High-temperature-resistant inorganic antibacterial ceramic glaze and preparation process thereof

Abstract

The invention discloses a high-temperature-resistant inorganic antibacterial ceramic glaze and a preparation process, and relates to the technical field of ceramic glaze preparation, the glaze is composed of a basic glaze and a zinc oxide-doped cerium dioxide inorganic antibacterial agent, and the basic glaze comprises feldspar, quartz, kaolin, calcite and talc. The preparation process comprises the following steps: mixing the raw materials, carrying out wet ball milling, adding the antibacterial agent and the dispergator, stirring at a high speed, sieving to remove iron, aging, glazing and sintering at a high temperature. In the process, an iron removal integrated unit integrating a two-stage vibration screening function and an automatic iron scraping function is adopted, and efficient and continuous iron removal operation is achieved. The obtained glaze can resist high-temperature sintering of 1150-1200 DEG C, the glaze surface is smooth and uniform, the glaze surface has lasting and efficient broad-spectrum antibacterial performance, glaze surface defects caused by iron impurities are effectively avoided, and the product yield and quality stability are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramic glaze preparation, and particularly relates to a high-temperature-resistant inorganic antibacterial ceramic glaze and a preparation process. BACKGROUND

[0002] The building and sanitary ceramic industry pays great attention to the use of advanced glaze technology. A large number of professional ceramic glaze and ceramic frit, colorant companies have appeared in China. The glazes used in building and sanitary ceramic products are increasingly diverse. The glaze products used by most ceramic enterprises can be roughly classified as follows: lead glaze and lead-free glaze; raw material glaze and frit glaze; one-time firing or two-time firing glaze; ceramic tile, tableware, sanitary ceramic and electric porcelain glaze; dipping glaze, spraying glaze and pouring glaze according to the glazing method; high-temperature glaze and low-temperature glaze; high-expansion glaze and low-expansion glaze; oxidizing flame, neutral flame and reducing flame according to the firing atmosphere; color glaze and colorless glaze; transparent glaze and opalescent glaze; glossy glaze, non-glossy glaze, semi-non-glossy glaze or patterned glaze, etc.

[0003] However, while pursuing the decorative effect and functionality of the glaze surface, the existing technology still faces some specific challenges. First, in terms of glaze purity control, the iron impurities introduced in the raw materials and production process are a major problem. If these impurities are not effectively removed, they will cause defects such as black spots and pinholes on the glaze surface during the subsequent high-temperature firing stage, seriously affecting the appearance grade and commercial value of the product. Traditional iron removal methods such as standing and settling or simple magnetic separation often have low efficiency, cannot be continuously operated, and require manual cleaning of the adsorbed iron, which cannot meet the needs of modern high-efficiency and clean production. Second, with the increasing emphasis on healthy living environments, there is an increasing demand for antibacterial ceramic products, but combining antibacterial functionality with ceramic glaze poses a technical bottleneck. Many organic antibacterial agents cannot withstand the sintering temperature of ceramic glaze, which is above 1100℃, and will decompose and lose effectiveness during the firing process. Some inorganic antibacterial agents may have narrow antibacterial spectrum, insufficient long-term effectiveness, or react with the glaze at high temperatures to affect the appearance of the glaze surface. Therefore, developing an antibacterial glaze that can withstand high-temperature sintering processes, maintain high-efficiency and broad-spectrum antibacterial properties, and not affect the quality of the glaze surface is a key difficulty. Third, from the perspective of production process, traditional glaze preparation involves multiple independent processes such as ball milling, sieving, iron removal, and aging, with frequent material flow, which not only needs to be improved in terms of production efficiency, but also increases the complexity of process control and uncertainty in the production process.

[0004] Therefore, there is an urgent need in the industry for an innovative solution that can systematically overcome the above-mentioned deficiencies and provide a high-temperature-resistant ceramic glaze with excellent glaze surface quality, durable and efficient antibacterial functionality, and high-purity glaze paste through an efficient and integrated production process. SUMMARY

[0005] The application aims to provide a high-temperature-resistant inorganic antibacterial ceramic glaze and a preparation process thereof.

[0006] To achieve the above-mentioned purpose, the application provides the following technical scheme: a high-temperature-resistant inorganic antibacterial ceramic glaze, which is composed of a base glaze and an antibacterial agent; the base glaze is composed of the following raw materials in mass fraction: feldspar 45-55%, quartz 22-30%, kaolin 10-15%, calcite 5-8%, and talc 5-7%, and the sum of the content of each component is 100%; the antibacterial agent is an inorganic antibacterial agent of zinc oxide doped with cerium dioxide, and the addition amount is 3-8% of the weight of the base glaze; the molar ratio or weight ratio of zinc oxide to cerium dioxide is (90:10)-(95:5).

[0007] Another technical purpose of the application is to provide a preparation process of the high-temperature-resistant inorganic antibacterial ceramic glaze, and the specific steps are as follows: Step one: the following base glaze raw materials are weighed according to the mass fraction: feldspar 45-55%, quartz 22-30%, kaolin 10-15%, calcite 5-8%, and talc 5-7%, and they are mixed uniformly; at the same time, an inorganic antibacterial agent of zinc oxide doped with cerium dioxide is prepared, and the weight of the inorganic antibacterial agent is 3-8% of the weight of the base glaze; Step two: ball milling preparation of the base glaze slurry: all the base glaze raw materials weighed in step one are put into a ball mill, and water equivalent to 40-50% of the total weight of the dry materials is added for wet ball milling, the ball milling time is 10-15 hours, and the slurry fineness is controlled to be 325 mesh with a sieve residue of ≤0.1%, so that the base glaze slurry is prepared; Step three: compounding of the antibacterial glaze slurry: the inorganic antibacterial agent accounts for 3-8% of the total mass of the base glaze, and sodium tripolyphosphate is added as a deagglomerating agent, which accounts for 0.1-0.3% of the total mass of the base glaze, and the mixture is high-speed stirred in a stirrer at a speed of 300-500 r / min for 30-45 minutes to ensure that the antibacterial agent is uniformly dispersed in the glaze slurry, so that the antibacterial glaze slurry is obtained; Step four: sieving, iron removal and aging of the glaze slurry: the glaze slurry is sieved and then subjected to iron removal treatment, finally, the glaze slurry after iron removal is poured into an aging tank and sealed for aging at room temperature for 24-48 hours to stabilize the performance of the glaze slurry; Step five: glazing: the antibacterial glaze slurry aged in step four is uniformly applied to the surface of the biscuit body by using the glazing process of glazing, spraying or dipping, and the dry glaze layer thickness is controlled to be 0.2-0.5 mm; Step six, high-temperature sintering: the ceramic body after glazing in step five is put into a roller kiln, and sintering is carried out in an oxidizing atmosphere, and the sintering schedule is: the temperature is raised from room temperature to 1150-1200 DEG C at a rate of 3-5 DEG C / min, and kept at this temperature for 15-30 min, and then naturally cooled to room temperature, to obtain the high-temperature-resistant inorganic antibacterial ceramic glaze product.

