A preparation process for gold-plated ceramic tiles made from ceramic frit dry particles

Abstract

The present invention discloses a preparation process for gold-plated ceramic tiles made of ceramic frit dry particles, and relates to the technical field of building decoration materials. The steps are as follows: blank preparation; frit dry particle preparation; frit dry particle application; blank sintering; imitation gold plating preparation; polishing and packaging. The present invention effectively solves the problems of high cost, large environmental pollution, and insufficient coating bonding strength in the prior art by optimizing the material formula and improving the process flow; by improving the nitrogen protective atmosphere sintering furnace, a circulating purification mechanism is set up, and the nitrogen in the box-type atmosphere sintering furnace body is discharged through the exhaust pipe into the recovery tower, the activated carbon in the recovery tower is adsorbed, and the molecular sieve is dehydrated to purify the nitrogen, and the purified nitrogen enters the air inlet pipe. The nitrogen in the air inlet pipe enters the box-type atmosphere sintering furnace body again through the air inlet hole, which can improve the utilization rate of nitrogen and reduce the consumption of protective atmosphere.

Description

Technical Field

[0001] The invention relates to the technical field of building decoration materials, in particular to a preparation process of gold-plated ceramic tiles made from ceramic frit dry particles. Background Art

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

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

[0004] The frit dry particle process offers significant advantages in the preparation of gold-plated ceramic tiles. By constructing a specially formulated frit transition layer on the surface of the ceramic substrate, this process not only effectively mitigates the difference in thermal expansion coefficients between the metal coating and the ceramic substrate, but also significantly enhances the bonding strength of the coating. Specifically, the active components in the frit dry particles chemically bond with the substrate during sintering, improving the adhesion of the coating. Furthermore, the low-temperature sintering characteristics of the frit dry particles reduce energy consumption compared to traditional glazes, significantly improving process economics while ensuring coating quality. However, when applied to the preparation of gold-plated ceramic tiles, existing frit dry particle technology still has room for improvement in terms of process stability, cost control, and environmental performance.

[0005] Based on the above analysis, the existing gold-plated ceramic tile preparation technology still faces many technical bottlenecks in industrial application, and it is necessary to develop a new preparation process with both excellent coating performance and good economy. The present invention targets these key technical difficulties by optimizing the frit dry particle formula, improving the coating process and developing special equipment, aiming to establish a set of efficient, stable and environmentally friendly gold-plated ceramic tile preparation system, providing the industry with reliable technical solutions and promoting the industrial development of gold-plated ceramic tiles. Summary of the Invention

[0006] The purpose of the present invention is to provide a preparation process for gold-plated ceramic tiles made of ceramic frit dry particles in order to solve the problems of high cost, severe environmental pollution, insufficient coating bonding strength and the like in the prior art.

[0007] To achieve the above object, the present invention provides the following technical solution: a preparation process for gold-plated ceramic tiles made of ceramic frit dry particles, the specific steps of which are as follows:

[0008] Step 1: Green body preparation: Mix the ceramic raw materials in the appropriate proportions and evenly grind them to a fineness of 0.8-1.0% on a 250-mesh sieve. After aging for 12-24 hours in an environment with a humidity of 60-70%, press them into shape under a pressure of 50-60 MPa and dry them in a chain drying kiln with hot air circulation at 110-120°C until the moisture content is less than 0.5%.

[0009] Step 2: Preparation of frit dry particles: Mix the frit raw materials in the appropriate proportions, melt them at 1500-1550°C, and then water quench them. XRD analysis shows an amorphous glass phase (crystallinity <5%), crush them, and sieve out 200-300 mesh particles for later use;

[0010] Step 3: Applying the frit dry particles. The frit dry particles prepared in step 2 are evenly applied to the surface of the green body using an application device. The application amount is controlled at 180-220g / m². The device uses a combination of vibration feeding (frequency 25±5Hz) and negative pressure adsorption (pressure -0.04±0.01MPa) to ensure that the deviation of the dry particle distribution uniformity does not exceed ±10%;

[0011] Step 4: Sintering of the green body: Use a nitrogen protective atmosphere sintering furnace to heat the green body to 600°C at 3-5°C / min, then to 900-920°C at 5-7°C / min, keep warm for 15-20 minutes, then cool to 500°C at ≤10°C / min, and then cool to below 150°C at 20-30°C / min. After sintering, test the green body surface flatness (≤0.1mm / m) and porosity (≤3%).

[0012] Step 5: Preparation of imitation gold plating: After ultrasonic cleaning, the sintered bricks are sent to the pretreatment chamber for plasma surface activation treatment for 3 to 5 minutes under the conditions of RF power of 200-300W and Ar gas flow of 50-100sccm. Then they are transferred to the coating chamber for sequential deposition of three functional coatings: a 0.2-0.3μm Cr transition layer; a 0.8-1.2μm Cu-Zn-Ti alloy layer (Cu content 60-70wt%, Zn content 20-30wt%, Ti content 2-5wt%); and a 0.1-0.2μm SiO2 protective layer. The thickness of each coating layer is detected by X-ray fluorescence spectrometer (XRF), and the error is controlled within ±5%.

