Sapphire single crystal diamond glaze super wear-resistant ceramic tile and preparation method thereof

Abstract

The invention relates to the technical field of ceramic tiles, in particular to a sapphire single crystal diamond glaze super-wear-resistant ceramic tile and a preparation method thereof. The sapphire single crystal diamond glaze super wear-resistant ceramic tile is prepared from the following raw materials in parts by weight: high-purity alpha-Al2O3 powder, nano-diamond turbid liquid, rare earth modified zirconium silicate, a gas-phase transport agent, a lattice matching cosolvent and zinc oxide whiskers. According to the invention, the high-purity alpha-Al2O3 epitaxially grows on the surface of the nano-diamond to form an atomic-scale coherent interface, the bonding strength is high, the high hardness of sapphire and the wear resistance of diamond are integrated, the self-sharpening characteristic is endowed to the glaze layer by a micro-scale interlocking structure, a new hard interface is exposed in the wear process, the surface wear resistance is continuously maintained, and the service life of the glaze layer is prolonged. The problem of performance degradation after traditional materials are abraded is solved.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic tiles, and particularly relates to a sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile and a preparation method thereof. Background Art

[0002] Traditional ceramic tiles have long suffered from deficiencies such as insufficient wear resistance and easy scratching on the surface. In daily use, behaviors such as furniture dragging, sole friction, and cleaning tool scratching will all cause micro-scratches or stain penetration on the tile surface. Especially in high-traffic areas or areas with high usage frequency in the family, the gloss and flatness of the tiles will significantly decline over time. In addition, traditional tiles often use high-hardness glazes to improve wear resistance, but this will result in an overly shiny surface or a rigid touch, making it difficult to balance aesthetic and functional requirements.

[0003] The surface hardness of ordinary ceramic tiles is difficult to withstand daily wear. Scenarios such as furniture dragging, sole friction, and pet scratching may all cause scratches. Even if some products improve hardness by adding silicon carbide or corundum particles, there are still shortcomings such as the inability to have both wear resistance and gloss, and insufficient stain resistance. Early ultra-wear-resistant ceramic tiles mainly enhanced surface performance through physical plating or chemical penetration, but there was a problem of weak bonding force of the plating. Summary of the Invention

[0004] In view of the technical problems existing in the prior art, the present invention provides a sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile and a preparation method thereof.

[0005] The technical solution of the present invention to solve the above technical problems is as follows: A sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile, by weight, the raw materials of the sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile include: 40-60 parts of high-purity α-Al2O3 powder, 3-8 parts of nano-diamond suspension, 15-25 parts of rare earth modified zirconium silicate, 5-10 parts of gas phase transfer agent, 2-5 parts of lattice matching co-solvent, and 1-3 parts of zinc oxide whiskers.

[0006] Preferably, the nano-diamond suspension is treated by plasma hydrogenation to form C-H bond terminals on its surface. The treatment parameters are: hydrogen plasma power 300-500W, treatment time 30-60min, and the absolute value of the Zeta potential of the treated suspension ≥ 40mV.

[0007] Preferably, the rare earth elements in the rare earth modified zirconium silicate are co-doped with cerium and europium, and the doping molar ratio is Ce 3 + :Eu 3+ = 3:1, and the total doping amount accounts for 0.5% - 1.2% of the molar fraction of zirconium silicate.

[0008] Preferably, the gas-phase transport agent is composed of NH4F and HF compounded at a molar ratio of 1:2. The gaseous HF gas generated by its decomposition at high temperature reacts with Al2O3 to form gaseous AlF3 and a transportable AlOF intermediate. The reaction temperature is 850 - 920 °C.

[0009] Preferably, a method for preparing a sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile includes the following steps: S1. Wet ball-mill the raw materials in an anhydrous ethanol medium using a zirconia ball-milling tank with a ball-milling ratio of 5:1, a rotation speed controlled at 250 rpm - 350 rpm, and a grinding time of 1.5 h - 2.5 h to obtain a uniform slurry with a particle size D50 = 0.8 - 1.2 μm. S2. Transport the slurry to a centrifugal spray drying tower, control the inlet temperature at 200 °C - 250 °C and the outlet temperature at 75 °C - 80 °C to obtain spherical granulated powder with a fluidity index ≥75. The granulated powder is isostatically pressed into a green body at 80 MPa - 120 MPa, and the relative density of the green body reaches 55% - 65%. S3. Sinter the green body in a reducing atmosphere: In the first step, place the green body in a molybdenum wire sintering furnace, introduce a reducing gas mixture of H2 / Ar = 1:9, heat it to 1350 - 1400 °C at a rate of 5 °C / min, and hold for 1 h to form a eutectic liquid phase of the BaO - B2O3 - Li2O flux. The liquid phase fills the particle gaps through capillary force to achieve densification of the green body. In the second step, continue to heat it to 1550 - 1600 °C at a rate of 3 °C / min to trigger the gas-phase transport reaction. The specific process is as follows: a. The HF gas generated by the decomposition of NH4F·HF reacts with α - Al2O3 to form AlF3. b. AlF3 reacts with the unreacted α - Al2O3 to form a gaseous AlOF transport medium. c. Make α - Al2O3 epitaxially grow on the surface of the nano-diamond. S4. Corrode and construct the microstructure of the green body to obtain an ultra-wear-resistant ceramic tile with a sapphire single crystal diamond glaze layer.

[0010] Preferably, the epitaxial growth process specifically includes: The gaseous AlOF undergoes a coordination decomposition reaction on the surface of the nano-diamond: 3AlOF → Al2O3↓ + AlF3↑. The generated Al2O3 grows with a plane-preferred orientation and forms a coherent interface with the plane of the diamond.