[0008] As a further scheme of the present application: the antibacterial glaze slurry prepared in step three is first coarsely sieved through an 80-mesh vibrating screen, then finely sieved through a 325-mesh vibrating screen, and then iron removal treatment is performed; the sieving and iron removal steps in step four are operated using a two-stage vibrating screen and iron removal integrated unit; the two-stage vibrating screen and iron removal integrated unit comprises a base, the top end of the base is fixedly connected with a supporting spring, the top end of the supporting spring is fixedly connected with a second vibrating frame, the top end of the second vibrating frame is fixedly connected with a first vibrating frame, the inner walls of the first vibrating frame and the second vibrating frame are both provided with a screen, the outer wall of the first vibrating frame and above the inner screen of the first vibrating frame are fixedly connected with a first discharge port, the lower part of the first discharge port is provided with a collecting box, the bottom of the second vibrating frame is provided with an inclined bottom plate, and the outer wall of the second vibrating frame between the inner screen and the bottom plate is fixedly connected with a second discharge port, the glaze slurry discharged from the second discharge port is subjected to iron removal operation by the iron removal mechanism.

[0009] As a further scheme of the present application: the iron removal mechanism comprises a guide groove, the guide groove is arranged below the second discharge port, supporting frames are arranged on both sides of the guide groove, a mounting shaft is rotatably connected in the supporting frame, a magnetic separation roller is fixedly connected to the outer wall of the mounting shaft, a slide rail is fixedly connected to one side of the supporting frame, a collecting box is arranged below the slide rail, a motor is mounted on the outer wall of one side of the supporting frame, a threaded rod is connected to the output end of the motor, a movable seat is slidably connected to the outer wall of the threaded rod, the top end of the movable seat is in contact with the inner wall top end of the supporting frame, a recess is formed in the bottom end of the movable seat, a horizontal plate is fixedly connected to the inner wall of the recess, a scraper is rotatably connected to one side of the horizontal plate, the top end of the scraper is fixedly connected with a rotating plate, an L-shaped block is fixedly connected to the outer wall of the supporting frame above the slide rail, and the magnetic separation roller is automatically rotated by the rotating mechanism.

[0010] As a further scheme of the present application: the rotating mechanism comprises a mounting frame, the mounting frame is fixedly connected to the side of the support frame away from the collecting frame, a vertical plate is fixedly connected to the outer wall of the support frame above the mounting frame, a pushing frame is slidingly connected to the outer wall of the vertical plate, a first spring is connected between the pushing frame and the vertical plate, a square rod is slidingly connected in the mounting frame, one end of the square rod is fixedly connected with an extrusion block, and a second spring is connected between the extrusion block and the mounting frame.

[0011] As a further scheme of the present application: the rotating mechanism further comprises a rotating disc, the rotating disc is fixedly connected to the outer wall of the mounting shaft and located between the pushing frame and the extrusion block, one end of the rotating disc is fixedly connected with a displacement plate, the other end of the rotating disc is fixedly connected with a displacement block, a first inclined surface is formed in one end of the displacement plate, a second inclined surface and a third inclined surface are formed in the outer wall of the displacement block.

[0012] As a further scheme of the present application: a threaded hole is formed in the outer wall of the movable seat, the threaded hole is matched with the threaded rod, and the top end of the outer wall of the movable seat is attached to the top end of the inner wall of the support frame.

[0013] As a further scheme of the present application: an arc-shaped surface is arranged at the bottom end of the scraper, and the arc-shaped surface is attached to the outer wall of the magnetic separation roller.

[0014] As a further scheme of the present application: a square groove is formed in the outer wall of the vertical plate, the inner wall of the square groove is attached to the outer wall of the pushing frame, a limiting block is fixedly connected to the top end of the pushing frame, and the limiting block is in contact with the vertical plate.

[0015] As a further scheme of the present application: a pointed end is arranged at the end of the extrusion block facing the rotating disc, a sliding groove is formed in the outer wall of the mounting frame, and the inner wall of the sliding groove is attached to the outer wall of the square rod.

[0016] Compared with the prior art, the present application has the following advantages: 1. The high-temperature-resistant inorganic antibacterial ceramic glaze material of the present application adopts a feldspar-quartz-kaolin system as a basic glaze material optimized through experiments, and matches an inorganic antibacterial agent doped with zinc oxide and cerium dioxide. The composite antibacterial agent can withstand high-temperature sintering of 1150-1200℃, stably exists in the glaze layer and plays a long-acting and broad-spectrum antibacterial role, overcoming the problems of organic antibacterial agents not being resistant to high temperature and some inorganic antibacterial agents affecting the quality of the glaze surface.

[0017] 2. The high-temperature-resistant inorganic antibacterial ceramic glaze of the present application is prepared by the optimized "wet ball milling-high-speed stirring degumming-multi-stage screening iron removal-sealing aging" process, which ensures the fineness, uniformity and purity of the glaze slurry. Combined with subsequent precise glazing thickness control and staged heating sintering process, the final glaze surface is smooth, uniform, high gloss, good thermal shock stability, and free of iron spots, pinholes and other defects, which systematically improves the consistency and yield of the product.

