Preparation process of gold-plated ceramic tile prepared from ceramic frit dry particles

Abstract

The invention discloses a preparation process of a gold-plated ceramic tile prepared from ceramic frit dry particles, and relates to the technical field of building decoration materials. The method comprises the following steps: preparing a green body; preparing frit dry particles; applying dry particles of the frit; sintering the green body; preparing a gold-imitating plating layer; and polishing and packaging. By optimizing the material formula and improving the technological process, the problems of high cost, serious environmental pollution, insufficient coating binding force and the like in the prior art are effectively solved; a nitrogen protective atmosphere sintering furnace is improved, a circulating purification mechanism is arranged, nitrogen in a box type atmosphere sintering furnace body is exhausted through an exhaust pipe and enters a recovery tower, activated carbon in the recovery tower is used for adsorption, a molecular sieve is used for dehydration, the nitrogen is purified, and the purified nitrogen enters a gas inlet pipe; nitrogen in the gas inlet pipe enters the box-type atmosphere sintering furnace body again through the gas inlet hole, the utilization rate of the nitrogen can be increased, and the consumption of the protective atmosphere is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of building decoration materials, and specifically to a preparation process of a gold-plated ceramic tile made of ceramic frit dry granules. Background Art

[0002] In the field of building decoration materials, gold-plated ceramic tiles, with their unique metallic texture and diverse decorative effects, have become important materials for high-end building decoration applications. Such products not only have excellent durability and outstanding functionality, but also can significantly enhance the practical value and extend the service life. In the preparation technology of gold-plated ceramic tiles, the frit dry granule process has attracted much attention by effectively solving the bonding problem between the metal coating and the ceramic substrate by constructing a frit dry granule transition layer on the surface of the ceramic substrate.

[0003] The preparation of existing gold-plated ceramic tiles mainly uses vacuum magnetron sputtering technology, electroplating process technology and transfer film technology, and each has its own advantages and disadvantages: the vacuum magnetron sputtering method realizes the metal coating through physical vapor deposition. Although the coating quality is good, the equipment investment is high; the electroplating process uses chemical plating, although the cost is low, but it needs to use cyanide-containing electroplating solution and the wastewater treatment is difficult; the transfer film technology uses physical transfer, but the pattern accuracy needs to be improved. These methods all have obvious technical limitations in practical applications, which to a certain extent restricts the industrial application and development of gold-plated ceramic tiles.

[0004] In the preparation technology of gold-plated ceramic tiles, the frit dry granule process has obvious technical advantages. By constructing a frit transition layer with a special formula on the surface of the ceramic substrate, this process can not only effectively alleviate the difference in thermal expansion coefficients between the metal coating and the ceramic substrate, but also significantly improve the coating bonding strength. Specifically, the active components in the frit dry granules form chemical bonds with the substrate during the sintering process, improving the coating bonding force. At the same time, the low-temperature sintering characteristics of the frit dry granules can also reduce energy consumption compared with traditional glazes, and greatly improve the process economy on the premise of ensuring the coating quality; however, when applied to the preparation of gold-plated ceramic tiles, the existing frit dry granule technology still has room for improvement in terms of process stability, cost control and environmental protection performance.

[0005] Based on the above analysis, the existing gold-plated ceramic tile preparation technology still faces many technical bottlenecks in industrial applications, and a new preparation process with both excellent coating performance and good economy needs to be developed. In view of these key technical problems, the present invention aims to establish a set of efficient, stable and environmentally friendly gold-plated ceramic tile preparation system by optimizing the frit dry granule formula, improving the coating process and developing special equipment, providing a reliable technical solution for the industry and promoting the industrial development of gold-plated ceramic tiles. Summary of the Invention

[0006] The object of the present invention is to provide a preparation process of a gold-plated ceramic tile made of ceramic frit dry granules in order to solve the problems of high cost, large environmental pollution, insufficient coating adhesion force, etc. existing in the prior art.

[0007] To achieve the above object, the present invention provides the following technical solution: A preparation process of a gold-plated ceramic tile made of ceramic frit dry granules, and the specific steps are as follows: Step 1: Preparation of the green body. Mix the proportioned ceramic raw materials evenly, ball mill until the fineness reaches 0.8 - 1.0% of the residue on a 250-mesh sieve, age for 12 - 24 hours in an environment with a humidity of 60 - 70%, press and mold at a pressure of 50 - 60 MPa, and dry in a chain dryer with hot air circulation at 110 - 120 °C until the moisture content is lower than 0.5%; Step 2: Preparation of the frit dry granules. Mix the proportioned frit raw materials evenly, melt at 1500 - 1550 °C and then water quench. After being detected by XRD as an amorphous glass phase (crystallinity < 5%), crush and screen to obtain 200 - 300-mesh particles for standby; Step 3: Application of the frit dry granules. Uniformly apply the frit dry granules prepared in Step 2 on the surface of the green body by using an application device, control the application amount to be 180 - 220 g / m². This device combines vibration feeding (frequency 25 ± 5 Hz) and negative pressure adsorption (pressure -0.04 ± 0.01 MPa) to ensure that the deviation of the dry granule distribution uniformity does not exceed ±10%; Step 4: Sintering of the green body. Use a nitrogen protection atmosphere sintering furnace to heat the green body with the applied frit dry granules in a nitrogen protection atmosphere, heat up to 600 °C at a rate of 3 - 5 °C / min, then heat up to 900 - 920 °C at a rate of 5 - 7 °C / min, keep warm for 15 - 20 minutes, then cool to 500 °C at a rate of ≤10 °C / min, and then cool to below 150 °C at a rate of 20 - 30 °C / min. After sintering, detect the surface flatness (≤0.1 mm / m) and porosity (≤3%) of the green body; Step 5: Preparation of the imitation gold coating. After ultrasonic cleaning, send the sintered brick blank into the pretreatment chamber, perform plasma surface activation treatment for 3 - 5 minutes under the conditions of a radio frequency power of 200 - 300 W and an Ar gas flow rate of 50 - 100 sccm, and then transfer it to the coating chamber to deposit three functional coatings in sequence: deposit a 0.2 - 0.3-μm Cr transition layer; deposit a 0.8 - 1.2-μm Cu-Zn-Ti alloy layer (Cu content 60 - 70 wt%, Zn content 20 - 30 wt%, Ti content 2 - 5 wt%); deposit a 0.1 - 0.2-μm SiO2 protective layer. Use an X-ray fluorescence spectrometer (XRF) to detect the thickness of each coating, and control the error within ±5%; Step 6: Polishing and packaging. The plated blank is gently polished with a planetary polishing machine (spindle speed 250 ± 50 rpm, pressure 0.05 - 0.1 MPa) using a diamond grinding head of 1500 - 2000 mesh. The adhesion of the plating layer (meeting Grade 4B according to ASTM D3359 standard) and the surface glossiness (≥90 GU, measured at a 60° angle) are detected. After passing the inspection, it is packaged.