[0011] Preferably, a pulsed magnetic field is synchronously applied during the second sintering stage. The magnetic field parameters are: Strength 0.5 - 1.2 T, frequency 10 - 50 Hz, duty cycle 30% - 50%, used to control the screw dislocation density of the sapphire single crystal to 103 -10 4 cm -2 Range.

[0012] Preferably, after sintering, a selective etching treatment is carried out: hot phosphoric acid is used to etch the residual flux phase, and then a hydrofluoric acid-nitric acid mixture is used to remove the surface amorphous layer, finally exposing the atomically smooth surface of the sapphire single crystal.

[0013] Preferably, a microtexture is constructed on the tile surface: a pit array with a period of 20 - 50 μm is formed by femtosecond laser etching, the ratio of the pit depth to the thickness of the sapphire single crystal layer is 1:3 - 1:5, and carbon nitride is deposited in the pits as a solid lubricant.

[0014] Preferably, a sapphire - diamond composite crystal structure with atomic - level coherent bonding is formed on the tile surface, where the sapphire single crystal grows epitaxially on the nano - diamond substrate with an orientation; The composite crystal structure presents a three - dimensional interlocking topological morphology at the microscale, endowing the glaze layer with self - sharpening wear characteristics; The rare - earth modified zirconium silicate produces a fluorescence labeling effect at the grain boundaries, and the wear state of the glaze layer can be monitored in real time by ultraviolet light irradiation; The synergistic effect of the surface microtexture and the carbon nitride lubricant realizes adaptive friction regulation in both dry and wet environments.

[0015] The beneficial effects of the present invention are as follows: In the present invention, high - purity α - Al2O3 grows epitaxially on the surface of nano - diamond, forming an atomic - level coherent interface with high bonding strength, combining the high hardness of sapphire and the wear resistance of diamond. The interlocking structure at the microscale endows the glaze layer with self - sharpening characteristics, exposing new hard interfaces during the wear process and continuously maintaining surface wear resistance, solving the problem of performance attenuation after wear of traditional materials. The rare - earth modified zirconium silicate forms a fluorescence label at the grain boundaries, and the wear degree of the glaze layer can be monitored in real time by the change of fluorescence intensity under ultraviolet light irradiation, realizing visual evaluation of the wear state. C3N4 solid lubricant is deposited in the pit array etched by femtosecond laser. Combining with the microtexture design, the friction coefficient can be reduced through lubricant slow release and surface texture coordination in both dry and wet environments, improving the anti - slip property and service life. The selective etching process accurately removes the residual flux and amorphous layer, exposing the atomically smooth surface, improving the gloss and chemical stability of the glaze layer, and avoiding crystal plane defects caused by impurity phases. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is a flowchart of the steps of the preparation method of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0017] Next, the technical solutions in the embodiments of the present application will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative efforts belong to the scope of protection of the present application.

[0018] In the description of the present application, the terms "first" and "second" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include one or more of the described features. In the description of the present application, the meaning of "a plurality" is two or more, unless otherwise specifically defined.

[0019] In the description of the present application, the term "for example" is used to mean "used as an example, illustration, or explanation". Any embodiment described as "for example" in the present application is not necessarily construed as being more preferred or more advantageous than other embodiments. In order for any person skilled in the art to implement and use the present invention, the following description is given. In the following description, details are set forth for purposes of explanation. It should be understood that those of ordinary skill in the art can recognize that the present invention can be implemented without the use of these specific details. In other instances, well-known structures and processes are not elaborated in detail to avoid unnecessary details from obscuring the description of the present invention. Therefore, the present invention is not intended to be limited to the embodiments shown, but is consistent with the broadest scope that conforms to the principles and features disclosed in the present application.

[0020] As Figure 1 , this embodiment provides: a sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile. By weight, the raw materials of the sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile include: 40-60 parts of high-purity α-Al2O3 powder, 3-8 parts of nano-diamond suspension, 15-25 parts of rare earth-modified zirconium silicate, 5-10 parts of gas-phase transport agent, 2-5 parts of lattice matching co-solvent, and 1-3 parts of zinc oxide whiskers.

[0021] It should be noted that the lattice matching co-solvent refers to an additive that promotes the growth of the target crystal phase, such as the directional growth of sapphire, by reducing the melt viscosity, adjusting the interfacial energy, or optimizing the lattice parameters during high-temperature sintering or crystal growth. The feasibility of using BaO-B2O3-Li2O as the lattice matching co-solvent is that Ba provided by BaO 2+ , can form a BaAl2O4 transition layer with Al2O3 to relieve the lattice matching between Al 3+ and the silicate in the glaze layer. Using B2O3 as a glass network former to reduce the melt viscosity and increase the diffusion of Al 3+ and Li in Li2O+ can partially replace Al 3+ in the vacant sites, enhance the charge compensation between the glaze layer and Al2O3, and the percentage composition of the lattice-matching cosolvent BaO - B2O3 - Li2O is: BaO (40% - 60%), B2O3 (20% - 35%), Li2O (10% - 25%).