[0018] 3. The dual-stage vibration screening and iron removal integrated unit realizes continuous and automatic operation of screening and iron removal, reduces material turnover and manual intervention, thereby simplifying the process flow and improving production efficiency, and systematically responding to the "complicated process" problem in the background technology. The dual-stage vibration screening and iron removal integrated unit is provided with an iron removal mechanism and a rotating mechanism. The glaze slurry falls onto the guide groove through the second discharge port. When the glaze slurry passes through the magnetic separation roller, the iron in the glaze slurry is adsorbed on the magnetic separation roller. When the movable seat moves away from the slide rail, the scraper moves the iron into the slide rail. When the movable seat moves away from the slide rail, the scraper does not contact the magnetic separation roller. Until the movable seat moves to the other end, the scraper rotates to the vertical state, and the magnetic separation roller automatically rotates by a certain angle, which facilitates the iron removal operation of the screened glaze slurry and ensures the purity of the glaze slurry. The iron is adsorbed on the magnetic separation roller, and the iron on the magnetic separation roller is conveniently scraped off for collection operation.

[0019] 4. By setting the rotating mechanism, when the movable seat moves away from the slide rail, the pusher and the rotating plate are in contact, so that the scraper is in a vertical state. The movable seat continues to displace. The pusher is displaced by the rotating plate. The pusher is in contact with the first inclined surface. The displacement plate and the rotating disc are rotated until they are inserted into the gap between the two displacement plates. When the movable seat moves towards the slide rail, the extrusion block slides along the third inclined surface to the second inclined surface and the third inclined surface. The extrusion block drives the rotating disc to rotate by the displacement block, which facilitates the automatic rotation of the magnetic separation roller by a certain angle during the reciprocating displacement of the movable seat, and facilitates the subsequent scraping of the iron on the magnetic separation roller. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 The structure diagram of the dual-stage vibration screening and iron removal integrated unit of the present application; Figure 2 The structure diagram of the first vibration frame and the second vibration frame of the dual-stage vibration screening and iron removal integrated unit of the present application; Figure 3 The structure diagram of the support frame of the dual-stage vibration screening and iron removal integrated unit of the present application; Figure 4 The internal structure diagram of the support frame of the dual-stage vibration screening and iron removal integrated unit of the present application; Figure 5The internal structure diagram of the movable seat of the double-stage vibration screen and iron removal integrated machine set is shown in the figure. Figure 6 The installation diagram of the pushing frame of the double-stage vibration screen and iron removal integrated machine set is shown in the figure. Figure 7 The installation diagram of the square rod of the double-stage vibration screen and iron removal integrated machine set is shown in the figure. Figure 8 The structure diagram of the rotating disc of the double-stage vibration screen and iron removal integrated machine set is shown in the figure.

[0021] In the figure: 1, base; 2, supporting spring; 3, first vibrating frame; 4, first discharge port; 5, collecting box; 6, second vibrating frame; 7, second discharge port; 8, iron removal mechanism; 801, guide groove; 802, supporting frame; 803, mounting shaft; 804, magnetic separation roller; 805, sliding rail; 806, collecting frame; 807, motor; 808, threaded rod; 809, movable seat; 810, groove; 811, cross plate; 812, scraper; 813, rotating plate; 814, L-shaped block; 9, rotating mechanism; 901, mounting frame; 902, vertical plate; 903, pushing frame; 904, first spring; 905, square rod; 906, extrusion block; 907, second spring; 908, rotating disc; 909, displacement plate; 910, displacement block; 911, first inclined surface; 912, second inclined surface; 913, third inclined surface; 10, screen; 11, limiting block. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0023] In the description of this invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicating orientation or positional relationships, are based on the orientation or positional relationships shown in the accompanying drawings and are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance. In the description of this invention, it should be noted that unless otherwise explicitly specified and limited, the terms "installed," "connected," "linked," and "set up" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal communication of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances. The following describes embodiments of the invention based on its overall structure.

[0024] Example 1: A preparation process for a high-temperature resistant inorganic antibacterial ceramic glaze, the specific steps of which are as follows: Step 1: Preparation of base glaze and antibacterial agent: Weigh the following base glaze raw materials according to the mass fraction: feldspar 50%, quartz 22%, kaolin 12%, calcite 8%, talc 5%, and mix them evenly.

[0025] The zinc oxide-doped cerium dioxide inorganic antibacterial agent used in this embodiment was prepared as follows: 95 parts by weight of analytical grade zinc oxide and 5 parts by weight of analytical grade cerium dioxide were weighed, and an appropriate amount of anhydrous ethanol was added as a dispersion medium. The mixture was then mixed in a planetary ball mill for 4 hours until homogeneous, and then dried at 100°C. The dried powder was placed in a muffle furnace and calcined at 800°C for 2 hours, followed by furnace cooling. The calcined powder was then ground and passed through a 325-mesh sieve to obtain zinc oxide-doped cerium dioxide composite antibacterial agent powder (ZnO:CeO2 molar ratio 95:5).

[0026] Prepare the above-mentioned antibacterial agent at a weight equivalent to 8% of the base glaze.

[0027] Step 2: Ball milling preparation of basic glaze slurry: Put all the basic glaze raw materials weighed in Step 1 into a ball mill, and add water equivalent to 45% of the total dry weight for wet ball milling. The ball milling time is 12 hours until the fineness of the glaze slurry reaches 325 mesh and the sieve residue is ≤0.1%, thus preparing the basic glaze slurry.

[0028] Step three, compounding of antibacterial slip: to the base slip prepared in step two above, add 8% of the above antibacterial agent based on the total mass of the base glaze, and add 0.2% of sodium tripolyphosphate as a deagglomerating agent based on the total mass of the base glaze, and mix the materials in a blender at a speed of 400 r / min for 40 minutes to ensure uniform dispersion of the antibacterial agent in the slip, and obtain the antibacterial slip.