[0008] Preferably, the ceramic raw materials for preparing the blank in Step 1 include the following components in weight percentages: Kaolin 50 - 55%; Quartz 25 - 35%; Feldspar 15 - 20%.

[0009] Preferably, the raw materials for preparing the frit dry granules in Step 2 include the following components in weight percentages: SiO2 50 - 55%; Al2O3 20 - 25%; ZrO2 3 - 5%; Na2O 5 - 8%; TiO2 1 - 3%.

[0010] As a further solution of the present invention: The nitrogen - protected atmosphere sintering furnace described in Step 4 includes a box - type atmosphere sintering furnace body. A furnace door is installed on the outer wall of the box - type atmosphere sintering furnace body. Electric heating elements are installed in the inner cavity of the box - type atmosphere sintering furnace body. The nitrogen gas in the box - type atmosphere sintering furnace body is circulated through a circulation and purification mechanism. The circulation and purification mechanism includes an air inlet hole, which is opened at the bottom end of the inner wall of the box - type atmosphere sintering furnace body. An air inlet pipe is fixedly connected to one side outer wall of the box - type atmosphere sintering furnace body, and a blower is installed on the air inlet pipe. An exhaust pipe is fixedly connected to the top end of the box - type atmosphere sintering furnace body. The air inlet pipe is communicated with the air inlet hole. A recovery tower is fixedly connected to one end of the exhaust pipe and the air inlet pipe. Two groups of upper air - permeable plates, lower air - permeable plates and square frames are arranged on the inner wall of the recovery tower. The upper air - permeable plate is located above the lower air - permeable plate, and the square frame is located between the upper air - permeable plate and the lower air - permeable plate. Activated carbon particles and molecular sieve particles are respectively stored in the cavities formed by the two groups of upper air - permeable plates, lower air - permeable plates and square frames, and the activated carbon particles and molecular sieve particles are replaced through a replacement mechanism.

[0011] As a further solution of the present invention: The replacement mechanism includes a storage box fixedly connected to the outer wall of one side of the recovery tower. A slot is provided on the outer wall of the other side of the recovery tower. A collection box is slidably connected to the inner wall of the slot. An activity groove for the square frame to slide is provided inside the storage box and the recovery tower. A connecting plate is fixedly connected to the outer wall of the square frame, and the connecting plate extends out of the storage box. A fixing groove is provided at the top of the activity groove inside the recovery tower. One end of the connecting plate is rotatably connected to a rotating column, and one end of the rotating column is fixedly connected to a threaded rod. A displacement rod is slidably connected to the outer wall of the threaded rod, and the displacement rod is slidably connected inside the connecting plate. One end of the displacement rod is rotatably connected to a connecting rod, and one end of the connecting rod is rotatably connected to a fixing block. The fixing block is slidably connected inside the connecting plate and extends above the connecting plate. A rotating plate is rotatably connected to one end of the outer wall of the recovery tower at the activity groove. A torsion spring is connected between the rotating plate and the recovery tower. A groove is provided at the bottom end of the rotating plate. A positioning frame extending into the inner cavity of the activity groove is slidably connected inside the recovery tower. A first spring is connected between the positioning frame and the recovery tower. The storage box is opened and closed through a connecting mechanism.

[0012] As a further solution of the present invention: The connecting mechanism includes a reinforcement groove provided at the top end of the connecting plate. A cover plate is provided at the top end of the storage box. A clamping groove is provided on one side of the inner wall of the storage box. A clamping block extending out of the cover plate is slidably connected inside the cover plate. A second spring is connected between the clamping block and the cover plate. A reinforcement rod is slidably connected inside the storage box. A third spring is connected between the reinforcement rod and the storage box. A spur gear is rotatably connected to the outer wall of the reinforcement rod inside the storage box. A pressing rod is slidably connected to the outer wall of the spur gear inside the storage box, and the pressing rod extends above the storage box.

[0013] As a further solution of the present invention: Threaded holes are provided on the outer wall of the displacement rod, and the threaded holes are matched with the threaded rod; both ends of the connecting rod are connected to the displacement rod and the fixing block through rotating shafts, and the outer wall of the top end of the fixing block is in contact with the inner wall of the fixing groove.

[0014] As a further solution of the present invention: The outer wall of the square frame is in contact with the inner wall of the activity groove; a triangular surface is provided at one end of the positioning frame located inside the square frame cavity, and the outer wall of the other end of the positioning frame is in contact with the inner wall of the groove.

[0015] As a further solution of the present invention: The bottom outer wall of the cover plate is in contact with the inner wall of the storage box, and the outer wall of one end of the clamping block is in contact with the inner wall of the clamping groove.