[0013] Step 6: Polishing and packaging: The coated blank is lightly polished with a planetary polisher (spindle speed 250±50rpm, pressure 0.05-0.1MPa) using a 1500-2000 mesh diamond grinding head. The coating adhesion (ASTM D3359 standard reaches 4B grade) and surface gloss (≥90GU, measured at a 60° angle) are tested. After passing the test, it is packaged.

[0014] Preferably, the ceramic raw material for preparing the green body in step 1 comprises the following components in weight percentage:

[0015] Kaolin 50~55%;

[0016] Quartz 25~35%;

[0017] Feldspar 15~20%.

[0018] Preferably, the raw materials for preparing the frit dry particles in step 2 include the following components in percentage by weight:

[0019] SiO2 50~55%;

[0020] Al2O3 20~25%;

[0021] ZrO2 3~5%;

[0022] Na2O 5~8%;

[0023] TiO2 1~3%.

[0024] As a further solution of the present invention: the nitrogen protective atmosphere sintering furnace described in step 4 includes a box-type atmosphere sintering furnace body, the outer wall of the box-type atmosphere sintering furnace body is installed with a furnace door, the inner cavity of the box-type atmosphere sintering furnace body is installed with an electric heating element, the nitrogen in the box-type atmosphere sintering furnace body is circulated through a circulation purification mechanism, the circulation purification mechanism includes an air inlet hole, the air inlet hole 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 the outer wall of one side of the box-type atmosphere sintering furnace body, a fan is installed on the air inlet pipe, the An exhaust pipe is fixedly connected to the top of the box-type atmosphere sintering furnace body, and the air inlet pipe is communicated with the air inlet hole. One end of the exhaust pipe and the air inlet pipe is fixedly connected to a recovery tower. The inner wall of the recovery tower is provided with two groups of upper air permeable plates, lower air permeable plates and square frames. 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 cavity formed by the two groups of upper air permeable plates, lower air permeable plates and square frames. The activated carbon particles and molecular sieve particles are replaced by a replacement mechanism.

[0025] As a further solution of the present invention: the replacement mechanism includes a storage box, the storage box is fixedly connected to the outer wall of one side of the recovery tower, the outer wall of the other side of the recovery tower is provided with a slot, the inner wall of the slot is slidably connected to the collection box, the storage box and the recovery tower are provided with a movable groove for the square frame to slide, the outer wall of the square frame is fixedly connected to a connecting plate, the connecting plate extends out of the storage box, the interior of the recovery tower is provided with a fixed groove at the top of the movable groove, one end of the connecting plate is rotatably connected to a rotating column, one end of the rotating column is fixedly connected to a threaded rod, and the outer wall of the threaded rod is slidably connected There is a displacement rod, which is slidably connected to the inside of the connecting plate, one end of the displacement rod is rotatably connected to a connecting rod, one end of the connecting rod is rotatably connected to a fixed block, the fixed block is slidably connected to the inside of the connecting plate and extends above the connecting plate, the outer wall of the recovery tower is located at one end of the movable groove and is rotatably connected to a rotating plate, 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, the interior of the recovery tower is slidably connected to a positioning frame extending to the inner cavity of the movable groove, a first spring is connected between the positioning frame and the recovery tower, and the storage box is switched by a connecting mechanism.

[0026] As a further solution of the present invention: the connecting mechanism includes a reinforcement groove, which is opened at the top of the connecting plate, a cover plate is provided at the top of the storage box, a card slot is opened on one side of the inner wall of the storage box, the cover plate is slidably connected to a card block extending from the cover plate, a second spring is connected between the card block and the cover plate, the storage box is slidably connected to a reinforcement rod, a third spring is connected between the reinforcement rod and the storage box, the storage box is located inside the outer wall of the reinforcement rod and is rotatably connected to a spur gear, the storage box is located inside the outer wall of the spur gear and is slidably connected to a downward pressure rod, and the downward pressure rod extends to the top of the storage box.

[0027] As a further solution of the present invention: a threaded hole is opened on the outer wall of the displacement rod, and the threaded hole matches the threaded rod; both ends of the connecting rod are connected to the displacement rod and the fixed block through a rotating shaft, and the top outer wall of the fixed block fits with the inner wall of the fixing groove.

[0028] As a further solution of the present invention: the outer wall of the square frame fits with the inner wall of the movable groove; the positioning frame is provided with a triangular surface at one end of the inner cavity of the square frame, and the outer wall of the other end of the positioning frame fits with the inner wall of the groove.

[0029] As a further solution of the present invention: the outer wall of the bottom of the cover plate is in contact with the inner wall of the storage box, and the outer wall of one end of the card block is in contact with the inner wall of the card slot.

[0030] As a further solution of the present invention: the outer wall of the bottom end of the reinforcement rod is in contact with the inner wall of the reinforcement groove, and the outer walls of the reinforcement rod and the lower pressure rod are both provided with tooth grooves, and the tooth grooves are engaged with the spur gears.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] 1. By optimizing the material formula and improving the process flow, the problems existing in the existing technology, such as high cost of frit process implementation, severe environmental pollution, and insufficient coating bonding strength, are effectively solved;

[0033] 2. By setting up a circulation purification mechanism, the nitrogen in the box-type atmosphere sintering furnace is discharged into the recovery tower through the exhaust pipe. The activated carbon in the recovery tower is adsorbed and the molecular sieve is used for dehydration to purify the nitrogen. The purified nitrogen enters the air inlet pipe and then enters the box-type atmosphere sintering furnace again through the air inlet hole, which can improve the utilization rate of nitrogen and reduce the consumption of protective atmosphere.

