Metal organic framework-based glaze, ceramic product and preparation method of ceramic product

Abstract

The invention discloses a metal organic framework (MOFs)-based glaze, a ceramic product and a preparation method of the ceramic product, and belongs to the technical field of ceramic materials. The provided metal organic framework-based glaze comprises a metal organic framework material and a basic glaze, and the basic glaze comprises the following components: white feldspar, quartz, calcite, wollastonite, copper ore, talc, bovine bone and tin oxide. According to the metal organic framework-based glaze disclosed by the invention, the MOFs are used as a core function regulation and control unit and matched with the white feldspar, the quartz, the calcite, the wollastonite, the copper ore, the tin oxide, the talc and the bovine bone to form a mineral composite system with a specific weight percentage; an integrated technical system of function regulation and control, structure forming and performance optimization is constructed through a stepped preparation process of precise raw material proportioning, high-energy ball milling pulping, multi-dimensional uniform glazing and controlled atmosphere glaze firing; the problems that a current ceramic glaze system is single in component regulation dimension, uncontrollable in transmutation effect, weak in glaze blank interface bonding and the like can be solved.

Description

Technical Field

[0001] This application belongs to the field of ceramic materials technology, specifically relating to a metal-organic framework-based glaze, ceramic products, and their preparation methods. Background Technology

[0002] Ceramics, as an important material carrier of China's outstanding traditional culture, represents the pinnacle of traditional porcelain-making techniques, integrating "technological complexity, glaze artistry, and cultural symbolism." Its unique kiln transformation phenomenon and rich glaze layers not only embody the essence of millennia-old ceramic civilization but also constitute the core content of contemporary cultural heritage revitalization and inheritance. Traditional ceramic firing techniques are characterized by "experience-based mineral formulations and uncontrollable kiln transformation processes." Relying on the compatibility of specific mineral components and complex kiln atmosphere control, while achieving unique aesthetic effects, the technological bottlenecks of the traditional system are becoming increasingly prominent as modern society upgrades its demands for "high-end, functional, and personalized" ceramics. On the one hand, traditional glazes are dominated by natural minerals, with limited room for component control, resulting in poor glaze color stability, significant batch-to-batch variations, and difficulty in coordinating and optimizing the mechanical properties such as glaze hardness and wear resistance with the aesthetic texture of jade-like luster. On the other hand, kiln transformation effects rely on empirical process parameters, making targeted design impossible and failing to meet the diverse application needs of contemporary high-end decorative and functional ceramics, thus hindering the cross-border development of ceramics from "cultural and artistic works" to "high-value-added functional products."

[0003] Currently, research in the ceramics field still focuses on the traditional paradigm of "fine-tuning of traditional glaze components" and "optimization of firing process parameters." Improvement methods are mostly limited to local adjustments of mineral ratios or minor corrections to kiln temperature curves. They have failed to break through the inherent framework of "mineral composition-process parameters" and are unable to achieve a leapfrog improvement in performance and aesthetics from the essential level of materials. Summary of the Invention

[0004] In view of the aforementioned problems, the present invention aims to at least partially solve one of the technical problems in the related art. Therefore, the present invention provides a metal-organic framework-based glaze, ceramic products, and a method for preparing the same, which can alleviate the technical problems existing in current ceramic glaze systems, such as limited component control dimensions, poor ceramic glaze surface performance, unsatisfactory kiln transformation effects, or weak glaze-body bonding, and overcome the shortcomings of the prior art.

[0005] To solve the above-mentioned technical problems, this application is implemented as follows: According to a first aspect of this application, an embodiment of this application provides a metal-organic framework-based glaze, the metal-organic framework-based glaze comprising: a metal-organic framework material and a base glaze, the base glaze comprising the following components: feldspar, quartz, calcite, wollastonite, copper ore, talc, bovine bone, and tin oxide.

[0006] In some embodiments, the metal-organic framework-based glaze is made by mixing glaze powder and water, wherein the glaze powder includes the metal-organic framework material and the base glaze; the mass ratio of the glaze powder to water is glaze powder:water = 1:(1.1~1.5).

[0007] In some embodiments, the mass ratio of the glaze powder to water is glaze powder:water = 1:(1.2~1.3).

[0008] In some embodiments, the metal-organic framework-based glaze comprises the following components in parts by weight: The composition includes 0.1 to 10 parts of metal-organic framework material, 40 to 50 parts of feldspar, 5 to 12 parts of quartz, 10 to 17 parts of calcite, 5 to 8 parts of wollastonite, 1 to 5 parts of copper ore, 8 to 10 parts of talc, 2 to 4 parts of bovine bone, and 2 to 5 parts of tin oxide.