[0016] As a further solution of the present invention: the outer wall of the bottom end of the reinforcing rod fits with the inner wall of the reinforcing groove, and tooth grooves are provided on the outer walls of both the reinforcing rod and the pressing rod, and the tooth grooves are meshed with the spur gears.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. By optimizing the material formula and improving the process flow, the problems existing in the prior art, such as high implementation cost of the frit process, large environmental pollution, and insufficient bonding force of the coating, are effectively solved; 2. By setting a circulating purification mechanism, the nitrogen gas in the box-type atmosphere sintering furnace body is discharged through the exhaust pipe and enters the recovery tower. The activated carbon in the recovery tower adsorbs, and the molecular sieve dehydrates, purifying the nitrogen gas. The purified nitrogen gas enters the inlet pipe, and the nitrogen gas in the inlet pipe enters the box-type atmosphere sintering furnace body again through the air inlet holes, which can improve the utilization rate of nitrogen gas and reduce the consumption of protective atmosphere; 3. By setting a replacement mechanism and a connection mechanism, it is convenient to quickly replace the activated carbon particles and molecular sieve particles; quickly open and close the top of the storage box, which is convenient to add the activated carbon particles or molecular sieve particles into the storage box. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is a schematic structural diagram of the nitrogen gas protection atmosphere sintering furnace of the present invention; Figure 2 It is an installation schematic diagram of the upper air-permeable plate and the lower air-permeable plate of the nitrogen gas protection atmosphere sintering furnace of the present invention; Figure 3 It is an internal structural schematic diagram of the recovery tower of the nitrogen gas protection atmosphere sintering furnace of the present invention; Figure 4 It is a schematic structural diagram of the square frame of the nitrogen gas protection atmosphere sintering furnace of the present invention; Figure 5 It is an installation schematic diagram of the rotating plate of the nitrogen gas protection atmosphere sintering furnace of the present invention; Figure 6 It is of the nitrogen gas protection atmosphere sintering furnace of the present invention Figure 5 The enlarged view of part A; Figure 7 It is an internal structural schematic diagram of the connecting plate of the nitrogen gas protection atmosphere sintering furnace of the present invention; Figure 8 It is an internal structural schematic diagram of the storage box of the nitrogen gas protection atmosphere sintering furnace of the present invention.

[0019] In the figure: 1. Box-type atmosphere sintering furnace body; 2. Furnace door; 3. Electric heating element; 4. Circulation and purification mechanism; 401. Air inlet hole; 402. Air inlet pipe; 403. Fan; 404. Exhaust pipe; 405. Recovery tower; 406. Upper air-permeable plate; 407. Lower air-permeable plate; 408. Square frame; 5. Replacement mechanism; 501. Storage box; 502. Slot; 503. Collection box; 504. Movable slot; 505. Connecting plate; 506. Fixed slot; 507. Rotating column; 508. Threaded rod; 509. Displacement rod; 510. Connecting rod; 511. Fixed block; 512. Rotating plate; 513. Torsion spring; 514. Groove; 515. Positioning frame; 516. First spring; 6. Connecting mechanism; 601. Reinforcement groove; 602. Cover plate; 603. Card slot; 604. Card block; 605. Second spring; 606. Reinforcement rod; 607. Third spring; 608. Straight gear; 609. Pressing rod. Detailed implementation manners

[0020] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0021] In the description of the present invention, it should be noted that the orientation or positional relationship indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. is based on the orientation or positional relationship shown in the accompanying drawings, and is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation to the present invention. In addition, the terms "first", "second", and "third" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance. In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, the terms "installation", "connection", "connection", and "setting" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the communication inside two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific situations. The following will describe the embodiments according to the overall structure of the present invention. Embodiment 1

[0022] Please refer to Figures 1 to 8, in the embodiments of the present invention, a preparation process of a gold-plated ceramic tile made of ceramic frit dry granules is as follows: Step 1, preparation of the green body; mix evenly the ceramic raw materials of 50wt% kaolin, 35wt% quartz, and 15wt% feldspar, and ball mill to a sieve residue of 1.0% through a 250-mesh sieve. Age for 24 hours in an environment with a humidity of 60%. Press and form under a pressure of 50MPa, and dry in a chain dryer with hot air circulation at 110°C for 4 hours, with a moisture content of 0.48%.

[0023] Step 2, preparation of the frit dry granules; mix evenly the frit raw materials containing the following components: SiO2 50wt%; Al2O3 25wt%; ZrO2 3wt%; Na2O 8wt%; TiO2 1wt% of the frit raw materials, melt at 1500°C for 1.5 hours and then water quench. After XRD detection, the crystallinity is 4.2%, break and sieve to obtain 200-mesh particles for standby.

[0024] Step 3, application of the frit dry granules; use an application device with a vibration frequency of 20Hz and a negative pressure adsorption pressure of -0.05MPa to evenly apply the frit dry granules on the surface of the green body at an application amount of 180g / m². The measured uniformity deviation is -9.8%.

[0025] Step 4, sintering of the green body; under a nitrogen protection atmosphere, heat up to 600°C at a rate of 3°C / min, then heat up to 900°C at a rate of 5°C / min, and hold for 20 minutes. Subsequently, cool to 500°C at a rate of 8°C / min, and then cool to 120°C at a rate of 30°C / min. After sintering, the surface flatness of the green body is 0.09mm / m, and the porosity is 2.8%.

[0026] Step 5, preparation of the imitation gold plating layer; after the brick blank is ultrasonically cleaned, it is plasma activated for 5 minutes under the conditions of a radio frequency power of 200W and an Ar gas flow rate of 50sccm. Subsequently, deposit in sequence: a 0.2μm Cr transition layer; a 0.8μm Cu-Zn-Ti alloy layer (Cu 65wt%, Zn 30wt%, Ti 5wt%); a 0.1μm SiO2 protective layer. The thickness error of the plating layer detected by XRF is +4.7%.