[0022] It should be noted that as the crystal growth matrix, the rhombohedral crystal structure of high-purity α - Al2O3 powder has a 4.2% lattice mismatch with the cubic crystal system of nanodiamond on the crystal plane, meeting the crystallographic tolerance threshold for epitaxial growth (<5%). The particle size range of 5 - 20 nm for the nanodiamond suspension is selected based on two key factors: one is to ensure a specific surface area ≥200 m² / g to provide sufficient epitaxial sites, and the other is to avoid the quantum confinement effect caused by too small particle size (<5 nm) interfering with crystal growth. In rare earth modified zirconium silicate, the co - doping of Ce 3+ / Eu 3+ forms stress compensation centers in the lattice through ion radius matching (Ce 3+ = 1.01 Å, Eu 3+ = 0.95 Å, Zr 4+ = 0.72 Å). The composite ratio (1:2 molar ratio) of the gas - phase transport agent NH4F·HF precisely corresponds to the stoichiometric generation requirement of the AlOF gas - phase compound at high temperature, and its decomposition temperature window (850 - 920 °C) forms a kinetic synergy with the eutectic point (893 °C) of the cosolvent BaO - B2O3 - Li2O.

[0023] Furthermore, the nanodiamond suspension is treated by plasma hydrogenation to form C - H bond terminations on its surface. The treatment parameters are: hydrogen plasma power 300 - 500 W, treatment time 30 - 60 min, hydrogen gas pressure 50 - 100 Pa. After treatment, the C - H bond coverage rate on the surface is ≥90% and the absolute value of the Zeta potential of the suspension is ≥40 mV.

[0024] It should be noted that the process parameters of plasma hydrogenation treatment are set for the nanodiamond suspension, and its technical principle includes three levels: First, the hydrogen plasma power range of 300 - 500W ensures that the sp³ hybridized carbon atoms on the diamond surface react with hydrogen radicals to form C-H bonds (bond energy 413 kJ / mol), and this energy window is lower than the bond energy of the diamond bulk (711 kJ / mol), thus avoiding bulk damage. Second, the positive correlation between the treatment time of 30 - 60 min and the particle size (45 min for 5 nm particles and 30 min for 20 nm particles) is determined by the surface atom ratio formula: N_surface / N_total≈4d / D (d is the atomic diameter, D is the particle size). Finally, the requirement of the absolute value of Zeta potential ≥ 40 mV is obtained through DLVO theory calculation. This value can overcome the van der Waals force barrier and ensure that the suspension stability meets the requirements of the subsequent ball milling process. The treated suspension needs to be stored under nitrogen protection to prevent the attenuation of the Zeta potential caused by the oxidation of C-H bonds.

[0025] Furthermore, the rare earth elements in the rare earth modified zirconium silicate are co-doped with cerium and europium, and the doping molar ratio is Ce 3+ : Eu 3+ = 3:1, and the total doping amount accounts for 0.5% - 1.2% of the molar fraction of zirconium silicate, and the matching degree of the 4f→5d transition energy level of Ce 3+ with the band gap width of Al2O3 is ≥ 95%.

[0026] It should be noted that the doping ratio of Ce 3+ : Eu 3+ = 3:1 is specified in zirconium silicate, and its mechanism of action is reflected in two aspects: crystal field effect and energy transfer. From the perspective of crystal structure, this ratio makes the change of the ZrSiO4 unit cell parameter Δa / a = 0.3% within the tolerance limit of lattice distortion. The limit of the total doping amount of 0.5 - 1.2 mol% is based on the concentration quenching effect test. When > 1.2 mol%, cross relaxation occurs due to the rare earth ion spacing < 0.5 nm, resulting in a decrease in the fluorescence quantum yield by more than 50%.

[0027] Furthermore, the gas-phase transport agent is composed of NH4F and HF compounded in a molar ratio of 1:2. The gaseous HF gas generated by its decomposition at high temperature reacts with Al2O3 to form gaseous AlF3 and the transportable AlOF intermediate, and the reaction temperature is 850 - 920 °C.

[0028] It should be noted that ammonium fluoride NH4F and hydrogen fluoride HF are compounded in a molar ratio of 1:2 and decomposed at high temperature (850℃-920℃). HF will react with Al2O3 in the system to generate gaseous AlF3, and then react with Al2O3 to generate transportable AlOF intermediate. AlF3 has high volatility at high temperatures, but can still exist in gaseous form within the temperature range (850℃-920℃). The decomposition products of NH4F participate in regulating the reaction atmosphere and reducing oxidation side reactions. The generated AlF3 can further react with incompletely reacted Al2O3 to form AlOF. AlOF has a high migration ability, which is conducive to the uniform distribution of the glaze layer crystal phase.

[0029] It should be noted that the gas phase transfer agent NH4F·HF undergoes a three-step decomposition reaction at high temperature: NH4F·HF→NH4HF2(150℃)→NH4F+HF(350℃)→NH3↑+2HF↑(600℃). In the working temperature range of 850-920℃, HF reacts with Al2O3 to form the key transmission medium AlOF: Al2O3+AlF3→3AlOF. The selection of this temperature range is based on thermodynamic calculations. In this range, the partial pressure of AlOF reaches 10 -3 -10 -2 atm, meeting the transmission rate requirements while avoiding excessive volatilization.

[0030] A method for preparing sapphire single crystal diamond glaze super wear-resistant ceramic tile comprises the following steps: S1. The raw materials are wet-milled in anhydrous ethanol medium using a zirconium oxide ball mill, with a ball milling ratio of 5:1, a rotation speed controlled at 250rpm-350rpm, and a grinding time of 1.5h-2.5h to obtain a uniform slurry with a particle size of D50 = 0.8-1.2μm; S2. The slurry is transported to a centrifugal spray drying tower, and the inlet temperature is controlled at 200°C-250°C and the outlet temperature is controlled at 75°C-80°C to obtain spherical granulation powder with a fluidity index ≥ 75. The granulation powder is formed into a green billet by isostatic pressing at 80MPa-120MPa, and the relative density of the green billet reaches 55%-65%; S3, sintering the green body in a reducing atmosphere: The first step is to keep the temperature at 1350-1400℃ for 1h to form a eutectic liquid phase of BaO-B2O3-Li2O co-solvent; The second step is to raise the temperature to 1550-1600℃ to trigger the gas phase transport reaction, so that α-Al2O3 grows epitaxially on the surface of nanodiamond; S4. The green body is subjected to corrosion treatment and micro-texture construction, and the green body after the above treatment is polished and cut to obtain a super wear-resistant ceramic tile with a sapphire single crystal diamond glaze layer.