[0029] Step four, sieving, iron removal and aging of the slip: use a two-stage vibrating screen and iron removal integrated unit to first coarsely sieve the antibacterial slip prepared in step three above through an 80-mesh vibrating screen, then finely sieve it through a 325-mesh vibrating screen, remove the iron from the sieved slip, and finally pour the iron-removed slip into an aging tank for sealed aging at room temperature for 36 hours.

[0030] Step five, glazing: apply the aged antibacterial slip from step four above to the surface of the biscuit by spraying, and control the dry glaze layer thickness to be 0.3 mm.

[0031] Step six, high-temperature sintering: place the glazed biscuit from step five above into a roller kiln, and sinter it in an oxidizing atmosphere with a sintering schedule of: heating from room temperature to 1180℃ at a rate of 4℃ / min, and holding at this temperature for 20 minutes, then naturally cooling to room temperature, to obtain a high-temperature resistant inorganic antibacterial ceramic glaze product, denoted as sample S1.

[0032] Please refer to Figures 1 to 2 , the two-stage vibrating screen and iron removal integrated unit used in step four includes a base 1, the top end of the base 1 is fixedly connected with a supporting spring 2, the top end of the supporting spring 2 is fixedly connected with a second vibrating frame 6, the top end of the second vibrating frame 6 is fixedly connected with a first vibrating frame 3, the inner walls of the first vibrating frame 3 and the second vibrating frame 6 are both installed with a screen 10, the outer wall of the first vibrating frame 3 and above the screen 10 in the first vibrating frame 3 is fixedly connected with a first discharge port 4, below the first discharge port 4 is arranged a collecting box 5, the bottom of the second vibrating frame 6 is installed with an inclined bottom plate, the outer wall of the second vibrating frame 6 between the screen 10 and the bottom plate is fixedly connected with a second discharge port 7, the glaze discharged from the second discharge port 7 is subjected to iron removal operation by an iron removal mechanism 8.

[0033] In this embodiment: the base 1 is installed with a vibrating motor, the vibrating motor drives the first vibrating frame 3 and the second vibrating frame 6 to vibrate, the screens 10 in the first vibrating frame 3 and the second vibrating frame 6 are 80-mesh and 325-mesh respectively, the glaze is poured into the first vibrating frame 3, passes through the two screens 10 in turn, falls onto the inclined bottom plate, and is collected along the slope and discharged through the second discharge port 7, the discharged glaze is subjected to iron removal operation by the iron removal mechanism 8.

[0034] Please refer toFigures 3 to 5 The iron removing mechanism 8 comprises a guide groove 801 arranged below the second discharge port 7, support frames 802 arranged on both sides of the guide groove 801, mounting shafts 803 rotatably connected in the support frames 802, magnetic selection rollers 804 fixedly connected to the outer walls of the mounting shafts 803, slide rails 805 fixedly connected to one side of the support frames 802, collection frames 806 arranged below the slide rails 805, motors 807 mounted on the outer walls of one side of the support frames 802, threaded rods 808 connected to the output ends of the motors 807, movable seats 809 slidably connected to the outer walls of the threaded rods 808, recesses 810 formed in the bottom ends of the movable seats 809, transverse plates 811 fixedly connected to the inner walls of the recesses 810, scrapers 812 rotatably connected to one side of the inner walls of the recesses 810, rotating plates 813 fixedly connected to the top ends of the scrapers 812, L-shaped blocks 814 fixedly connected to the outer walls of the support frames 802 above the slide rails 805, and the magnetic selection rollers 804 are automatically rotated through the rotating mechanism 9.

[0035] In this embodiment, the magnetic selection rollers 804 are internally provided with electromagnetic coils, and the magnetic selection rollers 804 generate magnetic force after being electrified. The glaze slurry is discharged through the second discharge port 7 and falls onto the guide groove 801, and flows slowly along the guide groove 801. When the glaze slurry passes through the magnetic selection rollers 804, the iron filings in the glaze slurry are attracted by the magnetic selection rollers 804 and are adsorbed on the magnetic selection rollers 804.

[0036] The motor 807 drives the threaded rod 808 to rotate, the threaded rod 808 drives the movable seat 809 to displace, so that the movable seat 809 reciprocatingly displaces in the support frame 802, when the movable seat 809 displaces towards the slide rail 805, at this time, the scraper 812 is in a vertical state and is in contact with the horizontal plate 811, the bottom end of the scraper 812 is in contact with the outer wall of the magnetic roller 804, the displacement of the movable seat 809 drives the scraper 812 to displace, the displacement of the scraper 812 scrapes the iron filings at the top end of the magnetic roller 804 into the slide rail 805, the iron filings fall into the collecting frame 806 along the slide rail 805 for collection, at the same time, the rotating plate 813 is in contact with the L-shaped block 814, the L-shaped block 814 pushes the rotating plate 813 to rotate relative to the movable seat 809, the rotation of the rotating plate 813 drives the scraper 812 to rotate to be inclined, so that the bottom end of the scraper 812 is no longer in contact with the magnetic roller 804; then the movable seat 809 displaces away from the slide rail 805, at this time, the scraper 812 is not in contact with the magnetic roller 804, preventing the iron filings from being scraped in the opposite direction, until the movable seat 809 displaces to the other end, the parts in the rotating mechanism 9 are in contact with the rotating plate 813, so that the rotating plate 813 rotates, the rotation of the rotating plate 813 drives the scraper 812 to rotate to be vertical, then through the cooperation of the parts in the rotating mechanism 9, the mounting shaft 803 is driven to rotate by a certain angle, so that the magnetic roller 804 is driven to rotate by a certain angle, after completion, the movable seat 809 again displaces towards the slide rail 805, and the iron at the top end of the magnetic roller 804 is scraped; the design facilitates the iron removal operation on the screened glaze, and the iron is adsorbed on the magnetic roller 804, and the iron on the magnetic roller 804 is scraped off for collection operation.