[0034] 3. By setting up a replacement mechanism and a connection mechanism, it is convenient to quickly replace the activated carbon particles and molecular sieve particles; the top of the storage box can be quickly opened and closed to facilitate the addition of activated carbon particles or molecular sieve particles into the storage box. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 Schematic diagram of the structure of the nitrogen protective atmosphere sintering furnace of the present invention;

[0036] Figure 2 Schematic diagram of the installation of the upper and lower air permeable plates of the nitrogen protective atmosphere sintering furnace of the present invention;

[0037] Figure 3 This is a schematic diagram of the internal structure of the recovery tower of the nitrogen protective atmosphere sintering furnace of the present invention;

[0038] Figure 4 This is a schematic structural diagram of a square frame of the nitrogen protective atmosphere sintering furnace of the present invention;

[0039] Figure 5 This is a schematic diagram of the installation of the rotating plate of the nitrogen protective atmosphere sintering furnace of the present invention;

[0040] Figure 6 The nitrogen protective atmosphere sintering furnace of the present invention Figure 5 Enlarged view of point A in the middle;

[0041] Figure 7 This is a schematic diagram of the internal structure of the connecting plate of the nitrogen protective atmosphere sintering furnace of the present invention;

[0042] Figure 8This is a schematic diagram of the internal structure of the storage box of the nitrogen protective atmosphere sintering furnace of the present invention.

[0043] Figure: 1. Box-type atmosphere sintering furnace body; 2. Furnace door; 3. Electric heating element; 4. Circulation purification mechanism; 401. Air inlet; 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, clamping slot; 604, clamping block; 605, second spring; 606, reinforcement rod; 607, third spring; 608, spur gear; 609, pressing rod. DETAILED DESCRIPTION

[0044] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0045] In the description of the present invention, it should be noted that the terms "center", "up", "down", "left", "right", "vertical", "horizontal", "inside", "outside" and the like indicate positions or positional relationships based on the positions or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or components referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as limiting the present invention. In addition, the terms "first", "second", and "third" are only used for descriptive purposes and should not be understood as indicating or implying relative importance. In the description of the present invention, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", and "set" should be understood in a broad sense, for example, they can be fixedly connected, detachably connected, or connected in one piece; they can be mechanically connected or electrically connected; they can be directly connected, or indirectly connected through an intermediate medium, or they can be internal connections between two components. 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 circumstances. The following describes an embodiment of the present invention based on its overall structure. Example 1

[0046] See also Figures 1 to 8 In an embodiment of the present invention, a process for preparing a gold-plated ceramic tile made of ceramic frit dry particles comprises the following specific steps:

[0047] Step 1: Prepare the green body: Mix 50wt% kaolin, 35wt% quartz, and 15wt% feldspar, then ball-mill until the residue on a 250-mesh sieve is 1.0%. Aged for 24 hours in a 60% humidity environment. Press into shape under a pressure of 50 MPa and dry in a chain drying kiln with hot air circulation at 110°C for 4 hours, achieving a moisture content of 0.48%.

[0048] Step 2: Preparation of dry frit particles; the following components are included:

[0049] SiO2 50wt%;

[0050] Al2O3 25wt%;

[0051] ZrO2 3wt%;

[0052] Na2O 8wt%;

[0053] The raw materials of the TiO2 1wt% frit were mixed evenly, melted at 1500℃ for 1.5 hours, and then quenched with water. XRD analysis showed a crystallinity of 4.2%. The particles were crushed and sieved to 200 mesh for later use.

[0054] Step 3: Applying frit dry particles: Using a 20Hz vibration frequency and -0.05MPa negative pressure adsorption equipment, the frit dry particles were evenly applied to the surface of the green body at a rate of 180g / m². The measured uniformity deviation was -9.8%.

[0055] Step 4: Sintering the green body: Under a nitrogen atmosphere, heat the body to 600°C at a rate of 3°C / min, then to 900°C at a rate of 5°C / min, and hold for 20 minutes. Cool the body to 500°C at a rate of 8°C / min, and then to 120°C at a rate of 30°C / min. The sintered green body has a surface flatness of 0.09 mm / m and a porosity of 2.8%.

[0056] Step 5: Preparation of the imitation gold coating: After ultrasonic cleaning, the brick was plasma activated for 5 minutes at 200W RF power and 50sccm Ar flow. Subsequently, the following layers were deposited: a 0.2μm thick Cr transition layer; a 0.8μm thick Cu-Zn-Ti alloy layer (65wt% Cu, 30wt% Zn, 5wt% Ti); and a 0.1μm thick SiO2 protective layer. XRF analysis of the coating thickness showed an error of +4.7%.

[0057] Step 6: Polishing and Packaging: Polishing is performed using a 1500-grit diamond grinding head on a planetary polisher at a spindle speed of 200 rpm and a pressure of 0.08 MPa. Coating adhesion meets ASTM D3359 standard 4B, with a surface gloss of 92 GU (measured at a 60° angle). Qualified products are packaged and stored.