[0027] Step 6, polishing and packaging; use a 1500-mesh diamond grinding head, and polish with a planetary polishing machine at a spindle speed of 200rpm and a pressure of 0.08MPa. Detect that the adhesion of the plating layer reaches grade 4B of the ASTM D3359 standard, and the surface glossiness is 92GU (measured at a 60° angle). Package the qualified products and store them in the warehouse.

[0028] In this embodiment, by optimizing the material formula and improving the process flow, the problems existing in the prior art, such as high cost, large environmental pollution, and insufficient coating adhesion, are effectively solved.

[0029] Please refer specifically to Figures 1 to 4 , the nitrogen protection atmosphere sintering furnace in step four includes a box-type atmosphere sintering furnace body 1. A furnace door 2 is installed on the outer wall of the box-type atmosphere sintering furnace body 1. An electric heating element 3 is installed in the inner cavity of the box-type atmosphere sintering furnace body 1. The nitrogen in the box-type atmosphere sintering furnace body 1 is circulated through a circulation and purification mechanism 4. The circulation and purification mechanism 4 includes an air inlet hole 401, which is opened at the bottom end of the inner wall of the box-type atmosphere sintering furnace body 1. A gas inlet pipe 402 is fixedly connected to one side outer wall of the box-type atmosphere sintering furnace body 1. A fan 403 is installed on the gas inlet pipe 402. A exhaust pipe 404 is fixedly connected to the top end of the box-type atmosphere sintering furnace body 1. The gas inlet pipe 402 is communicated with the air inlet hole 401. A recovery tower 405 is fixedly connected to one end of the exhaust pipe 404 and the gas inlet pipe 402. Two groups of upper air-permeable plates 406, lower air-permeable plates 407 and square frames 408 are arranged on the inner wall of the recovery tower 405. The upper air-permeable plates 406 are located above the lower air-permeable plates 407. The square frames 408 are located between the upper air-permeable plates 406 and the lower air-permeable plates 407. Activated carbon particles and molecular sieve particles are respectively stored in the cavities formed by the two groups of upper air-permeable plates 406, lower air-permeable plates 407 and square frames 408. The activated carbon particles and molecular sieve particles are replaced through a replacement mechanism 5.

[0030] In this embodiment, when the fan 403 operates, the nitrogen in the box-type atmosphere sintering furnace body 1 is discharged through the exhaust pipe 404 and enters the recovery tower 405. The activated carbon in the recovery tower 405 is used for adsorption and the molecular sieve is used for dehydration to purify the nitrogen. The purified nitrogen enters the gas inlet pipe 402, and the nitrogen in the gas inlet pipe 402 enters the box-type atmosphere sintering furnace body 1 again through the air inlet hole 401, which can improve the utilization rate of nitrogen and reduce the consumption of the protective atmosphere.

[0031] Please refer specifically to Figures 3 to 7, the replacement mechanism 5 includes a storage box 501, the storage box 501 is fixedly connected to the outer wall of one side of the recovery tower 405, a slot 502 is opened on the outer wall of the other side of the recovery tower 405, a collection box 503 is slidably connected to the inner wall of the slot 502, an activity groove 504 for the square frame 408 to slide is opened inside the storage box 501 and the recovery tower 405, a connecting plate 505 is fixedly connected to the outer wall of the square frame 408, the connecting plate 505 extends out of the storage box 501, a fixing groove 506 is opened at the top end of the activity groove 504 inside the recovery tower 405, one end of the connecting plate 505 is rotatably connected to a rotating column 507, one end of the rotating column 507 is fixedly connected to a threaded rod 508, a displacement rod 509 is slidably connected to the outer wall of the threaded rod 508, the displacement rod 509 is slidably connected to the inside of the connecting plate 505, one end of the displacement rod 509 is rotatably connected to a connecting rod 510, one end of the connecting rod 510 is rotatably connected to a fixing block 511, the fixing block 511 is slidably connected to the inside of the connecting plate 505 and extends above the connecting plate 505, a rotating plate 512 is rotatably connected to the outer wall of the recovery tower 405 at one end of the activity groove 504, a torsion spring 513 is connected between the rotating plate 512 and the recovery tower 405, a groove 514 is opened at the bottom end of the rotating plate 512, a positioning frame 515 extending into the inner cavity of the activity groove 504 is slidably connected to the inside of the recovery tower 405, a first spring 516 is connected between the positioning frame 515 and the recovery tower 405, and the storage box 501 is opened and closed through a connecting mechanism 6.

[0032] In this embodiment: The activated carbon particles and the molecular sieve particles are respectively stored in two storage boxes 501. When replacing the activated carbon particles and the molecular sieve particles, rotate the rotating column 507. The rotation of the rotating column 507 drives the threaded rod 508 to rotate. The rotation of the threaded rod 508 drives the displacement rod 509 to displace. The displacement of the displacement rod 509 drives the fixed block 511 to displace through the connecting rod 510. The fixed block 511 displaces out of the fixed groove 506, canceling the fixation of the connecting plate 505. At this time, the connecting plate 505 can be pushed. The displacement of the connecting plate 505 drives the square frame 408 to slide in the movable groove 504; Push the square frame 408 to displace towards the rotating plate 512. The square frame 408 contacts the positioning frame 515 and pushes the positioning frame 515 to displace, squeezing the first spring 516. At the same time, the square frame 408 contacts the rotating plate 512 and pushes the rotating plate 512 to rotate, twisting the torsion spring 513. The rotation of the rotating plate 512 opens one end of the movable groove 504. The square frame 408 displaces out of the movable groove 504, and the materials in the square frame 408 fall into the collection box 503 for collection operation; Then the square frame 408 displaces towards the inside of the movable groove 504. When the square frame 408 separates from the rotating plate 512, the rotating plate 512 is reset under the action of the torsion force of the torsion spring 513, and the rotating plate 512 resets to close one end of the movable groove 504. When the square frame 408 separates from the positioning frame 515, the positioning frame 515 is snapped into the groove 514 under the elastic force of the first spring 516 to fix the rotating plate 512. The rotating plate 512 blocks one end of the movable groove 504 to prevent nitrogen from leaking through the movable groove 504.