[0037] Please refer to Figures 4 to 8 , the rotating mechanism 9 comprises a mounting frame 901, the mounting frame 901 is fixedly connected to one side of the support frame 802 away from the collecting frame 806, the outer wall of the support frame 802 is fixedly connected with a vertical plate 902 above the mounting frame 901, the outer wall of the vertical plate 902 is slidably connected with a pushing frame 903, the first spring 904 is connected between the pushing frame 903 and the vertical plate 902, the square rod 905 is slidably connected in the mounting frame 901, one end of the square rod 905 is fixedly connected with a pressing block 906, the second spring 907 is connected between the pressing block 906 and the mounting frame 901, the rotating mechanism 9 further comprises a rotating disc 908, the rotating disc 908 is fixedly connected to the outer wall of the mounting shaft 803 and located between the pushing frame 903 and the pressing block 906, one end of the rotating disc 908 is fixedly connected with a displacement plate 909, the other end of the rotating disc 908 is fixedly connected with a displacement block 910, one end of the displacement plate 909 is provided with a first inclined surface 911, the outer wall of the displacement block 910 is provided with a second inclined surface 912 and a third inclined surface 913.

[0038] In the embodiment, one end of the extrusion block 906 is located between the second inclined surface 912 and the third inclined surface 913 of the two displacement blocks 910, and the angle of the rotating disc 908 is positioned.

[0039] When the movable seat 809 moves away from the slide rail 805 until the pusher 903 contacts the rotating plate 813, the pusher 903 pushes the rotating plate 813 to rotate, and the rotating plate 813 drives the scraper 812 to rotate, so that the scraper 812 is in a vertical state and contacts the horizontal plate 811, and the scraper 812 and the rotating plate 813 cannot rotate. The movable seat 809 continues to displace, thereby pushing the pusher 903 to displace through the rotating plate 813, stretching the first spring 904, and pushing the displacement plate 909 and the rotating disc 908 to rotate until the pusher 903 is inserted into the gap between the two displacement plates 909. At this time, one end of the extrusion block 906 slides along the second inclined surface 912 of one displacement block 910 to the third inclined surface 913 of the same displacement block 910, and the second spring 907 is in a compressed state. When the movable seat 809 moves towards the slide rail 805, the pusher 903 is reset under the action of the first spring 904. At this time, the extrusion block 906 is displaced under the action of the second spring 907, and the extrusion block 906 slides along the third inclined surface 913 to the second inclined surface 912 and the third inclined surface 913 of the two displacement blocks 910. The extrusion block 906 pushes the rotating disc 908 to rotate through the displacement block 910, so that the first inclined surface 911 of the next displacement plate 909 is aligned with the pusher 903, facilitating the rotation of the rotating disc 908 next time. The rotating disc 908 drives the mounting shaft 803 to rotate, and the mounting shaft 803 drives the magnetic roller 804 to rotate, so as to automatically drive the magnetic roller 804 to rotate by a certain angle during the reciprocating displacement of the movable seat 809, and continuously scrape the iron filings on the magnetic roller 804.

[0040] Please refer to Figures 3 to 5 , the outer wall of the movable seat 809 is provided with a threaded hole matched with the threaded rod 808, and the top outer wall of the movable seat 809 is attached to the inner wall top of the support frame 802.

[0041] In the embodiment, the motor 807 drives the threaded rod 808 to rotate, and the threaded rod 808 drives the movable seat 809 to displace, thereby driving the movable seat 809 to reciprocate in the support frame 802. The movable seat 809 slides along the inner wall top of the support frame 802.

[0042] Please refer to Figures 3 to 5 , the bottom end of the scraper 812 is provided with an arc surface attached to the outer wall of the magnetic roller 804.

[0043] In the embodiment, when the movable seat 809 moves towards the slide rail 805, the scraper 812 is in the vertical state and in contact with the horizontal plate 811, the bottom end of the scraper 812 is in contact with the outer wall of the magnetic roller 804, the movable seat 809 drives the scraper 812 to move, and the scraper 812 moves to scrape the iron at the top end of the magnetic roller 804 into the slide rail 805.

[0044] It should be noted that the contact surface of the scraper 812 and the groove 810 has a certain frictional resistance, when the L-shaped block 814 pushes the rotating plate 813 to rotate relative to the movable seat 809 and drives the scraper 812 to rotate, at this time, due to the existence of the foregoing frictional resistance, the rotating plate 813 and the scraper 812 can remain in the inclined state in the return process, so that the scraper 812 is not in contact with the outer wall of the magnetic roller 804, until the rotating plate 813 is pushed again by the pushing frame 903, and the scraper 812 returns to the vertical state.

[0045] Please refer to Figures 4 to 8 , the outer wall of the vertical plate 902 is provided with a square groove, the inner wall of the square groove is in contact with the outer wall of the pushing frame 903, and the top end of the pushing frame 903 is fixedly connected with a limiting block 11, and the limiting block 11 is in contact with the vertical plate 902.

[0046] In the embodiment, the movable seat 809 continues to move, so that the pushing frame 903 is driven by the rotating plate 813 to move and stretch the first spring 904; when the movable seat 809 moves towards the slide rail 805, the pushing frame 903 is reset under the action of the elastic force of the first spring 904, and the limiting block 11 is used for limiting the movement distance of the pushing frame 903, so that the first spring 904 is always in the stretched state.

[0047] Please refer to Figures 4 to 8 , one end of the extrusion block 906 towards the rotating disc 908 is provided with a sharp end, and the outer wall of the mounting frame 901 is provided with a sliding groove, and the inner wall of the sliding groove is in contact with the outer wall of the square rod 905.

[0048] In the embodiment, when the movable seat 809 moves away from the slide rail 805, the pushing frame 903 is in contact with the first inclined surface 911, the pushing displacement plate 909 and the rotating disc 908 are driven to rotate, one end of the extrusion block 906 slides along the second inclined surface 912 of the displacement block 910 to the third inclined surface 913 of the same displacement block 910, and the second spring 907 is in the extruded state; when the movable seat 809 moves towards the slide rail 805, the extrusion block 906 slides along the third inclined surface 913 to the second inclined surface 912 and the third inclined surface 913 between the two displacement blocks 910, and the extrusion block 906 drives the rotating disc 908 to rotate through the displacement block 910.

