set of deironing and sieving system (the deironing and sieving system comprises two three-layer vibrating sieves with 180 meshes, 200 meshes and 250 meshes of magnetic separators which are connected in series) to obtain qualified glaze slip for later use.

6. Glaze spraying

In the working procedure, a manual glaze spraying method and a mechanical glaze spraying method can be adopted to glaze the qualified biscuit product, and the thickness of the glaze layer is controlled to be between 0.5 and 1 mm. Obtaining the qualified glazed product. Drying in a drying room, controlling the water content to be about 2 parts, and preparing for glaze firing.

7. Glaze firing

The process can be completed in a natural gas tunnel kiln, a gas tunnel kiln and an electric burning shuttle kiln, and the burning temperature is 1130 ℃ to 1150 ℃. Obtaining the qualified product.

The firing curve is as follows:

example 2

An antibacterial magnesium porcelain is prepared from a blank and a glaze, wherein the blank comprises the following components in parts by weight: 25 parts of wulan tea spar, 28 parts of raw talc, 35 parts of cooked talc, 8 parts of Pingding trilobate gangue and 4 parts of Pingding dry surface; the glaze comprises the components of 94.6 parts of frit, 3 parts of Pingting dry powder, 2 parts of cellulose and 0.4 part of soda powder in parts by weight, and the preparation method is the same as that of example 1.

Example 3

An antibacterial magnesium porcelain is prepared from a blank and a glaze, wherein the blank comprises the following components in parts by weight: 25 parts of wulan tea spar, 38 parts of raw talc, 26 parts of cooked talc, 3 parts of Pingding trilobate gangue and 8 parts of Pingding dry surface; the glaze comprises, by weight, 94.6 parts of frit, 3 parts of Pingding dry powder, 2 parts of cellulose and 0.4 part of soda powder, and the preparation method is the same as that in example 1.

The antibacterial magnesium porcelain prepared in the above example 1 is sent to the national ceramic detection key laboratory alliance national building sanitary ceramic detection key laboratory Foshan customs integrated technology center for antibacterial detection. The number of samples is 12, and the specification of the samples is 50mm multiplied by 50mm; the inspection date is 2020-05-12 to 2020-05-15, and the inspection basis is as follows: the test result of JC/T897-2014 antibacterial ceramic article (antibacterial performance) is as follows:

the wulan tea spar used in the above examples was prepared from granite formed two hundred million years ago by the following steps: (1) Transporting the mine raw ore to an open-air storage yard, homogenizing and mixing for the first time, and then entering a coarse crushing production line;

(2) Coarse crushing ore blocks smaller than 300mm by a frequency crusher, stacking again by a forklift for second homogenization and mixing, then crushing in a middle stage, conveying the material smaller than 100mm to a hydraulic cone crusher by a belt, and continuously and uniformly mixing ore bodies from large to small in the whole production process through each working section to achieve stable material components;

(3) Materials smaller than 30mm are conveyed to a high-speed impact sand making machine by a belt, the conventional sand making machine achieves the purpose of crushing by mechanical collision, the mica in a mineral body is processed by adopting a self-existing technology to break walls, separate and enrich, the traditional turbine cavity wall is made of high manganese alloy wear-resistant materials to achieve the purpose of impact crushing of the materials, the equipment is subjected to cavity liner-free improvement, the materials are naturally stacked into a surface, the diameter of a feed inlet is larger than 150mm, the material is directly communicated with the center end of a high-speed rotating turbine, when the materials enter the center end of the turbine, the materials are uniformly distributed to each emission flow channel of an impeller by a distribution cone at the center of the impeller, a wear-resistant alloy projection plate is arranged at an emission flow channel opening, the impeller projects the materials at the rotating speed of 6575 m/and impacts the materials on the stacking inclined surface of the cavity to generate strong mutual collision among the materials so as to achieve the purpose that the magnetic mica in the materials keep the original state; an impeller grading system is improved at the top of a sand making machine body and is integrated into a machine, mica and amorphous light substances in the materials are subjected to collision wall breaking, separation and disintegration, and the ultrafine and light amorphous substances in the materials are enriched in a dust collecting system through a grading impeller and a draught fan system;