[0033] The square frame 408 continues to displace until the square frame 408 moves into the storage box 501. The materials in the storage box 501 fall into the square frame 408 under the action of gravity. Then push the connecting plate 505 to drive the square frame 408 to displace between the upper ventilation plate 406 and the lower ventilation plate 407. Then rotate the rotating column 507. The rotation of the rotating column 507 drives the fixed block 511 to insert into the fixed groove 506 to fix the positions of the square frame 408 and the connecting plate 505; This design can facilitate the rapid replacement operation of the activated carbon particles and the molecular sieve particles. The materials in the storage box 501 can be stacked from top to bottom in the form of material packages or material blocks so as to gradually fall into the square frame 408 for use.

[0034] Please refer specifically to Figures 7 to 8, the connecting mechanism 6 includes a reinforcement groove 601, the reinforcement groove 601 is opened at the top end of the connecting plate 505, a cover plate 602 is provided at the top end of the storage box 501, a clamping groove 603 is opened on one side of the inner wall of the storage box 501, a clamping block 604 extending out of the cover plate 602 is slidably connected inside the cover plate 602, a second spring 605 is connected between the clamping block 604 and the cover plate 602, a reinforcing rod 606 is slidably connected inside the storage box 501, a third spring 607 is connected between the reinforcing rod 606 and the storage box 501, a spur gear 608 is rotatably connected to the outer wall of the reinforcing rod 606 inside the storage box 501, a pressing rod 609 is slidably connected to the outer wall of the spur gear 608 inside the storage box 501, and the pressing rod 609 extends above the storage box 501.

[0035] In this embodiment: when closing the top end of the storage box 501, push the clamping block 604 to move into the cover plate 602, squeeze the second spring 605, move the cover plate 602 to the top end of the storage box 501, release the clamping block 604, and the clamping block 604 is inserted into the clamping groove 603 under the elastic force of the second spring 605 to fix the cover plate 602. At the same time, the cover plate 602 contacts the pressing rod 609, pushes the pressing rod 609 to displace, the displacement of the pressing rod 609 drives the spur gear 608 to rotate, the rotation of the spur gear 608 drives the reinforcing rod 606 to displace out of the reinforcement groove 601, squeezes the third spring 607, cancels the fixation of the connecting plate 505, and thus the connecting plate 505 can be pushed to displace.

[0036] When opening the top end of the storage box 501, push the clamping block 604 to displace, squeeze the second spring 605, the clamping block 604 displaces out of the clamping groove 603, cancels the fixation of the cover plate 602, and move the cover plate 602 to open the reinforcement groove 601. At this time, the reinforcing rod 606 is snapped into the reinforcement groove 601 under the elastic force of the third spring 607 to fix the connecting plate 505, which is convenient for quickly opening and closing the top end of the storage box 501, facilitating the replacement of activated carbon particles or molecular sieve particles and adding materials into the storage box 501. At the same time, it prevents the connecting plate 505 and the square frame 408 from moving when adding activated carbon particles or molecular sieve particles, and prevents nitrogen from leaking out through the opening of the storage box 501.

[0037] Please refer specifically to Figures 3 to 7 , a threaded hole is opened on the outer wall of the displacement rod 509, the threaded hole is matched with the threaded rod 508, both ends of the connecting rod 510 are connected to the displacement rod 509 and the fixed block 511 through rotating shafts, and the outer wall of the top end of the fixed block 511 is attached to the inner wall of the fixed groove 506.

[0038] In this embodiment: Rotate the rotating column 507. The rotation of the rotating column 507 drives the threaded rod 508 to rotate. The rotation of the threaded rod 508 drives the displacement rod 509 to displace. The displacement of the displacement rod 509 drives the fixed block 511 to displace through the connecting rod 510. The fixed block 511 displaces out of the fixed groove 506, canceling the fixation of the connecting plate 505.

[0039] Please refer particularly to Figures 3 to 7 , the outer wall of the square frame 408 fits against the inner wall of the movable groove 504.

[0040] In this embodiment: The connecting plate 505 can be pushed. The displacement of the connecting plate 505 drives the square frame 408 to slide within the movable groove 504.

[0041] Please refer particularly to Figures 3 to 7 , a triangular surface is provided at one end of the positioning frame 515 located inside the square frame 408, and the outer wall of the other end of the positioning frame 515 fits against the inner wall of the groove 514.

[0042] In this embodiment: Push the square frame 408 to displace towards the rotating plate 512. The square frame 408 contacts the positioning frame 515, pushing the positioning frame 515 to displace, squeezing the first spring 516. At the same time, the square frame 408 contacts the rotating plate 512, pushing the rotating plate 512 to rotate, twisting the torsion spring 513. The rotation of the rotating plate 512 opens one end of the movable groove 504. The square frame 408 displaces out of the movable groove 504, and the material inside the square frame 408 falls into the collection box 503 for collection operation; then the square frame 408 displaces towards the inside of the movable groove 504. When the square frame 408 separates from the rotating plate 512, the rotating plate 512 is reset under the action of the torsion force of the torsion spring 513, and the rotation of the rotating plate 512 closes one end of the movable groove 504. When the square frame 408 separates from the positioning frame 515, the positioning frame 515 is snapped into the groove 514 under the action of the elastic force of the first spring 516, fixing the rotating plate 512. The rotating plate 512 shields one end of the movable groove 504 to prevent nitrogen from leaking through the movable groove 504.

[0043] Please refer particularly to Figures 7 to 8 , the bottom outer wall of the cover plate 602 fits against the inner wall of the storage box 501, and the outer wall of one end of the clamping block 604 fits against the inner wall of the card slot 603.

[0044] In this embodiment: Push the clamping block 604 to move into the cover plate 602, squeezing the second spring 605. Move the cover plate 602 to the top of the storage box 501, release the clamping block 604, and the clamping block 604 is inserted into the card slot 603 under the action of the elastic force of the second spring 605 to fix the cover plate 602.