[0031] It should be noted that the two-step sintering process design is based on phase diagram analysis and diffusion dynamics: the first stage 1350-1400℃ corresponds to the eutectic region of the BaO-B2O3-Li2O ternary phase diagram, and the liquid phase fills the gaps between particles through capillary force to form a dense green body. The second stage 1550-1600℃ heating rate is controlled at 5℃ / min, and the reducing atmosphere H2 / Ar=1:9 ratio ensures that the oxygen partial pressure is maintained at 10 -12 -10 -10 atm range, under this condition, the aluminum vacancy concentration [V_Al”]≈(1-5)×10 17 cm -3 , which promotes Al 3+ Diffusion and avoid excessive reduction to form Al metal phase. The holding time of 1h and 0.5h is calculated by the Arrhenius equation to ensure that the density is greater than 98% and the grain size is less than 5μm, where (1-5)×10 17 cm -3 Indicates that the aluminum vacancy concentration range is 1×10 17 cm -3 Up to 5×10 17 cm -3 .

[0032] Furthermore, the epitaxial growth process specifically includes: gas phase AlOF undergoes coordination decomposition reaction on the surface of nanodiamond: 3AlOF→Al2O3↓+AlF3↑; the generated Al2O3 grows in a face-preferential orientation and forms a coherent interface with the face of diamond.

[0033] It should be noted that the central atom (Al) in the precursor (AlOF) combines with different ligands at the same time to form an unstable coordination structure. Under high temperature or surface catalysis, the coordination bonds break and reorganize, and decompose into two or more products with different coordination states (Al2O3 and AlF3). It does not involve changes in the oxidation state of the central atom, but the coordination form and physical state (solid / gas phase) of the products are significantly different. For AlOF generated by gas phase transport agent, its decomposition process can be described as: 3AlOF→Al2O3↓+AlF3↑.

[0034] Al in AlOF 3+ At the same time with O 2- and F - After coordination and decomposition, some Al 3+ One part is converted into hexacoordinated Al2O3 (stable crystal structure), and the other part is converted into tetracoordinated AlF3 (gas volatilization). The surface of nanodiamond provides heterogeneous nucleation sites, which reduces the crystallization barrier of Al2O3. AlF3 leaves the reaction system due to its gas phase volatility, pushing the equilibrium to the right.

[0035] It should be noted that the epitaxial growth process follows the vapor-liquid-solid mechanism: First, a wetting layer with a thickness of about 2 nm is formed on the diamond surface by the BaO-B2O3-Li2O liquid phase. Subsequently, the gas-phase AlOF undergoes a coordination decomposition reaction at the liquid / solid interface: 3AlOF → Al2O3↓ + AlF3↑. The newly formed Al2O3 grows by surface epitaxy, and the formation of the coherent interface is confirmed by HRTEM observation.

[0036] Furthermore, a pulsed magnetic field is applied synchronously during the second sintering stage. The magnetic field parameters are: intensity 0.5 - 1.2 T, frequency 10 - 50 Hz, and duty cycle 30% - 50%, which are used to control the screw dislocation density of the sapphire single crystal to the range of 10³ - 10 4 cm -2 range.

[0037] It should be noted that the pulsed magnetic field treatment improves the crystal quality through three physical effects: 1) The magneto-induced shear effect, where the Lorentz force F = qvB ≈ 10 -12 N / electron generated by a 1 T magnetic field causes the dislocation line to undergo a bowing-out motion; 2) The magneto-plastic effect, where the alternating magnetic field induces the electron spin to flip, promoting dislocation climb; 3) The magnetostrictive effect, where the 4f electrons of Ba 2+ ions are oriented and arranged in the magnetic field, generating a lattice distortion of about 0.01% to release the internal stress. The selection of the magnetic field strength of 0.5 - 1.2 T is based on the critical shear stress formula, and this range corresponds to the optimal interval of the dislocation density. The setting of the duty cycle of 30% - 50% avoids the temperature fluctuation caused by the Joule heat effect exceeding ±5°C.

[0038] Furthermore, after sintering, selective etching treatment is carried out: Hot phosphoric acid is used to etch the residual flux phase, and then a hydrofluoric acid-nitric acid mixture is used to remove the surface amorphous layer, finally exposing the atomically smooth surface of the sapphire single crystal.

[0039] It should be noted that the etching process includes two stages: selective dissolution and atomic-level planarization. The 85°C hot phosphoric acid removes the residual flux phase through the coordination dissolution mechanism, with a dissolution rate of 1.2 μm. The HF:HNO3 = 1:3 mixture etches the (001) plane with an etching rate of 0.8 nm / min because the Al 30 coordination number on this plane is 6 and the bond energy is relatively high, requiring strong acid dissociation. The (100) plane has an etching rate of 1.2 nm / min, and there are dangling bonds on this plane, which are more easily attacked by H +Attack, by controlling the etching time, achieve atomic-level flatness. Finally, the surface roughness Ra ≤ 0.5 nm, and the etching depth is controlled within 10% - 15% of the glaze layer thickness. This range is determined by TEM electron energy loss spectroscopy to ensure complete removal of the amorphous layer without damaging the epitaxial structure. Among them, the (001) plane refers to the crystal plane perpendicular to the c-axis of the sapphire single crystal α-Al2O3, with a relatively high atomic arrangement density and a slow etching rate. The (100) plane refers to the crystal plane perpendicular to the a-axis of the sapphire single crystal, with a relatively low atomic arrangement density and a fast etching rate. The above crystal plane indices are based on the standard orientation of the hexagonal crystal system, and the difference in their etching rates stems from the anisotropy of the Al-O bond breaking energy of each crystal plane.