(4) Materials smaller than 5mm are conveyed to a material collecting bin through a belt to be stored, are uniformly mixed for the fourth time, are ground by a lifter to a wet continuous ball mill, the ball mill is in metal-free contact grinding, the lining of the mill is a corundum lining plate, a grinding medium is a corundum ball, the materials with the grain size smaller than 26 meshes are ground by the ball mill and enter a desliming system, the desliming of the materials smaller than 325 meshes enters a thickener system in an overflow mode, the materials larger than 325 meshes enter a hindered settling grading system, and the materials larger than 50 meshes return to the ball mill system; the separated 5-0325-mesh material enters a magnetic separation system;

(5) The separated 50-325 mesh material is processed by a multi-stage magnetic separation system, and then the ceramic standard raw material, namely the Wulan tea stone functional material enters a packaging system.

The performance mechanism of the Wulan tea-crystal stone for preparing the magnesia ceramics is discussed:

1) With respect to strength it was first discovered that wulan tea stones significantly improve the strength of ceramic materials, which for domestic porcelain is focused on impact resistance. According to the test result, the impact strength of the central part is improved by more than one time when the proportion is 25%, the impact strength of the edge is improved by more than two times, and the breaking strength is the focus of attention for bricks and is improved by more than 10%. It is believed that this is due to the various rare earth trace elements contained in the wulan tea boulder, especially La ₂ O ₃ ，Sm ₂ O ₃ ，Y ₂ O ₃ Is a good substance, canImprove the wettability of multiple components in the material, reduce the sintering point and promote Al ₂ O ₃ And SiO ₂ The reaction between the particles and the liquid phase with low melting point is formed, and the filling of substances among the particles to the pores can be promoted through the capillary action among the particles, so that the porosity of the material is reduced, and the density is improved. This analysis was validated with a number of products exhibiting very low water absorption in this project. Meanwhile, the ion radius of the trace rare earth oxide is much larger than that of the ceramic material researched by us, except that a small part of the trace rare earth oxide participates in solid melting, most of the trace rare earth oxide mainly exists at the phase boundaries between a crystal phase and between glass and the crystal phase, and large ions on the phase boundaries like nails nailed on a glass network hinder the uneven structure caused by the abnormal growth of the crystal on one hand, and limit the migration and crystallization of amorphous substances to the crystal on the crystal boundary on the other hand, and reduce the migration rate of the crystal boundary. And a part of rare earth oxide is fused into the glass phase, so that the strength of the glass is improved, and the overall mechanical property of the material is improved.

2) Discussion about antibacterial property, far infrared and anion mechanism

The existing inorganic antibacterial agents are basically divided into two types, one is a metal ion taking a metal ion as an active component, such as Ag ⁺ 、Zn ²⁺ ，Cu ²⁺ (ii) a Another class is oxide photocatalysts, e.g. TiO ₂ The action mechanism of the metal ions such as ZnO, mgO and the like is roughly as follows, the first type of the metal ions has two reactions, namely a contact type reaction, wherein the metal ions are firmly adsorbed on a cell membrane by virtue of charge action force, then break down cell walls to enter cells, so that bacterial protein is solidified, the cells lose division and proliferation capacity and die, and meanwhile, the metal ions can damage a microorganism electron transmission system, a respiratory system and a substance transmission system. b, photocatalytic reaction, namely, under the action of light, metal ions can be excited to carry out electron transfer to water adsorbed on the surface of the glaze layer and O in the air ₂ Production of-OH and O ₂ ^- They destroy the proliferation ability of bacteria in a short time, and inhibit or kill bacteria. The first class of antimicrobial agents generally requires an active carrier to carry the metal ions, such as zeolites, activated carbon, silica gel, phosphates, and the likeCan be used as a metal ion type carrier. The second category of oxide photocatalytic antibacterial agents is primarily redox reactions under the action of light, such as TiO ₂ Type under ultraviolet irradiation, ti ³⁺ With Ti ⁴⁺ Electron transfer occurs, and a large number of negative oxygen ions and free radicals OH with extremely strong chemical activity are generated on the surface of the carbon dioxide, and when the free radicals contact with microorganisms, the carbon dioxide is oxidized into CO ₂ And HO, thereby performing a sterilization function in a short time. Both of these antibacterial agents are limited in terms of use because they require the action of light in addition to the contact reaction in the first type, and particularly, the second type of oxide photocatalytic type requires irradiation with high-energy light such as ultraviolet light or near ultraviolet light.