[0009] In some embodiments, the metal-organic framework-based glaze comprises the following components in parts by weight: The composition includes 0.2 to 10 parts of metal-organic framework material, 44 to 46 parts of feldspar, 6 to 11 parts of quartz, 12 to 17 parts of calcite, 5 to 7 parts of wollastonite, 2 to 4 parts of copper ore, 8 to 10 parts of talc, 2.5 to 3 parts of bovine bone, and 3 to 4 parts of tin oxide.

[0010] In some embodiments, the metal-organic framework-based glaze comprises the following components in parts by weight: The composition includes 0.5 to 2 parts of metal-organic framework material, 44 to 45 parts of feldspar, 7 to 10 parts of quartz, 15 to 17 parts of calcite, 5 to 7 parts of wollastonite, 2.5 to 4 parts of copper ore, 9 to 10 parts of talc, 2.5 to 2.8 parts of bovine bone, and 3 to 4 parts of tin oxide.

[0011] In some embodiments, the metal-organic framework material includes at least one of transition metal-based MOFs, rare earth metal-based MOFs, and their functionalized derivatives; wherein the transition metal-based MOFs include at least one of Fe-based MOFs, Co-based MOFs, Cu-based MOFs, Zn-based MOFs, Cr-based MOFs, Zr-based MOFs, Mn-based MOFs, or Al-based MOFs.

[0012] In some embodiments, the transition metal-based MOFs include at least one of MIL-88A, MIL-100 (Fe), MIL-101 (Fe), ZIF-67, MOF-74 (Ni), HKUST-1 (Cu), ZIF-68, ZIF-8, MOF-5, MIL-101 (Cr), MIL-100 (Cr), UiO-66 (Zr), UiO-67 (Zr), or MIL-53 (Al).

[0013] In some embodiments, the rare earth metal-based MOFs include Eu-MOF and / or Tb-MOF; the functionalized derivatives include complexes of the above MOFs and functionalized MOF materials.

[0014] In some embodiments, the metal-organic framework material is prepared by a green synthesis process, which includes at least one of room temperature stirring synthesis, hydrothermal synthesis, mechanical grinding synthesis, or microwave-assisted synthesis.

[0015] According to a second aspect of this application, embodiments of this application provide a method for preparing a metal-organic framework-based glaze, the method comprising: A metal-organic framework material, feldspar, quartz, calcite, wollastonite, copper ore, talc, bovine bone, and tin oxide are mixed to obtain a glaze powder. The glaze powder and water are added to a ball mill for ball milling and then sieved to obtain a metal-organic framework-based glaze.

[0016] In some embodiments, the mass ratio of the glaze powder, water and grinding media is glaze powder: water: grinding media = 1: (1.1~1.5): (2~3).

[0017] In some embodiments, the filling rate of the grinding media in the ball mill is 30% to 50%.

[0018] In some embodiments, the grinding media used in the ball milling includes a first grinding media, a second grinding media, and a third grinding media, wherein the size of the first grinding media, the second grinding media, and the third grinding media increases sequentially.

[0019] In some embodiments, the size of the first abrasive media is 10mm to 20mm, the size of the second abrasive media is 30mm to 40mm, and the size of the third abrasive media is 50mm to 70mm.

[0020] In some embodiments, the mass ratio of the first grinding media, the second grinding media, and the third grinding media is (1.5-2):(1-1.5):1.

[0021] In some embodiments, the ball milling time is 18h to 30h; and / or, the ball mill rotation speed is 100r / min to 500r / min.

[0022] In some embodiments, the mesh size of the sieved filter is 100 to 300 mesh.

[0023] In some embodiments, the Baumé concentration of the metal-organic framework-based glaze is 45 to 60 Baumé degrees.

[0024] According to a third aspect of this application, an embodiment of this application provides a ceramic article, the ceramic article comprising a ceramic body layer and a glaze layer in contact with the ceramic body layer; the glaze layer is made of the aforementioned metal-organic framework-based glaze and / or a metal-organic framework-based glaze prepared by the aforementioned preparation method.

[0025] According to a fourth aspect of this application, embodiments of this application provide a method for preparing a ceramic article, the method comprising: A metal-organic framework-based glaze is provided, which is made by mixing glaze powder and water. The glaze powder includes metal-organic framework materials, feldspar, quartz, calcite, wollastonite, copper ore, talc, bovine bone, and tin oxide. The metal-organic framework-based glaze is applied to a ceramic green body to obtain a green body to be fired. The blank to be fired is sintered to obtain the ceramic product.