[0058] In this embodiment, by optimizing the material formula and improving the process flow, the problems of high cost, severe environmental pollution, and insufficient coating bonding strength existing in the prior art are effectively solved.

[0059] Please refer to Figures 1 to 4 The nitrogen protection atmosphere sintering furnace 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, and the nitrogen in the box-type atmosphere sintering furnace body 1 is circulated through a circulation purification mechanism 4. The circulation purification mechanism 4 includes an air inlet 401, and the air inlet 401 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 the outer wall of one side of the box-type atmosphere sintering furnace body 1, and a fan 403 is installed on the air inlet pipe 402. The top of the box-type atmosphere sintering furnace body 1 is fixedly connected to an exhaust pipe 4 04, the air inlet pipe 402 is connected to the air inlet hole 401, and one end of the exhaust pipe 404 and the air inlet pipe 402 is fixedly connected to a recovery tower 405. The inner wall of the recovery tower 405 is provided with two groups of upper air permeable plates 406, lower air permeable plates 407 and square frames 408. The upper air permeable plates 406 are located above the lower air permeable plates 407, and the square frame 408 is 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 cavity formed by the two groups of upper air permeable plates 406, the lower air permeable plates 407 and the square frame 408. The activated carbon particles and molecular sieve particles are replaced by the replacement mechanism 5.

[0060] In this embodiment: the blower 403 is running, and the nitrogen in the box-type atmosphere sintering furnace body 1 is discharged into the recovery tower 405 through the exhaust pipe 404. 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 air inlet pipe 402, and the nitrogen in the air 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 protective atmosphere.

[0061] Please refer to Figures 3 to 7The replacement mechanism 5 includes a storage box 501, which is fixedly connected to the outer wall of one side of the recovery tower 405, and a slot 502 is provided on the outer wall of the other side of the recovery tower 405. The inner wall of the slot 502 is slidably connected to the collection box 503. The storage box 501 and the recovery tower 405 are provided with a movable slot 504 for the square frame 408 to slide. The outer wall of the square frame 408 is fixedly connected to a connecting plate 505, and the connecting plate 505 extends out of the storage box 501. The interior of the recovery tower 405 is provided with a fixed slot 506 at the top of the movable slot 504. One end of the connecting plate 505 is rotatably connected to a rotating column 507, and one end of the rotating column 507 is fixedly connected to a threaded rod 508. The outer wall of the threaded rod 508 is slidably connected to a displacement rod 509. The displacement rod 509 is slidably connected to the inside of the connecting plate 505, and one end of the displacement rod 509 is rotatably connected to the connecting rod 510, and one end of the connecting rod 510 is rotatably connected to the fixed block 511. The fixed block 511 is slidably connected to the inside of the connecting plate 505 and extends to the top of the connecting plate 505. The outer wall of the recovery tower 405 is located at one end of the movable groove 504 and is rotatably connected to a rotating plate 512. A torsion spring 513 is connected between the rotating plate 512 and the recovery tower 405. A groove 514 is provided at the bottom end of the rotating plate 512. The interior of the recovery tower 405 is slidably connected to a positioning frame 515 extending to the inner cavity of the movable groove 504. A first spring 516 is connected between the positioning frame 515 and the recovery tower 405. The storage box 501 is switched by the connecting mechanism 6.

[0062] In this embodiment, the activated carbon particles and the molecular sieve particles are stored in two storage boxes 501 respectively. When the activated carbon particles and the molecular sieve particles are replaced, the rotating column 507 is rotated, and the rotating column 507 rotates to drive the threaded rod 508 to rotate, and the threaded rod 508 rotates to drive the displacement rod 509 to displace, and the displacement rod 509 drives the fixed block 511 to displace through the connecting rod 510. The fixed block 511 moves out of the fixed groove 506, and the fixation of the connecting plate 505 is cancelled. At this time, the connecting plate 505 can be pushed, and the displacement of the connecting plate 505 drives the square frame 408 to slide in the movable groove 504; the square frame 408 is pushed toward the rotating plate 512 to displace, and the square frame 408 contacts the positioning frame 515, pushing the positioning frame 515 to displace, causing the first spring 516 to be squeezed. At the same time, the square frame 408 and the rotating plate 5 12 contacts, pushes the rotating plate 512 to rotate, causing the torsion spring 513 to twist, and the rotating plate 512 rotates to open one end of the movable groove 504, and the square frame 408 moves out of the movable groove 504, and the material in the square frame 408 falls into the collecting box 503 for collection; then the square frame 408 moves toward the movable groove 504, and when the square frame 408 separates from the rotating plate 512, the rotating plate 512 is reset by the torsion force of the torsion spring 513, and the rotating plate 512 is reset 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 engaged into the groove 514 by the elastic force of the first spring 516, fixing the rotating plate 512, and the rotating plate 512 blocks one end of the movable groove 504 to prevent nitrogen from leaking through the movable groove 504.