In order to expand the photoresponse range of the antibacterial agent and enable the antibacterial agent to continuously play an antibacterial role under visible light or no light conditions, a great deal of research work is carried out by technical workers in recent years, a rare earth activation and compounding technology is adopted, so that a new energy level is added on the surface of a metal oxide photocatalytic material, multiband photocatalytic reaction under the conditions of visible light and ultraviolet light is realized, the generation capacity of free radicals is improved, and the function of the material is enhanced through a photocatalysis and rare earth valence-change synergistic component.

All products developed by the invention do not need to be added with any antibacterial agent. Conventional chemical analysis and X fluorescence spectrum analysis in the components of the blank and glaze do not have Ag ions, so the invention does not belong to the first type of contact participation reaction type antibacterial mechanism, but because of the existence of rare earth elements with rich species in the wulan tea crystalloid and the existence of magnesium oxide, zinc oxide, titanium oxide, calcium oxide, berkelium oxide, iron oxide and a plurality of trace oxides with relatively large atomic weight in the glaze of the ceramic blank, the surface energy level can be improved under the excitation of the rare earth elements, and the same action and mechanism of a second type of antibacterial agent can also be generated. In addition, as mentioned above, the various rare earth elements after sintering enter into amorphous states, namely crystals and crystal boundaries, and a large amount of rare earth element oxides in the crystal boundaries inhibit the migration of the crystals, so that the whole material is in a high energy state, so that the ceramic material prepared by taking wulan tea crystal as a main raw material is an 'energy porcelain', and metal ions in the ceramic material can release certain energy waves outwards through vibration, coupling, rotation and the like among the ions without special excitation conditions. Due to the fact that the types of the contained rare earth elements are various, the rare earth elements enter an aluminosilicate structure due to the special electronic layer structure of the elements, under the synergistic effects of hybridization among orbitals, entanglement of electronegativity among orbitals, mutual activation and the like, the material shows certain particularity in the aspects of light and electricity, and the complex system action is reflected on the surface, such as the generation of far infrared rays, the increase of surface free radicals, the generation of negative ions and the like. We believe this is the primary antimicrobial mechanism for this project.

In addition, a mechanism is discussed here, which is based on the analysis result of trace elements in wulan tea spar, that rubidium, a light metal with a content of more than 195pm, is a very strong photoelectric material, and can release electrons under normal visible light, and if it participates in the reaction of aluminosilicate, does it have the function? If the nano-TiO-like nano-particles exist, nano-TiO-like nano-particles can be generated on the surface of the material ₂ Effect of the photosensitive material. Due to the excitation of various rare earth elements, rubidium in the material can generate escape of electrons in a normal state, electrons on a valence band can easily jump to a conduction band, positive charge holes are left, and c and H can be in contact with O adsorbed on the surface of the material ₂ OH and water to produce OH and O ₂ And H ₂ O ₂ Etc., OH has oxidizing properties and H ₂ O ₂ (active oxygen, atomic oxygen) has stronger oxidizability, O ₂ ^- Has stronger reducibility, which is another mechanism for generating antibacterial and anion functions. The method is limited by the technical level and detection means, has no theory or data support, and is only a research.

3) The research on the mechanism of selenium dissolution is known from chemical analysis, both raw ore and processed wulan tea crystal stone belong to selenium-rich raw materials, and the products aiming at planting and cooking are expected to be dissolved out of selenium. However, the existence of selenium in minerals has not been known so far, and is a gas-solid substance that can be gasified and sublimated at very low temperature (around 800 ℃), and is present in which part of minerals in what form? This problem we have no clear recognition or conclusion by XRD, XRF, SEM, energy spectrum analysis.

5) Regarding the easy-to-clean aspect, the wulan tea crystal stone ceramic shows easy-to-clean performance no matter whether the glaze contains wulan tea crystal stone components or not, as long as the blank has a sufficient amount of proportion, the blank is a high-energy substance after being fired, and the stronger far infrared ray function and free radicals are changed from 'macromolecules' into 'micromolecules' (the molecular accumulation degree is reduced), so that the surface tension of water is reduced, the wettability on the surface of the material is enhanced, and the easy-to-clean effect is generated. In addition, O2 and-OH are formed on the surface of the rare earth multi-element, which is also beneficial to wetting the joint surface of the product and water and enhances the easy cleaning property. At present, the index of easy cleaning is not based on a test method and a standard, the aspect is only the respective experience of users, how to quantify the concept needs further work, and reference can be made to only determine the wetting angle of water after contacting with a product.