[0049] Embodiment 2: Preparation process of a high-temperature-resistant inorganic antibacterial ceramic glaze, the specific steps are as follows: Step one, preparation of base glaze and preparation of antibacterial agent: the following base glaze raw materials are weighed according to mass fraction: feldspar 45%, quartz 28%, kaolin 15%, calcite 7%, and talc 5%, and mixed uniformly.

[0050] The zinc oxide doped cerium dioxide inorganic antibacterial agent used in this embodiment is prepared as follows: 90 parts by weight of analytical pure zinc oxide and 10 parts by weight of analytical pure cerium dioxide are weighed, and an appropriate amount of anhydrous ethanol is added as a dispersion medium, which is mixed in a planetary ball mill for 4 hours. After mixing uniformly, it is dried at 100°C. The dried mixed powder is placed in a muffle furnace and calcined at 800°C for 2 hours, and then cooled in the furnace. The calcined block is ground and sieved through a 325 mesh sieve to obtain zinc oxide doped cerium dioxide composite antibacterial agent powder (ZnO:CeO2 molar ratio 90:10).

[0051] Prepare the above antibacterial agent equivalent to 7% of the weight of the base glaze.

[0052] Step two, ball milling preparation of base glaze slurry: all the base glaze raw materials weighed in step one are put into a ball mill, and water equivalent to 45% of the total weight of the dry materials is added for wet ball milling. The ball milling time is 14 hours, until the fineness of the glaze slurry reaches 325 mesh, and the sieve residue is ≤0.1%, to prepare the base glaze slurry.

[0053] Step three, compounding of antibacterial glaze slurry: to the base glaze slurry prepared in step two, add the above antibacterial agent accounting for 7% of the total mass of the base glaze, and add sodium tripolyphosphate accounting for 0.25% of the total mass of the base glaze as a deagglomerating agent. Mix the materials in a blender at a speed of 450 r / min for 35 minutes to ensure uniform dispersion of the antibacterial agent in the glaze slurry, and obtain the antibacterial glaze slurry.

[0054] Step four, sieving, iron removal and aging of the glaze slurry: use a two-stage vibration sieve-iron removal integrated machine set to first coarsely sieve the antibacterial glaze slurry prepared in step three through an 80 mesh vibration sieve, and then finely sieve it through a 325 mesh vibration sieve. After sieving, the glaze slurry is treated for iron removal. Finally, the iron-removed glaze slurry is poured into an aging tank and sealed for aging at room temperature for 30 hours.

[0055] Step five, glazing: the antibacterial glaze slurry aged in step four is uniformly applied to the surface of the biscuit ceramic body using the spray glazing process, and the dry glaze layer thickness is controlled at 0.3 mm.

[0056] Step six, high-temperature sintering: the ceramic body after glazing in step five is placed in a roller hearth kiln and sintered in an oxidizing atmosphere, with a sintering schedule of: heating from room temperature to 1160°C at a rate of 4°C / min, and keeping the temperature for 25 min, and then naturally cooling to room temperature, to obtain a high-temperature-resistant inorganic antibacterial ceramic glaze product, denoted as sample S2.

[0057] Example 3: a preparation process of a high-temperature-resistant inorganic antibacterial ceramic glaze, with the specific steps as follows: Step one, preparation of base glaze and preparation of antibacterial agent: the following base glaze raw materials are weighed according to the mass fraction: feldspar 52%, quartz 28%, kaolin 10%, calcite 5%, and talc 5%, and mixed uniformly.

[0058] The inorganic antibacterial agent used in this example is prepared in the same way as in Example 1, and a composite antibacterial agent powder with a ZnO:CeO2 molar ratio of 95:5 is obtained.

[0059] An antibacterial agent equivalent to 3% of the weight of the base glaze is prepared.

[0060] Step two, ball milling preparation of base glaze slurry: all the base glaze raw materials weighed in step one are put into a ball mill, and water equivalent to 45% of the total weight of the dry materials is added for wet ball milling, with a ball milling time of 12 hours, until the fineness of the glaze slurry reaches 325 mesh with a sieve residue ≤0.1%, to prepare the base glaze slurry.

[0061] Step three, compounding of antibacterial glaze slurry: to the base glaze slurry prepared in step two, the above-mentioned antibacterial agent is added, accounting for 3% of the total mass of the base glaze, and sodium tripolyphosphate is added as a deagglomerating agent, accounting for 0.15% of the total mass of the base glaze, and the mixture is high-speed stirred in a stirrer at a speed of 350 r / min for 45 minutes to ensure uniform dispersion of the antibacterial agent in the glaze slurry, to obtain the antibacterial glaze slurry.

[0062] Step four, sieving, iron removal and aging of the glaze slurry: a two-stage vibration sieve-iron removal integrated machine set is used to first coarsely sieve the antibacterial glaze slurry prepared in step three through an 80-mesh vibration sieve, and then finely sieve it through a 325-mesh vibration sieve, and then remove iron from the sieved glaze slurry, and finally, the iron-removed glaze slurry is poured into an aging tank and sealed for aging at room temperature for 48 hours.

[0063] Step five, glazing: the antibacterial glaze slurry aged in step four is evenly applied to the surface of the bisque-fired ceramic body using a spraying glazing process, with a dry glaze layer thickness of 0.3 mm.

[0064] Step six, high-temperature sintering: the ceramic body after glazing in step five is placed in a roller hearth kiln, and sintering is carried out in an oxidizing atmosphere, with a sintering schedule of: heating from room temperature to 1200°C at a rate of 5°C / min, and keeping at this temperature for 15 min, and then naturally cooling to room temperature, to obtain a high-temperature-resistant inorganic antibacterial ceramic glaze product, denoted as sample S3.

[0065] Preparation process of a ceramic glaze, the specific steps are as follows: The base glaze formula of this comparative example is exactly the same as that of Example 1.

[0066] The specific steps of the preparation process and the application equipment are exactly the same as those of Example 1, the only difference is that no antibacterial agent is added in step three, and the obtained sample is denoted as D1.

[0067] Preparation process of a ceramic glaze, the specific steps are as follows: The base glaze formula of this comparative example is exactly the same as that of Example 1.