[0063] Square frame 408 continues to move until it moves into storage box 501. The material in storage box 501 falls into square frame 408 due to gravity. Then, connecting plate 505 is pushed to move square frame 408 between upper air permeable plate 406 and lower air permeable plate 407. Rotating column 507 is then rotated, which drives fixing block 511 to insert into fixing slot 506, thereby fixing the position of square frame 408 and connecting plate 505. This design facilitates the rapid replacement of activated carbon particles and molecular sieve particles. The material in storage box 501 can be stacked from top to bottom in the form of material bags or material blocks, so that they can fall into square frame 408 step by step for use.

[0064] Please refer to Figures 7 and 8The connecting mechanism 6 includes a reinforcement groove 601, which is opened at the top of the connecting plate 505, a cover plate 602 is provided at the top of the storage box 501, and a card slot 603 is opened on one side of the inner wall of the storage box 501. The inner part of the cover plate 602 is slidably connected with a card block 604 extending from the cover plate 602, and a second spring 605 is connected between the card block 604 and the cover plate 602. The inner part of the storage box 501 is slidably connected with a reinforcement rod 606, and a third spring 607 is connected between the reinforcement rod 606 and the storage box 501. The outer wall of the interior of the storage box 501 is located at the reinforcement rod 606 and is rotatably connected to a spur gear 608. The outer wall of the interior of the storage box 501 is located at the spur gear 608 and is slidably connected to a downward pressure rod 609, which extends to the top of the storage box 501.

[0065] In this embodiment: when the top of the storage box 501 is closed, the block 604 is pushed to move into the cover 602, causing compression on the second spring 605, and the cover 602 is moved to the top of the storage box 501, and the block 604 is released. The block 604 is inserted into the card slot 603 under the elastic force of the second spring 605, and the cover 602 is fixed. At the same time, the cover 602 contacts the lower pressure rod 609, pushing the lower pressure rod 609 to move. The displacement of the lower pressure rod 609 drives the spur gear 608 to rotate. The rotation of the spur gear 608 drives the reinforcement rod 606 to move out of the reinforcement slot 601, causing compression on the third spring 607, and canceling the fixation of the connecting plate 505, thereby pushing the connecting plate 505 to move.

[0066] When the top of the storage box 501 is opened, the block 604 is pushed to move, which squeezes the second spring 605, and the block 604 moves out of the slot 603, canceling the fixation of the cover 602. The cover 602 is moved to open the reinforcement slot 601. At this time, the reinforcement rod 606 is engaged into the reinforcement slot 601 by the elastic force of the third spring 607, and the connecting plate 505 is fixed, which facilitates the rapid opening and closing of the top of the storage box 501, and facilitates the addition of activated carbon particles or molecular sieve particles as replacement 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 through the opening of the storage box 501.

[0067] Please refer to Figures 3 to 7 A threaded hole is provided on the outer wall of the displacement rod 509, which matches the threaded rod 508. Both ends of the connecting rod 510 are connected to the displacement rod 509 and the fixed block 511 through a rotating shaft, and the top outer wall of the fixed block 511 fits into the inner wall of the fixed groove 506.

[0068] In this embodiment: rotate the rotating column 507, the rotating column 507 drives the threaded rod 508 to rotate, the threaded rod 508 drives the displacement rod 509 to displace, the displacement rod 509 drives the fixed block 511 to displace through the connecting rod 510, and the fixed block 511 moves out of the fixing groove 506, canceling the fixation of the connecting plate 505.

[0069] Please refer to Figures 3 to 7 The outer wall of the square frame 408 fits with the inner wall of the movable groove 504 .

[0070] In this embodiment, the connecting plate 505 can be pushed, and the displacement of the connecting plate 505 drives the square frame 408 to slide in the movable groove 504 .

[0071] Please refer to Figures 3 to 7 The positioning frame 515 is located at one end of the inner cavity of the square frame 408 and is provided with a triangular surface, and the outer wall of the other end of the positioning frame 515 is in contact with the inner wall of the groove 514.

[0072] In this embodiment, the square frame 408 is pushed toward the rotating plate 512 to move, the square frame 408 contacts the positioning frame 515, and the positioning frame 515 is pushed to move, causing compression on the first spring 516. At the same time, the square frame 408 contacts the rotating plate 512, pushing the rotating plate 512 to rotate, causing torsion on the torsion spring 513. The rotating plate 512 rotates to open one end of the movable groove 504, and the square frame 408 moves out of the movable groove 504. The material in the square frame 408 falls into the collection box 503 for collection. The square frame 408 moves toward the movable groove 504. When the square frame 408 is separated from the rotating plate 512, the rotating plate 512 is reset by the torsion force of the torsion spring 513. The reset of the rotating plate 512 closes one end of the movable groove 504. When the square frame 408 is separated from the positioning frame 515, the positioning frame 515 is engaged into the groove 514 by 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.

[0073] Please refer to Figures 7 and 8 The outer wall of the bottom of the cover plate 602 is in contact with the inner wall of the storage box 501 , and the outer wall of one end of the card block 604 is in contact with the inner wall of the card slot 603 .

[0074] In this embodiment: push the block 604 to move into the cover 602, squeezing the second spring 605, move the cover 602 to the top of the storage box 501, release the block 604, and the block 604 is inserted into the slot 603 under the elastic force of the second spring 605 to fix the cover 602.