[0026] In some embodiments, in the step of providing the metal-organic framework-based glaze, the glaze powder and water are mixed and ball-milled at a mass ratio of 1:(1.1 to 1.5) for 18 to 30 hours, and the ball mill speed is 100 to 500 r / min; then the mixture is sieved through a 100 to 300 mesh filter.

[0027] In some embodiments, the prepared metal-organic framework-based glaze has a Baumé concentration of 45 to 60 Baumé degrees.

[0028] In some embodiments, during the glazing process, the metal-organic framework-based glaze is continuously stirred at a speed of 30 r / min to 60 r / min.

[0029] In some embodiments, the glazing method includes immersion glazing, which includes immersing a surface-cleaned ceramic blank into a metal-organic framework-based glaze for immersion glazing.

[0030] In some embodiments, the thickness of the glaze layer obtained after glazing is 4 mm to 5 mm.

[0031] In some embodiments, the sintering is carried out in a staged temperature-controlled manner, and the peak temperature of the staged temperature-controlled sintering is 1240℃~1300℃; the sintering atmosphere includes an oxidizing atmosphere or a reducing atmosphere.

[0032] In some embodiments, the sintering process in the oxidizing atmosphere includes: S10, Preheating stage: The temperature is increased to 300℃~400℃ at a heating rate of 10℃ / min~15℃ / min, and held for 2h~3h; the preheating stage utilizes natural air inside the kiln to maintain the oxidation state. S20, Oxidation Stage: First, the temperature is increased to 1140℃~1200℃ at a heating rate of 5℃ / min~10℃ / min, and held for 20min~30min. Then, the temperature is increased to 1240℃~1300℃ at a heating rate of 3℃ / min~5℃ / min, and held for 50min~60min. During the oxidation stage, air is introduced through the pre-set ventilation openings of the kiln to ensure sufficient oxygen in the kiln. S30, Cooling stage: Turn off the kiln heating system to reduce the kiln temperature from 1240℃~1300℃ to room temperature.

[0033] In some embodiments, the sintering process in the reducing atmosphere includes: S10, Atmosphere transition stage: Reducing gas is introduced into the kiln, and the gas flow rate is controlled to reduce the oxygen content in the kiln to below 1% and maintain the reducing gas concentration in the kiln at 3% to 5%. S20. During the preheating stage, the temperature is increased to 300℃ to 400℃ at a heating rate of 10℃ / min to 15℃ / min, and held for 2h to 3h. S30, First reduction stage: Heat to 1050℃~1150℃ at a heating rate of 5℃ / min~10℃ / min, and hold for 1h~1.5h; S40, Second reduction stage: Heat to 1150℃~1280℃ at a heating rate of 3℃ / min~5℃ / min, and hold for 2h~3h; S50, Neutral heat preservation stage: reduce the concentration of reducing gas in the kiln to ≤1%, raise the temperature to 1280℃~1300℃ at a heating rate of 1℃ / min~3℃ / min, and keep it at that temperature for 0.5h~1h. S60. In the stage of segmented cooling, the heating system of the kiln is turned off. The temperature is first reduced from 1280℃~1300℃ to 500℃~600℃ at a cooling rate of 10℃ / min~15℃ / min. Then, the temperature inside the kiln is reduced to room temperature through natural cooling.

[0034] Implementing the technical solution of the present invention has at least the following beneficial effects: In the embodiments of this application, the provided metal-organic framework-based glaze includes metal-organic framework materials (MOFs) and a base glaze. The base glaze includes raw material components such as feldspar, quartz, calcite, wollastonite, copper ore, talc, bovine bone, and tin oxide. This invention incorporates MOFs into ceramic glazes, using MOFs as the core functional control unit, combined with specific base glaze components such as feldspar, quartz, calcite, wollastonite, copper ore, tin oxide, talc, and bovine bone to form a mineral composite system. Thus, on the one hand, by utilizing the molecular-level color-regulating mechanism of MOF materials, the color limitations of traditional mineral color-regulating systems can be overcome, enabling the directional formation of a novel kiln-transformation effect with "dynamic optical effects and multi-dimensional color layers." Simultaneously, the porous structure of MOFs optimizes the uniformity of glaze melting, giving the glaze an extremely smooth and delicate jade-like texture, thus solving the problems of poor color stability and significant batch-to-batch variations in traditional ceramic glazes. On the other hand, in terms of mechanical properties, the metal ions uniformly released by MOFs at high temperatures react with the glaze matrix to form a dense crystalline network (such as a Zr-O-Si bonded network and an Fe-based spinel phase). This, combined with the phosphorus element in the bovine bone, enhances the interfacial bonding energy between the glaze and the body, increasing the hardness of the glaze layer by approximately 20% to 30%, wear resistance by approximately 35% to 45%, and the bonding strength between the glaze and the body by over 40%. This effectively avoids the failure risks of peeling and cracking of traditional ceramic glaze layers, extending the product's service life. Furthermore, in terms of functional characteristics, the introduction of specific MOFs can endow ceramic glaze layers with additional functions such as photoluminescence, antibacterial properties, and resistance to acid and alkali corrosion. This breaks through the limitations of traditional ceramics' "single decorative attribute," expanding into diversified application scenarios such as high-end decorative and functional ceramics.