[0068] The specific steps of the preparation process and the application equipment are basically the same as those of Example 1, the difference is that in step three, an equal amount (8% of the total mass of the base glaze) of ordinary micron-sized zinc oxide (ZnO, purity > 99.9%, average particle size about 1.0 μm) is used instead of zinc oxide doped with cerium dioxide composite antibacterial agent, and the obtained sample is denoted as D2.

[0069] Preparation process of a ceramic glaze, the specific steps are as follows: The glaze composition (base glaze and antibacterial agent) of this comparative example is exactly the same as that of Example 1.

[0070] The specific steps of the preparation process and the application equipment are basically the same as those of Example 1, the difference is that in step four, the sieved glaze slurry is not subjected to iron removal treatment, but is directly injected into the aging tank for aging, and the obtained sample is denoted as D3.

[0071] Performance test and result analysis The above example samples S1-S3 and comparative example samples D1-D3 are tested as follows: 1. Antibacterial performance test, according to the film method in "GB / T 21510-2008 Nanometer Inorganic Materials Antibacterial Performance Test Method". The test bacteria are Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 6538). The bacterial suspension is added to the surface of the sample, covered with a film, incubated for 24 hours, then eluted and counted, and the antibacterial rate is calculated. Antibacterial rate (%) = (control sample viable count-test sample viable count) / control sample viable count x 100%.

[0072] 2. Glossiness test: The glossiness of the glaze center and the periphery of five points was measured using a 60° gloss meter (Model: KGZ-60), and the average value was taken.

[0073] 3. Thermal shock stability test: The sample was placed in a (180±5) °C muffle furnace for 30 minutes, and then quickly immersed in (20±5) °C water for rapid cooling. After drying, the glaze was observed. This cycle was repeated until the glaze had visible cracks, and the number of cycles was recorded.

[0074] 4. Glaze appearance evaluation: Under standard light source box (D65 light source), three experienced inspectors visually observed the sample glaze and recorded whether there were defects such as black spots, rust spots, pinholes, etc.

[0075] The antibacterial performance test table and the glaze performance test results are shown in the following table:

[0076] Table 1 Performance test results

[0077] As can be seen from the above table, the glaze products prepared by examples 1-3 (S1-S3) of the present application all exhibit excellent antibacterial performance (antibacterial rate > 97.5%) against two test bacteria. Comparative example D1 (without adding antibacterial agent) has basically no antibacterial effect, confirming that the antibacterial agent is the key to giving the product antibacterial function. The antibacterial rate of comparative example D2 (using ordinary ZnO) is significantly lower than all examples, which indicates that the doping and compounding of zinc oxide and cerium dioxide produce a synergistic effect, significantly improving the antibacterial performance, proving the technical advantage of using a specific composite antibacterial agent in the present application. Regarding the glaze quality and iron removal effect: As can be seen from Table 1, all samples passed the thermal shock cycle more than 5 times, indicating that the basic glaze formula has good thermal stability.

[0078] The glazes of examples S1-S3 and comparative examples D1, D2 (all subjected to iron removal treatment) are smooth and clean, without defects caused by iron impurities. However, the glaze of comparative example D3 (without iron removal) has obvious black / brown spots and pinholes, and the glossiness is significantly reduced (85.7 GU), which forms a more striking contrast with the examples (89.8-93.2 GU). This directly and powerfully proves that the iron removal treatment specified in step four of the preparation process of the present application is an indispensable key step for effectively removing iron impurities from the glaze slurry, avoiding defects on the glaze after firing, and ensuring the appearance quality of the final product, solving the problems pointed out in the background technology.

[0079] In summary, the high-temperature-resistant inorganic antibacterial ceramic glaze and the preparation process thereof provided by the application successfully obtain ceramic products with excellent antibacterial performance, high glaze quality and stable comprehensive performance through the specific composition of the base glaze, the application of the zinc oxide-doped cerium dioxide high-efficiency composite antibacterial agent and the fine process flow including forced iron removal. The embodiment data fully support the technical solutions and beneficial effects of the claims.

[0080] The above merely describes a preferred specific embodiment of the application, but the protection scope of the application is not limited thereto, and any person skilled in the art can make equivalent replacements or changes to the technical solutions and inventive concepts of the application within the technical scope disclosed by the application, which should be covered within the protection scope of the application.

Claims

1. A high-temperature-resistant inorganic antibacterial type ceramic glaze, consisting of a base glaze and an antibacterial agent, characterized in that The base glaze is composed of the following raw materials in mass fraction: feldspar 45-55%, quartz 22-30%, kaolin 10-15%, calcite 5-8%, talc 5-7%, and the sum of the content of each component is 100%; the antibacterial agent is zinc oxide doped with cerium dioxide inorganic antibacterial agent, and the addition amount is 3-8% of the weight of the base glaze; the molar ratio or weight ratio of zinc oxide to cerium dioxide is (90:10)-(95:5).

2. The preparation process of the high-temperature-resistant inorganic antibacterial ceramic glaze according to claim 1, characterized in that The specific steps are as follows: Step one, the following base glaze raw materials are weighed according to the mass fraction: feldspar 45-55%, quartz 22-30%, kaolin 10-15%, calcite 5-8%, talc 5-7%, and mixed uniformly; at the same time, prepare zinc oxide doped with cerium dioxide inorganic antibacterial agent equivalent to 3-8% of the weight of the base glaze; Step two, ball milling preparation of base glaze slurry: put all the base glaze raw materials weighed in step one into the ball mill, and add water equivalent to 40-50% of the total weight of the dry materials for wet ball milling, the ball milling time is 10-15 hours, until the fineness of the glaze slurry reaches 325 mesh, the sieve residue is ≤0.1%, and the base glaze slurry is prepared; Step three, compounding of antibacterial glaze slurry: add inorganic antibacterial agent accounting for 3-8% of the total mass of the base glaze to the base glaze slurry prepared in step two, and add sodium tripolyphosphate as a deagglomerating agent accounting for 0.1-0.3% of the total mass of the base glaze, and high-speed stir the mixture in a stirrer at a speed of 300-500 r / min for 30-45 minutes to ensure uniform dispersion of the antibacterial agent in the glaze slurry, and obtain the antibacterial glaze slurry; Step four, sieving, iron removal and aging of the glaze slurry: sieve the glaze slurry and then perform iron removal treatment, and finally, pour the iron-removed glaze slurry into an aging tank for sealed aging at room temperature for 24-48 hours to stabilize the performance of the glaze slurry; Step five, glazing: apply the antibacterial glaze slurry aged in step four to the surface of the biscuit ceramic body by using the glazing process of spraying, spraying or dipping, and control the dry glaze layer thickness to be 0.2-0.5 millimeters; Step six, high temperature sintering: put the ceramic body glazed in step five into a roller kiln and sinter it in an oxidizing atmosphere, and the sintering schedule is: increase the temperature from room temperature to 1150-1200℃ at a rate of 3-5℃ / min, and keep the temperature for 15-30 minutes, and then naturally cool to room temperature, and the high-temperature resistant inorganic antibacterial ceramic glaze product is obtained.