[0075] Please refer to Figures 7 and 8 The outer wall of the bottom end of the reinforcing rod 606 is in contact with the inner wall of the reinforcing groove 601 , and the outer walls of the reinforcing rod 606 and the lower pressure rod 609 are both provided with tooth grooves, which mesh with the spur gear 608 .

[0076] In this embodiment: at the same time, the cover plate 602 contacts the lower pressure rod 609, pushing the lower pressure rod 609 to move. The displacement of the lower pressure rod 609 drives the spur gear 608 to rotate. The rotation of the spur gear 608 drives the reinforcement rod 606 to move out of the reinforcement groove 601, causing compression on the third spring 607, canceling the fixation of the connecting plate 505, and thereby pushing the connecting plate 505 to move. Example 2

[0077] Step 1: Prepare the green body: Mix 53wt% kaolin, 30wt% quartz, and 17wt% feldspar, then ball-mill until the residue on a 250-mesh sieve is 0.9%. Aged for 18 hours in a 65% humidity environment. Pressed into shape at 55MPa, the green body was dried in a chain drying kiln with hot air circulation at 115°C for 3.5 hours, resulting in a moisture content of 0.42%.

[0078] Step 2: Preparation of dry frit particles; the following components are included:

[0079] SiO2 53wt%;

[0080] Al2O3 23wt%;

[0081] ZrO2 4wt%;

[0082] Na2O 6.5wt%;

[0083] The TiO2 2wt% frit raw materials were mixed evenly, melted at 1525℃ for 1.2 hours, and then quenched with water. XRD analysis showed a crystallinity of 2.1%. The particles were crushed and sieved to 250 mesh for later use.

[0084] Step 3: Applying frit dry particles: Using a 25Hz vibration frequency and -0.04MPa negative pressure adsorption device, apply 200g / m² of frit dry particles evenly to the surface of the green body. The measured uniformity deviation is +2.3%.

[0085] Step 4: Sintering the green body: Under a nitrogen atmosphere, heat the green body to 600°C at a rate of 4°C / min, then to 910°C at a rate of 6°C / min, and hold for 18 minutes. Cool the green body to 500°C at a rate of 7°C / min, and then to 100°C at a rate of 25°C / min. The green body has a surface flatness of 0.06 mm / m and a porosity of 1.9%.

[0086] Step 5: Preparation of the imitation gold coating: After ultrasonic cleaning, the brick was plasma activated for 4 minutes at 250W RF power and 75sccm Ar flow. Subsequently, the following layers were deposited: a 0.25μm thick Cr transition layer; a 1.0μm thick Cu-Zn-Ti alloy layer (Cu content: 68wt%, Zn content: 27wt%, Ti content: 5wt%); and a 0.15μm SiO2 protective layer. XRF analysis revealed a coating thickness error of -1.8%.

[0087] Step 6: Polishing and Packaging: Polishing is performed using an 1800-grit diamond grinding head on a planetary polisher at a spindle speed of 250 rpm and a pressure of 0.10 MPa. Coating adhesion meets ASTM D3359 standard 5B, and the surface gloss is 98 GU (measured at a 60° angle). Qualified products are packaged and stored.

[0088] The nitrogen protective atmosphere sintering furnace and other supporting equipment are the same as those in Example 1 and will not be described in detail here. Example 3

[0089] Step 1: Prepare the green body: Mix 55wt% kaolin, 25wt% quartz, and 20wt% feldspar, then ball-mill until the residue on a 250-mesh sieve is 0.8%. Aged for 12 hours at 70% humidity. Pressed into shape at 60MPa, the green body was dried in a chain drying kiln with hot air circulation at 120°C for 3 hours, resulting in a moisture content of 0.38%.

[0090] Step 2: Preparation of dry frit particles; the following components are included:

[0091] SiO2 55wt%;

[0092] Al2O3 20wt%;

[0093] ZrO2 5wt%;

[0094] Na2O 5wt%;

[0095] The raw materials of the TiO2 3wt% frit were mixed evenly, melted at 1550℃ for 1 hour, and then quenched with water. The crystallinity was 0.8% as determined by XRD. The particles were crushed and sieved to obtain 300 mesh particles for later use.

[0096] Step 3: Applying frit dry particles: Using a 30Hz vibration frequency and -0.03MPa negative pressure adsorption equipment, the frit dry particles were evenly applied to the surface of the green body at a rate of 220g / m². The measured uniformity deviation was +8.7%.

[0097] Step 4: Sintering the green body: Under a nitrogen atmosphere, heat the green body to 600°C at a rate of 5°C / min, then to 920°C at a rate of 7°C / min, and hold for 15 minutes. Cool the green body to 500°C at a rate of 5°C / min, and then to 80°C at a rate of 20°C / min. The green body has a surface flatness of 0.04 mm / m and a porosity of 1.2%.

[0098] Step 5: Preparation of the imitation gold coating: After ultrasonic cleaning, the brick was plasma activated for 3 minutes at 300W RF power and 100sccm Ar gas flow. Subsequently, the following layers were deposited: a 0.3μm thick Cr transition layer; a 1.2μm thick Cu-Zn-Ti alloy layer (70wt% Cu, 25wt% Zn, 5wt% Ti); and a 0.2μm SiO2 protective layer. XRF analysis revealed a -3.2% coating thickness error.