Claims

1. The antibacterial magnesium porcelain is characterized by being prepared from a blank and a glaze, wherein the blank comprises the following components in parts by weight: 25 parts of wulan tea spar, 28-38 parts of raw talc, 25-40 parts of cooked talc, 3-8 parts of Pingding trilobate gangue and 1-8 parts of Pingding dry surface; the glaze comprises the components of 94.6 parts of frit, 3 parts of flat dry surface, 2 parts of cellulose and 0.4 part of alkali surface in parts by weight; the chemical composition of the Pingding three-flower gangue is SiO ₂ 70 parts of Al ₂ O ₃ 25 parts of Fe ₂ O ₃ 0.14 part of TiO ₂ 0.03 part, caO0.28 part, mgO0.5 part, K ₂ O2.1 parts, na ₂ 0.3 part of O and 1.7 parts of ignition loss; the chemical composition of the flat dry surface is SiO ₂ 46.5 parts of Al ₂ O ₃ 39.7 parts, caO0.37 part, mgO0.18 part and 13.3 parts of ignition loss.

2. The antibacterial magnesium porcelain according to claim 1, wherein the blank comprises the following components in parts by weight: 25 parts of wulan tea spar, 28 parts of raw talc, 35 parts of cooked talc, 8 parts of Pingding trilobate gangue and 4 parts of Pingding dry surface; the glaze comprises, by weight, 94.6 parts of frit, 3 parts of Pingting dry powder, 2 parts of cellulose and 0.4 part of soda powder.

3. The antibacterial magnesium porcelain according to claim 1, wherein the blank comprises the following components in parts by weight: 25 parts of wulan tea spar, 38 parts of raw talc, 26 parts of cooked talc, 3 parts of Pingding trilobate gangue and 8 parts of Pingding dry surface; the glaze comprises, by weight, 94.6 parts of frit, 3 parts of Pingting dry flour, 2 parts of cellulose and 0.4 part of soda flour.

4. The method for preparing the antibacterial magnesium porcelain according to claim 1, which is characterized by comprising the following steps:

step one, proportioning blanks in parts by weight, ball-milling the blanks, sieving for removing iron, filtering mud, performing vacuum mud refining and ageing of mud, performing second vacuum mud refining and ageing of mud, shaping blanks after blank making and shaping, performing biscuit firing after the biscuit making, and polishing to obtain a smooth and fine biscuit firing product without impurities;

step two, proportioning glaze materials in parts by weight, performing wet ball milling on the glaze materials, preparing glaze slip, and deironing and sieving the glaze slip to obtain standby glaze slip;

step three, spraying glaze on the biscuit firing product obtained in the step one by using the standby glaze slip prepared in the step two, and firing after glaze spraying to obtain the antibacterial magnesium porcelain;

biscuiting is completed in a natural gas tunnel kiln, a gas tunnel kiln or an electric-burning shuttle kiln, wherein the firing temperature is 1230-1250 ℃, and the firing curve is as follows: room temperature-200 deg.C, 60 min; at 200-400 deg.c for 90 min; 400-600 ℃ for 100 minutes; 600-900 ℃ for 120 minutes; 900-1000 ℃ for 30 minutes; 75 minutes at 1000-1200 ℃; 1200-1250 ℃ for 30 minutes; keeping the temperature for 1 hour, and cooling to 700 ℃ for two hours;

the firing after the glaze spraying in the step three is finished in a natural gas tunnel kiln, a gas tunnel kiln or an electric-firing shuttle kiln, and the firing temperature is 1130-1150 ℃ to obtain a qualified product; the firing curve is as follows: room temperature-200 deg.C for 60 min; at 200-400 deg.c for 90 min; 400-600 ℃ for 100 minutes; 600-900 ℃ for 120 minutes; 900-1000 ℃ for 45 minutes; 1000-1150 ℃ for 80 minutes; keeping the temperature for 1 hour, and cooling to 700 ℃ for two hours.