[0040] Furthermore, construct micro-textures on the tile surface: form a pit array with a period of 20 - 50 μm by femtosecond laser etching. The ratio of the pit depth to the sapphire single crystal layer thickness is 1:3 - 1:5, and carbon nitride is deposited in the pits as a solid lubricant.

[0041] It should be noted that femtosecond laser etching is based on the principle of nonlinear absorption: the 1030 laser generates localized plasma in the focal region through two-photon absorption to achieve material removal. The design basis for the pit period of 20 - 50 μm is the contact mechanics formula a=(PR / E)^(1 / 2), where a is the contact radius, P is the load, and R is the abrasive radius. This size range ensures that the abrasive (typical abrasive 5 - 15 μm) is always in contact with the raised part of the texture. The deposition of C3N4 is completed by pulsed laser deposition. The interlayer spacing of its layered structure is 3.3 Å, and the lattice mismatch with the sapphire surface is only 3.6%, forming a strong interfacial bond.

[0042] Furthermore, a sapphire-diamond composite crystal structure with atomic-level coherent bonding is formed on the tile surface, where the sapphire single crystal grows epitaxially on the nano-diamond substrate; The composite crystal structure presents a three-dimensional interlocking topological morphology at the microscale, endowing the glaze layer with self-sharpening wear characteristics; The rare earth-modified zirconium silicate produces a fluorescence labeling effect at the grain boundaries, and the wear state of the glaze layer is monitored in real time by ultraviolet light irradiation; The synergistic effect of the surface micro-texture and the carbon nitride lubricant realizes adaptive friction regulation in dry and wet environments.

[0043] Example 1 A sapphire single crystal diamond glaze ultra-wear-resistant tile, including 50 parts of high-purity α-Al2O3 powder, 5 parts of nano-diamond, 20 parts of rare earth-modified zirconium silicate, 8 parts of gas-phase transport agent, 3 parts of lattice matching co-solvent, and 2 parts of zinc oxide whiskers as raw materials; A preparation method of a sapphire single crystal diamond glaze ultra-wear-resistant tile, including the following steps: S1. Subject the nanodiamond suspension to 400W plasma hydrogenation treatment for 45 minutes to form C-H bond terminations on the surface; S2. Wet-mill the raw materials in anhydrous ethanol using a zirconia ball milling tank with a ball milling ratio of 5:1, a rotation speed of 300 rpm, and a grinding time of 2 hours to obtain a slurry with a particle size D50 = 1.0 μm; S3. Process the slurry through a centrifugal spray drying tower with an inlet temperature of 230 °C and an outlet temperature of 78 °C to obtain spherical granulated powder with a fluidity index ≥ 75. The granulated powder is isostatically pressed into a green body at 100 MPa, and the relative density of the green body is 60%; S4. Conduct two-step sintering in a reducing atmosphere: First step: In a reducing atmosphere of H2 / Ar = 1:9, heat up to 1380 °C at a rate of 5 °C / min and hold for 1 hour to form a eutectic liquid phase of the flux; Second step: Heat up to 1580 °C at a rate of 3 °C / min to trigger a gas-phase transport reaction, and simultaneously apply a 0.8T pulsed magnetic field; S5. First, corrode the residual flux phase with hot phosphoric acid, and then remove the surface amorphous layer with a hydrofluoric acid-nitric acid mixture; S6. Form a pit array with a period of 30 μm by femtosecond laser etching. The ratio of the pit depth to the thickness of the sapphire single crystal layer is 1:4, and carbon nitride is deposited in the pits as a solid lubricant.

[0044] Example 2 A sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile comprises 55 parts of high-purity α-Al2O3 powder, 7 parts of nanodiamonds, 18 parts of rare earth-modified zirconium silicate, 6 parts of gas-phase transport agent, 4 parts of lattice-matching flux, and 1.5 parts of zinc oxide whiskers as raw materials; A preparation method of a sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile comprises the following steps: S1. Subject the nanodiamond suspension to 350W plasma hydrogenation treatment for 50 minutes to form C-H bond terminations on the surface; S2. Wet-mill the raw materials in anhydrous ethanol using a zirconia ball milling tank with a ball milling ratio of 5:1, a rotation speed of 250 rpm, and a grinding time of 2.5 hours to obtain a slurry with a particle size D50 = 1.2 μm; S3. Process the slurry through a centrifugal spray drying tower with an inlet temperature of 200 °C and an outlet temperature of 80 °C to obtain spherical granulated powder with a fluidity index of 75. The granulated powder is isostatically pressed into a green body at 80 MPa, and the relative density of the green body is 55%; S4. Conduct two-step sintering in a reducing atmosphere: First step: In a reducing atmosphere of H2 / Ar = 1:9, heat up to 1360 °C at a rate of 5 °C / min and hold for 1 hour to form a eutectic liquid phase of the flux; Step 2: Heat up to 1560 °C at a rate of 3 °C / min to trigger the gas-phase transport reaction, and simultaneously apply a 1.0 T pulsed magnetic field; S5. First, etch the residual flux phase with hot phosphoric acid, and then remove the surface amorphous layer with a hydrofluoric acid-nitric acid mixture; S6. Form a pit array with a period of 25 μm by femtosecond laser etching. The ratio of the pit depth to the thickness of the sapphire single crystal layer is 1:3, and carbon nitride is deposited in the pits as a solid lubricant.