[0035] Additional aspects and advantages of this application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0036] Figure 1 This is an X-ray diffraction (XRD) pattern of the metal-organic framework material MIL-88A used in Example 1 of the present invention.

[0037] Figure 2 This is a scanning electron microscope (SEM) image of the metal-organic framework material MIL-88A used in Example 1 of the present invention.

[0038] Figure 3 This is a photograph of the MIL-88A glazed Kung Fu tea cup fired in an oxidizing atmosphere in Example 1 of the present invention.

[0039] Figure 4 This is an optical microscope image of the glaze surface of the MIL-88A glaze Kung Fu tea cup fired under an oxidizing atmosphere in Example 1 of the present invention.

[0040] Figure 5 This is a SEM image of the glaze surface of the MIL-88A glaze Kung Fu tea cup fired under an oxidizing atmosphere in Example 1 of the present invention.

[0041] Figure 6 This is a SEM image of the cross-section of the MIL-88A glaze Kung Fu tea cup fired in an oxidizing atmosphere in Example 1 of the present invention after the glaze surface is broken.

[0042] Figure 7 This is a photograph of the MIL-88A glaze Kung Fu tea cup fired in a reducing atmosphere in Embodiment 2 of the present invention.

[0043] Figure 8 This is an optical microscope image of the glaze surface of the MIL-88A glaze Kung Fu tea cup fired under a reducing atmosphere in Embodiment 2 of the present invention.

[0044] Figure 9 This is a SEM image of the glaze surface of the MIL-88A glaze Kung Fu tea cup fired under a reducing atmosphere in Embodiment 2 of the present invention.

[0045] Figure 10 This is a SEM image of the cross-section of the MIL-88A glaze Kung Fu tea cup fired in a reducing atmosphere in Embodiment 2 of the present invention after the glaze surface is broken.

[0046] Figure 11 This is an X-ray diffraction (XRD) pattern of ZIF-67, the metal-organic framework material used in Example 3 of this invention.

[0047] Figure 12 This is a scanning electron microscope (SEM) image of ZIF-67, the metal-organic framework material used in Example 3 of the present invention.

[0048] Figure 13 This is a photograph of the ZIF-67 glazed Kung Fu tea cup fired in an oxidizing atmosphere in Example 3 of the present invention.

[0049] Figure 14 This is an optical microscope image of the glaze surface of the ZIF-67 glaze Kung Fu tea cup fired under an oxidizing atmosphere in Example 3 of the present invention.

[0050] Figure 15 This is a SEM image of the glaze surface of the ZIF-67 glazed Kung Fu tea cup fired under an oxidizing atmosphere in Example 3 of the present invention.

[0051] Figure 16 This is a SEM image of the cross-section of the ZIF-67 glaze Kung Fu tea cup fired in an oxidizing atmosphere in Example 3 of the present invention after the glaze surface is broken.

[0052] Figure 17 This is a photograph of the ZIF-67 glaze Kung Fu tea cup fired in a reducing atmosphere in Embodiment 4 of the present invention.

[0053] Figure 18 This is an optical microscope image of the glaze surface of the ZIF-67 glaze Kung Fu tea cup fired under a reducing atmosphere in Example 4 of the present invention.

[0054] Figure 19 This is a SEM image of the glaze surface of the ZIF-67 glazed Kung Fu tea cup fired under a reducing atmosphere in Example 4 of the present invention.

[0055] Figure 20 This is a SEM image of the cross-section of the ZIF-67 glaze Kung Fu tea cup fired in a reducing atmosphere in Example 4 of the present invention after the glaze surface is broken.