[0045] Please refer particularly toFigures 7 to 8 The outer wall of the bottom end of the reinforcing rod 606 fits against the inner wall of the reinforcing groove 601. Tooth grooves are provided on the outer walls of both the reinforcing rod 606 and the pressing rod 609, and the tooth grooves mesh with the spur gear 608.

[0046] In this embodiment: Meanwhile, the cover plate 602 contacts the pressing rod 609, pushing the pressing rod 609 to displace. The displacement of the pressing rod 609 drives the spur gear 608 to rotate. The rotation of the spur gear 608 drives the reinforcing rod 606 to displace out of the reinforcing groove 601, squeezing the third spring 607 and canceling the fixation of the connecting plate 505, so as to push the connecting plate 505 to displace. Embodiment 2

[0047] Step 1, green body preparation; Mix the ceramic raw materials of 53 wt% kaolin, 30 wt% quartz, and 17 wt% feldspar evenly, and ball mill to a sieve residue of 0.9% through a 250-mesh sieve. Age for 18 hours in an environment with a humidity of 65%. Press and form at a pressure of 55 MPa, and dry in a chain dryer with hot air circulation at 115 °C for 3.5 hours, with a moisture content of 0.42%.

[0048] Step 2, frit dry granule preparation; Mix the frit raw materials containing the following components: SiO2 53 wt%; Al2O3 23 wt%; ZrO2 4 wt%; Na2O 6.5 wt%; TiO2 2 wt% evenly, melt at 1525 °C for 1.2 hours and then water quench. After XRD detection, the crystallinity is 2.1%, break and sieve to obtain 250-mesh particles for standby.

[0049] Step 3, frit dry granule application; Use an application device with a vibration frequency of 25 Hz and a negative pressure adsorption pressure of -0.04 MPa to evenly apply the frit dry granules on the surface of the green body at an application rate of 200 g / m². The measured uniformity deviation is +2.3%.

[0050] Step 4, green body sintering; Under a nitrogen protection atmosphere, heat up to 600 °C at a rate of 4 °C / min, then heat up to 910 °C at a rate of 6 °C / min, and hold for 18 minutes. Subsequently, cool to 500 °C at a rate of 7 °C / min, and then cool to 100 °C at a rate of 25 °C / min. After sintering, the surface flatness of the green body is 0.06 mm / m, and the porosity is 1.9%.

[0051] Step Five: Preparation of Imitation Gold Coating; After ultrasonic cleaning, the brick blanks are plasma-activated for 4 minutes under the conditions of a radio frequency power of 250 W and an Ar gas flow rate of 75 sccm. Subsequently, the following layers are deposited in sequence: a 0.25-μm Cr transition layer; a 1.0-μm Cu-Zn-Ti alloy layer (Cu content 68 wt%, Zn content 27 wt%, Ti content 5 wt%); a 0.15-μm SiO2 protective layer. The thickness error of the coating detected by XRF is -1.8%.

[0052] Step Six: Polishing and Packaging; A 1800-mesh diamond grinding head is used, and the main shaft speed of the planetary polishing machine is 250 rpm and the pressure is 0.10 MPa for polishing. The adhesion of the coating is detected to reach Grade 5B of ASTM D3359 standard, and the surface glossiness is 98 GU (measured at a 60° angle). The qualified products are packaged and stored in the warehouse.

[0053] The supporting equipment such as the nitrogen protection atmosphere sintering furnace is the same as that in Example 1 and will not be elaborated here. Example 3

[0054] Step One: Preparation of Green Bodies; The ceramic raw materials of 55 wt% kaolin, 25 wt% quartz, and 20 wt% feldspar are mixed evenly and ball-milled to a sieve residue of 0.8% through a 250-mesh sieve. They are aged for 12 hours in an environment with a humidity of 70%. They are pressed into shape under a pressure of 60 MPa and dried in a chain dryer with hot air circulation at 120 °C for 3 hours, with a moisture content of 0.38%.

[0055] Step Two: Preparation of Frit Granules; The frit raw materials containing the following components: SiO2 55 wt%; Al2O3 20 wt%; ZrO2 5 wt%; Na2O 5 wt%; TiO2 3 wt% are mixed evenly, melted at 1550 °C for 1 hour and then water-quenched. The crystallinity detected by XRD is 0.8%, and they are broken and sieved to obtain 300-mesh particles for standby.

[0056] Step Three: Application of Frit Granules; Using an application device with a vibration frequency of 30 Hz and a negative pressure adsorption pressure of -0.03 MPa, the frit granules are evenly applied to the surface of the green bodies at an application rate of 220 g / m². The measured uniformity deviation is +8.7%.

[0057] Step Four: Sintering of Green Bodies; Under a nitrogen protection atmosphere, it is heated to 600 °C at a rate of 5 °C / min, and then heated to 920 °C at a rate of 7 °C / min and held for 15 minutes. Subsequently, it is cooled to 500 °C at a rate of 5 °C / min, and then cooled to 80 °C at a rate of 20 °C / min. After sintering, the surface flatness of the green bodies is 0.04 mm / m, and the porosity is 1.2%.

[0058] Step 5: Preparation of Imitation Gold Coating; After ultrasonic cleaning, the brick blanks are plasma-activated for 3 minutes under the conditions of a radio frequency power of 300 W and an Ar gas flow rate of 100 sccm. Subsequently, the following layers are deposited in sequence: a 0.3-μm Cr transition layer; a 1.2-μm Cu-Zn-Ti alloy layer (Cu 70 wt%, Zn 25 wt%, Ti 5 wt%); a 0.2-μm SiO2 protective layer. The thickness error of the coating detected by XRF is -3.2%.