3. The process for preparing a high-temperature-resistant inorganic antibacterial ceramic glaze according to claim 2, characterized in that, The antibacterial slurry prepared in step three is first coarsely screened through an 80-mesh vibrating screen, then finely screened through a 325-mesh vibrating screen, and then iron removal treatment is performed; the screening and iron removal steps in step four are operated using a two-stage vibrating screen iron removal integrated unit; the two-stage vibrating screen iron removal integrated unit comprises a base (1), the top end of the base (1) is fixedly connected with a support spring (2), the top end of the support spring (2) is fixedly connected with a second vibrating frame (6), the top end of the second vibrating frame (6) is fixedly connected with a first vibrating frame (3), the inner walls of the first vibrating frame (3) and the second vibrating frame (6) are both provided with a screen (10), the outer wall of the first vibrating frame (3) and above the screen (10) in the first vibrating frame (3) is fixedly connected with a first discharge port (4), the lower part of the first discharge port (4) is provided with a collecting box (5), the bottom of the second vibrating frame (6) is provided with an inclined bottom plate, the outer wall of the second vibrating frame (6) between the screen (10) and the bottom plate is fixedly connected with a second discharge port (7), the glaze slurry discharged from the second discharge port (7) is subjected to iron removal operation by an iron removal mechanism (8).

4. The preparation process of the high-temperature-resistant inorganic antibacterial ceramic glaze according to claim 3, characterized in that, The iron removal mechanism (8) comprises a guide groove (801), the guide groove (801) is arranged below the second discharge port (7), the two sides of the guide groove (801) are provided with support frames (802), the inside of the support frame (802) is rotatably connected with a mounting shaft (803), the outer wall of the mounting shaft (803) is fixedly connected with a magnetic separation roller (804), one side of the support frame (802) is fixedly connected with a sliding rail (805), the lower part of the sliding rail (805) is provided with a collecting box (806), the outer wall of one side of the support frame (802) is provided with a motor (807), the output end of the motor (807) is connected with a threaded rod (808), the outer wall of the threaded rod (808) is slidably connected with a movable seat (809), the top end of the movable seat (809) is in contact with the inner wall top end of the support frame (802), the bottom end of the movable seat (809) is provided with a groove (810), the inner wall of the groove (810) is fixedly connected with a transverse plate (811), the inner wall of the groove (810) is rotatably connected with a scraper (812) on one side of the transverse plate (811), the top end of the scraper (812) is fixedly connected with a rotating plate (813), the outer wall of the support frame (802) is fixedly connected with an L-shaped block (814) above the sliding rail (805), the magnetic separation roller (804) is automatically rotated through a rotating mechanism (9).

5. The process for preparing a high-temperature-resistant inorganic antibacterial ceramic glaze according to claim 4, characterized in that, The rotating mechanism (9) includes a mounting frame (901), which is fixedly connected to the support frame (802) on the side away from the collection frame (806). A vertical plate (902) is fixedly connected to the outer wall of the support frame (802) above the mounting frame (901). A pusher (903) is slidably connected to the outer wall of the vertical plate (902). A first spring (904) is connected between the pusher (903) and the vertical plate (902). A square rod (905) is slidably connected inside the mounting frame (901). A pressing block (906) is fixedly connected to one end of the square rod (905). A second spring (907) is connected between the pressing block (906) and the mounting frame (901).

6. The process for preparing a high-temperature-resistant inorganic antibacterial ceramic glaze according to claim 5, characterized in that, The rotating mechanism (9) further includes a rotating disk (908), which is fixedly connected to the outer wall of the mounting shaft (803) and located between the push frame (903) and the extrusion block (906). One end of the rotating disk (908) is fixedly connected to a displacement plate (909), and the other end of the rotating disk (908) is fixedly connected to a displacement block (910). One end of the displacement plate (909) is provided with a first inclined surface (911), and the outer wall of the displacement block (910) is provided with a second inclined surface (912) and a third inclined surface (913).

7. The process for preparing a high-temperature-resistant inorganic antibacterial type ceramic glaze according to claim 4, characterized in that, The outer wall of the movable seat (809) is provided with a threaded hole, which matches the threaded rod (808). The top outer wall of the movable seat (809) is in contact with the top inner wall of the support frame (802).

8. The process for preparing a high-temperature-resistant inorganic antibacterial ceramic glaze according to claim 4, characterized in that, The bottom end of the scraper (812) is provided with an arc-shaped surface, which is in contact with the outer wall of the magnetic separator (804).

9. The process for preparing a high-temperature-resistant inorganic antibacterial ceramic glaze according to claim 6, characterized in that, The outer wall of the vertical plate (902) is provided with a square groove, the inner wall of the square groove is in contact with the outer wall of the push frame (903), and the top of the push frame (903) is fixedly connected to a limiting block (11), which is in contact with the vertical plate (902).

10. The process for preparing a high-temperature-resistant inorganic antibacterial ceramic glaze according to claim 6, characterized in that, The extrusion block (906) has a pointed end facing the rotating disk (908), and the outer wall of the mounting bracket (901) has a sliding groove, the inner wall of the sliding groove being in contact with the outer wall of the square rod (905).

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