[0099] Step 6: Polishing and Packaging: Polishing is performed using a 2000-grit diamond grinding head on a planetary polisher at a spindle speed of 300 rpm and a pressure of 0.10 MPa. Coating adhesion meets ASTM D3359 standard 5B, with a surface gloss of 105 GU (measured at a 60° angle). Qualified products are packaged and stored.

[0100] The nitrogen protective atmosphere sintering furnace and other supporting equipment are the same as those in Example 1 and will not be described in detail here.

[0101] Performance Testing

[0102] The following performance tests were conducted on the gold-plated ceramic tiles prepared in Examples 1-3 above. All tests were conducted under standard laboratory conditions (temperature 23±2°C, humidity 50±5%). The test items focused on material performance and coating quality, using internationally accepted standard methods:

[0103] 1. Coating adhesion: Conduct tape peel test according to ASTM D3359 standard (cut 1mm×1mm grid, 3M600 tape vertically peeled).

[0104] 2. Surface gloss: measured using a 60° angle gloss meter according to ISO-2813 standard.

[0105] 3. Porosity of green body: Based on GB / T25995-2010 vacuum water absorption method (dry weighing → vacuum immersion for 24 hours → saturated surface dry weighing → boiling for 5 hours and weighing).

[0106] 4. Weathering resistance: Use Q-SUN Xe-3 aging chamber according to ASTM G154 for 1000 hours of UV accelerated aging (0.51W / m²@340nm, light / spray cycle).

[0107] 5. Coating uniformity: The thickness of 9 points is analyzed by surface scanning using an X-ray fluorescence spectrometer (XRF).

[0108] 6. Product qualification rate: Batch inspection (n≥100) shall be carried out according to the company's internal control standards (no peeling of coating / gloss ≥90GU / color difference ΔE≤2.0).

[0109] Example Preparation of Gold-plated Ceramic Tile Performance Test Data Table

[0110]

[0111] Note: 1. Comparative data source: Traditional electroplating process: "White Paper on Electroplating Ceramic Tile Industry" (2023), magnetron sputtering process: J.Mater.Sci.Technol.45(2)112-120; 2. ΔE value explanation: color difference change value (ΔE≤2.0 is not discernible to the naked eye).

[0112] In summary, the present invention significantly improves the coating adhesion to level 4B-5B (two levels higher than the traditional electroplating process) through the synergistic effect of the frit dry particle transition layer and the nitrogen protected sintering process, while reducing the green body porosity to 1.2-2.8% (a decrease of 65%), fundamentally solving the problem of easy peeling of the coating; after 1000 hours of UV accelerated aging test, the color difference ΔE value is stabilized 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.

[0113] The above is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with this technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solutions and inventive concepts of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A process for preparing gold-plated ceramic tiles made of ceramic frit dry particles, characterized in that: The specific steps are as follows: Step 1: Green body preparation: Mix the ceramic raw materials in the appropriate proportions, ball-mill until the fineness reaches 250 mesh, age for 12-24 hours in an environment with a humidity of 60-70%, press into shape under a pressure of 50-60 MPa, and dry in a chain drying kiln with hot air circulation at 110-120°C until the moisture content is less than 0.5%; Step 2: Preparation of frit dry particles: Mix the frit raw materials in the appropriate proportions, melt at 1500-1550°C, quench with water, crush and sieve to obtain 200-300 mesh particles for later use; Step 3: Applying the frit dry particles, the frit dry particles prepared in step 2 are evenly applied on the surface of the green body using an application device, with an application amount of 180~220g / m²; Step 4: Sintering of the green body: Use a nitrogen protective atmosphere sintering furnace to heat the green body to 600°C at 3-5°C / min, then to 900-920°C at 5-7°C / min, keep warm for 15-20 minutes, then cool to 500°C at ≤10°C / min, and then cool to below 150°C at 20-30°C / min. After sintering, test the surface flatness and porosity of the green body. Step 5: Preparation of imitation gold plating: the bricks sintered in step 4 are ultrasonically cleaned and sent to the pretreatment chamber for plasma surface activation treatment for 3 to 5 minutes under the conditions of RF power 200-300W and Ar gas flow rate 50-100sccm. Then they are transferred to the coating chamber and three functional coatings are deposited in sequence: a 0.2-0.3μm Cr transition layer is deposited; a 0.8-1.2μm Cu-Zn-Ti alloy layer is deposited, wherein the alloy components meet the following mass percentages: Cu content 60-70wt%, Zn content 20-30wt%, Ti content 2-5wt%; and a 0.1-0.2μm SiO2 protective layer is deposited; Step 6: Polishing and packaging. Use a planetary polishing machine to lightly polish the coated blank with a 1500~2000 mesh diamond grinding head, and package it after passing the inspection.

2. The process for preparing gold-plated ceramic tiles using ceramic frit dry particles according to claim 1, characterized in that: Step 1: The ceramic raw material for preparing the green body comprises the following components in weight percentage: Kaolin 50~55%; Quartz 25~35%; Feldspar 15~20%.