[0045] Example 3 A sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile, comprising 45 parts of high-purity α-Al2O3 powder, 4 parts of nano-diamond, 22 parts of rare earth-modified zirconium silicate, 9 parts of gas-phase transport agent, 2 parts of lattice-matching flux, and 3 parts of zinc oxide whiskers as raw materials; A preparation method of a sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile, comprising the following steps: S1. Subject the nano-diamond suspension to 450 W plasma hydrogenation treatment for 30 min to form C-H bond terminations on the surface; S2. Wet-mill the raw materials in an anhydrous ethanol using a zirconia ball mill pot, with a ball-to-powder ratio of 5:1, a rotation speed of 350 rpm, and a grinding time of 1.5 h to obtain a slurry with a particle size D50 = 0.8 μm; S3. Process the slurry through a centrifugal spray drying tower at an inlet temperature of 250 °C and an outlet temperature of 75 °C to obtain spherical granulated powder with a fluidity index of 85. The granulated powder is isostatically pressed into a green body at 120 MPa, and the relative density of the green body is 65%; S4. Perform two-step sintering in a reducing atmosphere: First step: In a H2 / Ar = 1:9 reducing atmosphere, heat up to 1400 °C at a rate of 5 °C / min and hold for 1 h to form a eutectic liquid phase of the flux; Second step: Heat up to 1600 °C at a rate of 3 °C / min to trigger the gas-phase transport reaction, and simultaneously apply a 0.5 T pulsed magnetic field; S5. First, etch the residual flux phase with hot phosphoric acid, and then remove the surface amorphous layer with a hydrofluoric acid-nitric acid mixture; S6. Form a pit array with a period of 40 μm by femtosecond laser etching. The ratio of the pit depth to the thickness of the sapphire single crystal layer is 1:5, and carbon nitride is deposited in the pits as a solid lubricant.

[0046] Example 4 A sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile, comprising 60 parts of high-purity α-Al2O3 powder, 8 parts of nano-diamond, 15 parts of rare earth-modified zirconium silicate, 5 parts of gas-phase transport agent, 5 parts of lattice-matching flux, and 1 part of zinc oxide whiskers as raw materials; A preparation method of a sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile, comprising the following steps: S1. Subject the nanodiamond suspension to 500W plasma hydrogenation treatment for 60 min to form C-H bond terminations on the surface; S2. Wet-mill the raw materials in an anhydrous ethanol using a zirconia ball milling tank with a ball milling ratio of 5:1, a rotation speed of 320 rpm, and a grinding time of 2.2 h to obtain a slurry with a particle size D50 = 0.9 μm; S3. Process the slurry through a centrifugal spray drying tower with an inlet temperature of 220 °C and an outlet temperature of 76 °C to obtain spherical granulated powder with a fluidity index of 82. The granulated powder is isostatically pressed at 90 MPa to form a green body, and the relative density of the green body is 62%; S4. Conduct two-step sintering in a reducing atmosphere: First step: In a reducing atmosphere of H2 / Ar = 1:9, heat up to 1350 °C at a rate of 5 °C / min and hold for 1 h to form a eutectic liquid phase of the flux; Second step: Heat up to 1550 °C at a rate of 3 °C / min to trigger the gas-phase transport reaction and simultaneously apply a 1.2T pulsed magnetic field; S5. First, etch the residual flux phase with hot phosphoric acid, and then use a hydrofluoric acid-nitric acid mixture to remove the surface amorphous layer; S6. Form a pit array with a period of 20 μm through femtosecond etching. The depth of the pit is in a ratio of 1:3 to the thickness of the sapphire single crystal. Deposit carbon nitride in the pits as a solid lubricant.

[0047] Table 1 It can be concluded from Table 1 that: For α-Al2O3 powder, its dosage varies between 45 - 60 parts. Appropriate increase can provide more crystal growth skeletons, which is beneficial to the formation of a continuous epitaxial layer of sapphire single crystal and improve properties such as wear resistance. However, too high dosage may affect the performance of other components. The appropriate ratio is crucial for constructing a stable structure. The number of nanodiamond parts fluctuates between 4 - 8 parts. Increasing the content may enhance the strength and wear resistance of the composite structure. However, too much may affect the dispersion uniformity due to the increased risk of agglomeration. It is necessary to reasonably control the dosage to balance the enhancement effect and dispersibility. When the dosage is between 15 - 22 parts, its ratio affects the fluorescence labeling effect. The appropriate proportion ensures effective labeling at the grain boundaries for monitoring the wear state of the glaze layer. Different ratios may affect the luminescence intensity and stability. The dosage changes of gas-phase transport agents, lattice-matching fluxes, zinc oxide whiskers, etc. have effects on aspects such as gas-phase transport reactions, reducing sintering temperature, and toughening respectively. The interaction of each component affects the performance of the final product.

[0048] The plasma treatment power is adjusted between 350 - 500 W. The power affects the surface modification effect of nanodiamonds. An appropriate power forms C-H terminations on the surface, increases the absolute value of the Zeta potential, and enhances the dispersion stability. Improper power may lead to poor dispersion and affect the overall performance. The two-step sintering temperature fluctuates in the range of 1350 - 1400 °C for the first step and 1550 - 1600 °C for the second step. The temperature of the first step affects the formation of eutectic liquid phase of the flux, and the temperature of the second step triggers the gas-phase transport reaction. Precise control of the temperature ensures the orderly progress of the reaction and affects the growth quality of sapphire single crystals. The pulsed magnetic field intensity is in the range of 0.5 - 1.2 T. The magnetic field intensity is used to regulate the screw dislocation density of sapphire single crystals. An appropriate intensity optimizes the crystal defect structure and balances the strength and toughness. Unsuitable intensity cannot effectively regulate dislocations and affects the material performance. The laser pit period varies from 20 - 40 μm. This parameter affects the microtexture of the tile surface. Different periods, in combination with the pit depth and the thickness of the sapphire single crystal layer, affect the friction regulation effect in dry and wet environments. Appropriate parameters need to be selected according to the application scenario.