[0059] Step 6: Polishing and Packaging; Polishing is carried out using a 2000-mesh diamond grinding head with the main shaft speed of the planetary polishing machine being 300 rpm and the pressure being 0.10 MPa. The adhesion of the coating is detected to reach Grade 5B of ASTM D3359 standard, and the surface glossiness is 105 GU (measured at a 60° angle). The qualified products are packaged and stored in the warehouse.

[0060] The supporting equipment such as the nitrogen protection atmosphere sintering furnace is the same as that in Example 1 and will not be elaborated here. Performance Testing

[0061] For the gold-plated ceramic tiles prepared in the above Examples 1-3, the following performance tests are carried out, and all tests are carried out in a standard laboratory environment (temperature 23±2°C, humidity 50±5%). The test items focus on material properties and coating quality, and the internationally common standard methods are adopted: 1. Coating Adhesion: Tape peeling test is carried out according to ASTM D3359 standard (cutting a 1 mm×1 mm grid and vertically peeling with 3M600 tape).

[0062] 2. Surface Glossiness: Measured according to ISO-2813 standard using a 60° angle gloss meter.

[0063] 3. Porosity of Green Body: According to GB / T25995-2010 vacuum water absorption method (dry weighing → vacuum immersion for 24 h → saturated surface dry weighing → boiling for 5 h and weighing).

[0064] 4. Weather Resistance: 1000 hours of ultraviolet accelerated aging is carried out using a Q-SUN Xe-3 aging chamber according to ASTM G154 (0.51 W / m²@340 nm, light / spray cycle).

[0065] 5. Coating Uniformity: Analyze the thickness at 9 points through surface scanning with an X-ray fluorescence spectrometer (XRF).

[0066] 6. Product Qualification Rate: Batch sampling inspection (n≥100) is carried out according to the enterprise internal control standard (no peeling of the coating / glossiness ≥ 90 GU / color difference ΔE ≤ 2.0).

[0067] Performance Test Data Sheet of the Gold-Plated Ceramic Tiles Prepared in the Examples

[0068] Note: 1. Sources of comparative data: Traditional electroplating process: "White Paper on the Electroplated Ceramic Tile Industry" (2023); Magnetron sputtering process: J. Mater. Sci. Technol. 45(2) 112 - 120. 2. Explanation of ΔE value: Color difference change value (ΔE ≤ 2.0 is indistinguishable to the naked eye).

[0069] In summary, through the synergistic effect of the frit dry granule transition layer and the nitrogen - protected sintering process, the present invention significantly improves the coating adhesion to grade 4B - 5B (a 2 - level improvement compared to the traditional electroplating process), while reducing the porosity of the green body to 1.2 - 2.8% (a 65% reduction), fundamentally solving the problem of easy coating peeling. After 1000 - hour ultraviolet accelerated aging test, the color difference ΔE value is stable at 1.8 - 2.0, proving the effective isolation of the SiO2 protective layer from the environment. The simultaneous improvement of the coating thickness uniformity (deviation ±4.7%) and the product qualification rate (95.3%) reflects the stability advantage of the process.

[0070] The above - mentioned is only the preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and should be covered within the protection scope of the present invention.

Claims

1. A preparation process of a gilded ceramic tile made of ceramic frit dry granules, characterized in that, The specific steps are as follows: Step 1: Green body preparation. Mix the ceramic raw materials in proportion evenly, ball mill them until the fineness reaches 250 mesh sieve, age them for 12 - 24 hours in an environment with a humidity of 60 - 70%, then press and form them under a pressure of 50 - 60 MPa, and dry them in a chain dryer with hot air circulation at 110 - 120 °C until the moisture content is less than 0.5%; Step 2: Frit dry granule preparation. Mix the frit raw materials in proportion evenly, melt them at 1500 - 1550 °C and then quench them with water, crush and sieve to obtain 200 - 300 mesh particles for standby; Step 3: Frit dry granule application. Apply the frit dry granules prepared in Step 2 evenly on the surface of the green body by an application device, and the application amount is 180 - 220 g / m²; Step 4: Green body sintering. Use a nitrogen - protected atmosphere sintering furnace to heat the green body with the applied frit dry granules in a nitrogen - protected atmosphere. Heat it to 600 °C at a rate of 3 - 5 °C / min, then heat it to 900 - 920 °C at a rate of 5 - 7 °C / min, keep it warm for 15 - 20 minutes, then cool it to 500 °C at a rate of ≤10 °C / min, and then cool it to below 150 °C at a rate of 20 - 30 °C / min. After sintering, detect the surface flatness and porosity of the green body; Step 5: Imitation gold plating preparation. Send the brick blank sintered in Step 4 into the pretreatment chamber after ultrasonic cleaning, perform plasma surface activation treatment for 3 - 5 minutes under the conditions of a radio frequency power of 200 - 300 W and an Ar gas flow rate of 50 - 100 sccm, and then transfer it to the coating chamber to deposit three functional coatings in sequence: deposit a 0.2 - 0.3 μm Cr transition layer; deposit a 0.8 - 1.2 μm Cu - Zn - Ti alloy layer, where the alloy components meet the following mass percentages: Cu content 60 - 70 wt%, Zn content 20 - 30 wt%, Ti content 2 - 5 wt%; deposit a 0.1 - 0.2 μm SiO2 protective layer; Step 6: Polishing and packaging. Gently polish the coated blank with a planetary polishing machine using a 1500 - 2000 mesh diamond grinding head, and package it after passing the inspection.

2. The preparation process of a gold-plated ceramic tile made of ceramic frit dry granules according to claim 1, characterized in that, The ceramic raw materials for preparing the green body in Step 1 contain the following components by weight percentage: Kaolin 50 - 55%; Quartz 25 - 35%; Feldspar 15 - 20%.

3. The preparation process of a gold-plated ceramic tile made of ceramic frit dry granules according to claim 1, characterized in that, The raw materials for preparing the frit dry granules in Step 2 contain the following components by weight percentage: SiO2 50 - 55%; Al2O3 20 - 25%; ZrO2 3 - 5%; Na2O 5 - 8%; TiO2 1 - 3%.