3. The process for preparing gold-plated ceramic tiles using ceramic frit dry particles according to claim 1, characterized in that: Step 2: The raw materials for preparing the frit dry particles include the following components in percentage by weight: SiO2 50~55%; Al2O3 20~25%; ZrO2 3~5%; Na2O 5~8%; TiO2 1~3%.

4. The process for preparing gold-plated ceramic tiles using ceramic frit dry particles according to claim 1, characterized in that: The nitrogen protective atmosphere sintering furnace described in step 4 includes a box-type atmosphere sintering furnace body (1), the outer wall of the box-type atmosphere sintering furnace body (1) is installed with a furnace door (2), the inner cavity of the box-type atmosphere sintering furnace body (1) is installed with an electric heating element (3), the nitrogen in the box-type atmosphere sintering furnace body (1) is circulated through a circulation purification mechanism (4), the circulation purification mechanism (4) includes an air inlet hole (401), the air inlet hole (401) 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 the outer wall of one side of the box-type atmosphere sintering furnace body (1), a fan (403) is installed on the air inlet pipe (402), and the top of the box-type atmosphere sintering furnace body (1) is fixedly connected to an exhaust pipe (404). The air inlet pipe (402) is connected to the air inlet hole (401), and one end of the exhaust pipe (404) and the air inlet pipe (402) is fixedly connected to a recovery tower (405). The inner wall of the recovery tower (405) is provided with two groups of upper air permeable plates (406), lower air permeable plates (407) and square frames (408). The upper air permeable plates (406) are located above the lower air permeable plates (407), and the square frame (408) is 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 cavity 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 by the replacement mechanism (5).

5. The process for preparing gold-plated ceramic tiles using ceramic frit dry particles 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), the outer wall of the other side of the recovery tower (405) is provided with a slot (502), the inner wall of the slot (502) is slidably connected to a collection box (503), the interior of the storage box (501) and the recovery tower (405) is provided with a movable groove (504) for the square frame (408) to slide, the outer wall of the square frame (408) is fixedly connected to a connecting plate (505), the connecting plate (505) extends out of the storage box (501), the interior of the recovery tower (405) is provided with a fixed groove (506) at the top of the movable groove (504), 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), the outer wall of the threaded rod (508) is slidably connected to a displacement rod (509), The displacement rod (509) is slidably connected to the interior 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 interior of the connecting plate (505) and extends to the top of the connecting plate (505), the outer wall of the recovery tower (405) is located at one end of the movable groove (504) and is rotatably connected to a rotating plate (511). 2), a torsion spring (513) is connected between the rotating plate (512) and the recovery tower (405), a groove (514) is provided at the bottom end of the rotating plate (512), a positioning frame (515) extending to the inner cavity of the movable 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 by a connecting mechanism (6).

6. The process for preparing gold-plated ceramic tiles using ceramic frit dry particles according to claim 5, characterized in that: The connecting mechanism (6) includes a reinforcement groove (601), the reinforcement groove (601) is opened at the top of the connecting plate (505), the top of the storage box (501) is provided with a cover plate (602), a card slot (603) is opened on one side of the inner wall of the storage box (501), the inner part of the cover plate (602) is slidably connected to a card block (604) extending from the cover plate (602), a second spring (605) is connected between the card block (604) and the cover plate (602), and the The interior of the storage box (501) is slidably connected to a reinforcement rod (606), a third spring (607) is connected between the reinforcement rod (606) and the storage box (501), the interior of the storage box (501) is located on the outer wall of the reinforcement rod (606) and is rotatably connected to a spur gear (608), the interior of the storage box (501) is located on the outer wall of the spur gear (608) and is slidably connected to a pressing rod (609), and the pressing rod (609) extends to the top of the storage box (501).

7. The process for preparing gold-plated ceramic tiles using ceramic frit dry particles according to claim 5, characterized in that: A threaded hole is provided on the outer wall of the displacement rod (509), and the threaded hole matches the threaded rod (508); both ends of the connecting rod (510) are connected to the displacement rod (509) and the fixed block (511) through a rotating shaft, and the outer wall of the top end of the fixed block (511) is in contact with the inner wall of the fixing groove (506).

8. The process for preparing gold-plated ceramic tiles using ceramic frit dry particles according to claim 5, characterized in that: The outer wall of the square frame (408) is in contact with the inner wall of the movable groove (504); the positioning frame (515) is provided with a triangular surface at one end of the inner cavity of the square frame (408), and the outer wall of the other end of the positioning frame (515) is in contact with the inner wall of the groove (514).

9. The process for preparing gold-plated ceramic tiles using ceramic frit dry particles according to claim 6, characterized in that: The outer wall of the bottom of the cover plate (602) fits in contact with the inner wall of the storage box (501), and the outer wall of one end of the clamping block (604) fits in contact with the inner wall of the clamping slot (603).

10. The process for preparing gold-plated ceramic tiles using ceramic frit dry particles according to claim 6, characterized in that: The outer wall of the bottom end of the reinforcing rod (606) is in contact with the inner wall of the reinforcing groove (601), and the outer walls of the reinforcing rod (606) and the lower pressing rod (609) are both provided with tooth grooves, which mesh with the spur gear (608).

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