[0049] Comparative Example 1 Compared with Example 1, the high-purity α-Al2O3 powder was reduced to 30 parts, and the proportions of other raw materials were similar to those in Example 1. The preparation process was the same as that in Example 1. However, due to insufficient α-Al2O3, the crystal growth framework was insufficient, resulting in discontinuous epitaxial layers with a coverage rate of less than 50%. Finally, the wear resistance only reached Class 3.

[0050] Comparative Example 2 The raw material ratio of Example 2 was adopted, but the nanodiamond suspension was not subjected to plasma hydrogenation treatment. Due to the lack of this treatment, the surface energy of nanodiamonds was unbalanced, and the dispersion failed, resulting in agglomeration. After agglomeration, the particle size was greater than 100 nm, causing microstructural defects. Affected by this, the hardness of the tile decreased to 1800 HV, showing performance degradation. The mechanism was that the surface energy of nanodiamonds was unbalanced and could not be evenly dispersed, resulting in internal structural defects of the material and a decrease in hardness.

[0051] Comparative Example 3 The raw material ratio and sintering process of Example 3 were adopted, but the pulsed magnetic field was cancelled. The dislocation multiplication was not inhibited, and the dislocation density reached 10 6 cm -2 , causing microstructural defects. After 20 thermal shock cycles, the tile cracked, showing performance degradation. The mechanism was the absence of a pulsed magnetic field, which could not regulate the dislocation density. Dislocations multiplied in large numbers, and stress concentration during thermal shock caused cracking.

[0052] Comparative Example 4 The raw materials and sintering process of Example 4 are adopted, but the laser etching step is cancelled. The fluid lubrication structure formed by laser etching is lacking on the tile surface, resulting in microstructural defects, leading to a relatively high friction coefficient of the tile and performance deterioration. The mechanism is that the microtexture cannot be constructed by laser etching, an effective lubrication structure cannot be formed, and the frictional resistance is large.

[0053] Table 2 The following conclusions can be drawn based on Table 2: Critical value of raw material ratio (Comparative Example 1) When the content of high-purity powder decreases to 30 parts, due to the severe shortage of Al atomic flux, the complete three-dimensional crystal growth framework cannot be maintained, resulting in structural defects in the epitaxial layer. This state of insufficient Al source supply leads to a significant decrease in the concentration of AlOF intermediate in the gas-phase transport process, causing the epitaxial growth mode on the surface of the nanodiamond substrate to change from the ideal layer-by-layer growth to island growth. It is difficult to form effective coherent interface connections between crystal islands, and there are a large number of unbonded dangling bonds at the grain boundaries, becoming stress concentration points and crack sources.

[0054] Necessity of surface treatment of nanodiamond (Comparative Example 2) When the nanodiamond suspension is not subjected to plasma hydrogenation treatment, the imbalance of its surface energy leads to severe agglomeration (particle size > 100 nm), directly causing the hardness to drop sharply to 1800 HV (significantly lower than 2200 - 2500 HV in Example 2). Surface modification of nanodiamond (such as plasma hydrogenation) is a key step to avoid agglomeration and ensure uniform dispersion. The regulation of its surface functional groups (such as C-H bonds) directly affects the binding force with the matrix and the mechanical properties of the material.

[0055] Regulatory effect of pulsed magnetic field on dislocation density (Comparative Example 3) After cancelling the pulsed magnetic field, the dislocation density of the sapphire single crystal layer rises to 10 6 cm -2 (controlled at 10 4 -10 5 cm -2 ) in the example, resulting in cracking of the tile after 20 thermal shock cycles. The pulsed magnetic field can improve the thermal shock resistance and structural stability of the material by suppressing dislocation proliferation and reducing the crystal defect density. The lack of magnetic field regulation will cause internal stress concentration and brittle fracture.

[0056] Optimization of friction coefficient by laser etching (Comparative Example 4) When laser etching is not carried out, the surface of the ceramic tile lacks a fluid lubrication structure (such as micron-sized pits), and the friction coefficient is as high as 0.65 (in the examples, the friction coefficient is controlled between 0.30 and 0.45 through etching). The micro-textures formed by laser etching (such as periodic pits) can store lubricating media (such as water or grease) between interfaces, reduce the direct contact area, and significantly reduce the frictional resistance. Surface texture design is the key process for regulating friction performance.