4. The preparation process of a gold-plated ceramic tile made of ceramic frit dry granules according to claim 1, characterized in that, The nitrogen protection atmosphere sintering furnace described in Step 4 includes a box-type atmosphere sintering furnace body (1). A furnace door (2) is installed on the outer wall of the box-type atmosphere sintering furnace body (1). An electric heating element (3) is installed in the inner cavity of the box-type atmosphere sintering furnace body (1). Nitrogen in the box-type atmosphere sintering furnace body (1) is circulated through a circulation and purification mechanism (4). The circulation and purification mechanism (4) includes an air inlet hole (401) which is opened at the bottom end of the inner wall of the box-type atmosphere sintering furnace body (1). An air inlet pipe (402) is fixedly connected to one side outer wall of the box-type atmosphere sintering furnace body (1). A blower (403) is installed on the air inlet pipe (402). An exhaust pipe (404) is fixedly connected to the top end of the box-type atmosphere sintering furnace body (1). The air inlet pipe (402) is communicated with the air inlet hole (401). A recovery tower (405) is fixedly connected to one end of the exhaust pipe (404) and the air inlet pipe (402). Two groups of upper air-permeable plates (406), lower air-permeable plates (407) and square frames (408) are arranged on the inner wall of the recovery tower (405). The upper air-permeable plates (406) are located above the lower air-permeable plates (407). The square frames (408) are located between the upper air-permeable plates (406) and the lower air-permeable plates (407). Activated carbon particles and molecular sieve particles are respectively stored in the cavities formed by the two groups of upper air-permeable plates (406), lower air-permeable plates (407) and square frames (408). The activated carbon particles and molecular sieve particles are replaced through a replacement mechanism (5).

5. The preparation process of a gold-plated ceramic tile made of ceramic frit dry granules according to claim 4, characterized in that, The replacement mechanism (5) includes a storage box (501), the storage box (501) is fixedly connected to the outer wall of one side of the recovery tower (405), a slot (502) is opened on the outer wall of the other side of the recovery tower (405), a collection box (503) is slidably connected to the inner wall of the slot (502), an activity groove (504) for the square frame (408) to slide is opened inside the storage box (501) and the recovery tower (405), a connecting plate (505) is fixedly connected to the outer wall of the square frame (408), the connecting plate (505) extends out of the storage box (501), a fixing groove (506) is opened at the top end of the activity groove (504) inside the recovery tower (405), one end of the connecting plate (505) is rotatably connected to a rotating column (507), one end of the rotating column (507) is fixedly connected to a threaded rod (508), a displacement rod (509) is slidably connected to the outer wall of the threaded rod (508), the displacement rod (509) is slidably connected to the inside of the connecting plate (505), one end of the displacement rod (509) is rotatably connected to a connecting rod (510), one end of the connecting rod (510) is rotatably connected to a fixing block (511), the fixing block (511) is slidably connected to the inside of the connecting plate (505) and extends above the connecting plate (505), a rotating plate (512) is rotatably connected to the outer wall of the recovery tower (405) at one end of the activity groove (504), a torsion spring (513) is connected between the rotating plate (512) and the recovery tower (405), a groove (514) is opened at the bottom end of the rotating plate (512), a positioning frame (515) extending into the inner cavity of the activity groove (504) is slidably connected to the inside of the recovery tower (405), a first spring (516) is connected between the positioning frame (515) and the recovery tower (405), and the storage box (501) is opened and closed through a connection mechanism (6).

6. The preparation process of a gold-plated ceramic tile made of ceramic frit dry granules according to claim 5, characterized in that, The connecting mechanism (6) includes a reinforcement groove (601) which is opened at the top end of the connecting plate (505). A cover plate (602) is provided at the top end of the storage box (501). A clamping groove (603) is opened on one side of the inner wall of the storage box (501). A clamping block (604) extending out of the cover plate (602) is slidably connected inside the cover plate (602). A second spring (605) is connected between the clamping block (604) and the cover plate (602). A reinforcement rod (606) is slidably connected inside the storage box (501). A third spring (607) is connected between the reinforcement rod (606) and the storage box (501). A spur gear (608) is rotatably connected to the outer wall of the reinforcement rod (606) inside the storage box (501). A pressing rod (609) is slidably connected to the outer wall of the spur gear (608) inside the storage box (501). The pressing rod (609) extends above the storage box (501).

7. The preparation process of a gold-plated ceramic tile made of ceramic frit dry granules according to claim 5, characterized in that, Threaded holes are opened on the outer wall of the displacement rod (509), and the threaded holes are matched with the threaded rod (508); both ends of the connecting rod (510) are connected to the displacement rod (509) and the fixed block (511) through rotating shafts, and the outer wall of the top end of the fixed block (511) is attached to the inner wall of the fixed groove (506).

8. The preparation process of a gold-plated ceramic tile made of ceramic frit dry granules according to claim 5, characterized in that, The outer wall of the square frame (408) is attached to the inner wall of the movable groove (504); a triangular surface is provided at one end of the positioning frame (515) located inside the square frame (408), and the outer wall of the other end of the positioning frame (515) is attached to the inner wall of the groove (514).

9. The preparation process of a gold-plated ceramic tile made of ceramic frit dry granules according to claim 6, characterized in that, The bottom outer wall of the cover plate (602) is attached to the inner wall of the storage box (501), and one end outer wall of the clamping block (604) is attached to the inner wall of the clamping groove (603).

10. The preparation process of a gold-plated ceramic tile made of ceramic frit dry granules according to claim 6, characterized in that, The bottom outer wall of the reinforcement rod (606) is attached to the inner wall of the reinforcement groove (601). Tooth grooves are provided on the outer walls of both the reinforcement rod (606) and the pressing rod (609), and the tooth grooves are meshed with the spur gear (608).

Images