[0057] Table 3 It can be obtained from Table 3 that: In Comparative Example 1, the wear resistance of α-Al2O3 only reaches Class 3. In Examples 1-4, by controlling the amount of α-Al2O3 at 45-60 parts and combining with the gas-phase transport process, the continuity of the wear-resistant layer is ensured; In Comparative Example 2, the hardness of the nanodiamond agglomerates drops to 1800 HV. In Examples 1-4, the nanodiamond suspension is subjected to plasma hydrogenation treatment to achieve surface C-H bond regulation and uniform dispersion, and synergistically strengthen with the sapphire substrate; In Comparative Example 3, the dislocation density soars after canceling the pulsed magnetic field and cracks after 20 thermal shocks. In Examples 1-4, a pulsed magnetic field is applied synchronously in the second step of sintering to effectively regulate the dislocation density by 10 4 -10 5 cm -2 to relieve stress concentration; In Comparative Example 4, the laser etching friction coefficient is canceled. In Examples 1-4, femtosecond laser etching is used to construct micro-textures to achieve lubricating medium storage; Examples 1-4 all implement the "hot phosphoric acid + hydrofluoric acid - nitric acid corrosion to remove the amorphous layer + gas-phase transport epitaxial growth process" and combine the atomic-level flatness of epitaxial growth to be close to atomic-level smoothness; In Comparative Example 1, due to insufficient α-Al2O3, the coverage rate is less than 50%. In Examples 1-4, by controlling the amount of α-Al2O3 and combining with the gas-phase transport process regulated by the eutectic phase of the cosolvent + pulsed magnetic field, continuous growth of the sapphire epitaxial layer on the surface of the nanodiamond is achieved, with a coverage rate ≥ 93%, ensuring structural integrity.

[0058] It should be noted that in the above examples, the descriptions of each example have their own emphases. For the parts not described in detail in a certain example, reference can be made to the relevant descriptions of other examples.

[0059] Although the preferred embodiments of the present invention have been described, those skilled in the art can make additional changes and modifications to these embodiments once they know the basic creative concept. Therefore, the appended claims are intended to be construed as including the preferred embodiments and all changes and modifications falling within the scope of the present invention.

[0060] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention is also intended to include these modifications and variations.

Claims

1. A sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile, characterized in that The raw materials of the sapphire single crystal diamond glaze super wear-resistant ceramic tile include, by weight: 40-60 parts of high-purity α-Al2O3 powder, 3-8 parts of nano-diamond suspension, 15-25 parts of rare earth modified zirconium silicate, 5-10 parts of gas phase transmission agent, 2-5 parts of lattice matching auxiliary solvent, and zinc oxide whisker; The lattice matching auxiliary solvent is a BaO-B2O3-Li2O ternary system.

2. The super wear-resistant ceramic tile with sapphire single crystal diamond glaze according to claim 1, wherein The nano-diamond suspension is treated by plasma hydrogenation to form CH bond terminals on its surface. The treatment parameters are: hydrogen plasma power 300-500W, treatment time 30-60min, and the absolute value of Zeta potential of the treated suspension is ≥40mV.

3. The super wear-resistant ceramic tile with sapphire single crystal diamond glaze according to claim 1, characterized in that, The rare earth elements in the rare earth modified zirconium silicate are co-doped with cerium and europium, and the doping molar ratio is Ce 3+ : Eu 3+ = 3:1, and the total doping amount accounts for 0.5% - 1.2% of the molar fraction of zirconium silicate.

4. A sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile according to claim 1, wherein The gas phase transmission agent is composed of NH4F and HF in a molar ratio of 1:

2. The gaseous HF gas generated by the decomposition at high temperature reacts with Al2O3 to generate gaseous AlF3 and a transportable AlOF intermediate. The reaction temperature is 850-920°C.

5. A method for preparing a sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile as described in any one of claims 1-4, characterized in that, The following steps are involved: S1. The raw materials are wet-milled in anhydrous ethanol medium using a zirconium oxide ball mill, with a ball milling ratio of 5:1, a rotation speed controlled at 250rpm-350rpm, and a grinding time of 1.5h-2.5h to obtain a uniform slurry with a particle size of D50 = 0.8-1.2μm; S2. The slurry is transported to a centrifugal spray drying tower, and the inlet temperature is controlled at 200°C-250°C and the outlet temperature is controlled at 75°C-80°C to obtain spherical granulation powder with a fluidity index ≥ 75. The granulation powder is formed into a green billet by isostatic pressing at 80MPa-120MPa, and the relative density of the green billet reaches 55%-65%; S3, sintering the green body in a reducing atmosphere: The first step is to keep the temperature at 1350-1400℃ for 1h to form a eutectic liquid phase with BaO-B2O3-Li2O lattice matching solvent; The second step is to raise the temperature to 1550-1600℃ to trigger the gas phase transport reaction, so that α-Al2O3 grows epitaxially on the surface of nanodiamond; S4, subjecting the green body to corrosion treatment and micro-texture construction to obtain the sapphire single crystal diamond glaze super wear-resistant ceramic tile.

6. The preparation method of a sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile according to claim 5, characterized in that, The epitaxial growth process specifically includes: The gas phase AlOF undergoes a coordination decomposition reaction on the surface of nanodiamond: 3AlOF→Al2O3↓+AlF3↑. The generated Al2O3 grows in a face-preferential orientation and forms a coherent interface with the diamond surface.

7. The preparation method of a sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile according to claim 5, characterized in that, In the second sintering stage, a pulsed magnetic field is applied synchronously, and the magnetic field parameters are: Intensity 0.5 - 1.2T, frequency 10 - 50Hz, duty cycle 30% - 50%, used to regulate the screw dislocation density of sapphire single crystal to 10 3 -10 4 cm -2 range.

8. The preparation method of a sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile according to claim 5, characterized in that Selective corrosion treatment is carried out after sintering: Hot phosphoric acid is used to etch the residual flux phase, and then a hydrofluoric acid-nitric acid mixture is used to remove the surface amorphous layer, ultimately exposing the atomically smooth surface of the sapphire single crystal.

9. The preparation method of a sapphire single crystal diamond glaze ultra-wear-resistant ceramic tile according to claim 5, characterized in that, After sintering and etching, a micro texture is created on the tile surface: A pit array with a period of 20-50 μm is formed by femtosecond laser etching. The ratio of the pit depth to the sapphire single crystal layer thickness is 1:3-1:5, and carbon nitride is deposited in the pit as a solid lubricant.

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