[0056] Figure 21 This is an optical microscope image of the ZIF-67 glaze specimen fired under an oxidizing atmosphere in Comparative Example 1 of this invention.

[0057] Figure 22 This is an optical microscope image of the cobalt oxide glaze specimen fired under an oxidizing atmosphere in Comparative Example 1 of the present invention. Detailed Implementation

[0058] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply.

[0059] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the ranges, the endpoint values ​​of the ranges or individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges.

[0060] It should be noted that the terms "and / or" or " / " used herein are merely descriptions of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. The singular forms "a," "the," and "the" used in the embodiments of this application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0061] In the description of this application, the list of items connected by the terms "at least one of," "at least one of," or other similar terms may mean any combination of the listed items. For example, if items A and B are listed, then the phrase "at least one of A and B" means only A; only B; or A and B. In another instance, if items A, B, and C are listed, then the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may contain a single element or multiple elements. Item B may contain a single element or multiple elements. Item C may contain a single element or multiple elements.

[0062] Metal-organic frameworks (MOFs), as emerging porous materials, are self-assembled from metal ions or clusters and organic ligands. They have the characteristics of high porosity, large specific surface area, diverse structure and function, and unsaturated metal sites, and have great potential in fields such as gas storage, molecular separation, and catalysis.

[0063] Metal-organic frameworks (MOFs), as star materials in contemporary materials science, are porous materials formed by the self-assembly of metal ions / clusters and organic ligands through coordination bonds. Their core advantages lie in "structural designability, performance controllability, and functional customization"—high porosity (typically 1000-5000 μm). 2 / g) can construct a controllable microporous network, and the large specific surface area provides abundant interfacial interaction sites. Furthermore, the diverse selection of metal nodes and organic ligands can achieve targeted regulation from "microstructure" to "macro performance". It has already shown disruptive application potential in fields such as gas storage, catalysis, sensing, and optics. Introducing MOFs into ceramic glaze systems is not only a cross-disciplinary innovation of "modern materials science empowering traditional craftsmanship," but also holds the promise of breaking through the technical bottlenecks of traditional ceramics at the molecular design level. First, the high porosity of MOFs can construct a gradient microporous network during the melting process of the glaze layer, regulating the fluidity and compositional uniformity of the molten glaze, suppressing the generation of defects such as bubbles and pinholes, and giving the glaze an extremely smooth and delicate texture. Second, its large specific surface area can significantly increase the contact area and interfacial bonding energy between the glaze and the body, enhancing the adhesion strength of the glaze layer to the body and solving the problem of easy peeling of traditional ceramic glaze layers. Third, the controllable exposure of metal nodes and the optical response characteristics of organic ligands in MOFs can achieve the directional arrangement and valence state regulation of chromogenic ions, breaking through the color limitations of traditional mineral chromogenic systems, and is expected to create a new kiln transformation effect with "dynamic optical effects and multi-dimensional color levels," opening up a new dimension for ceramic aesthetics.

[0064] Currently, research in the ceramics field still focuses on the traditional paradigm of "fine-tuning of traditional glaze components" and "optimization of firing process parameters." Improvement methods are mostly limited to local adjustments of mineral ratios or minor modifications to kiln temperature curves, failing to break through the inherent framework of "mineral composition - process parameters," and making it difficult to achieve a leapfrog improvement in performance and aesthetics from the fundamental level of materials. The inventors of this application have discovered that there are currently no literature reports, domestically or internationally, on the deep integration of MOF materials with ceramic glaze systems, the construction of MOF-based glaze layers, and the preparation process of matching MOF-glazed ceramics, indicating a significant gap in this technological field. Based on this, this invention innovatively proposes the concept of "MOFs-ceramic glaze synergistic design," constructs an MOFs-based glaze system, and develops corresponding preparation processes. The aim is to overcome the limitations of traditional ceramics across the entire chain of "material design-process control-performance optimization." This not only injects the innovative genes of modern materials science into the ceramics industry, promoting the transformation of ceramics from "experience-driven" to "science-driven," but also has the potential to provide core technological support for the creative transformation and innovative development of excellent traditional Chinese porcelain-making techniques through the cross-disciplinary integration of "traditional craftsmanship + modern materials," thus meeting the diversified needs of contemporary society for high-quality, personalized, and functional ceramic products.

[0065] In light of this, the core technological bottlenecks of traditional ceramic glaze systems are as follows: First, the component control dimension is singular, and the fixed formula based on natural minerals makes it difficult to coordinate and optimize the mechanical properties such as glaze gloss and wear resistance with aesthetic texture. Second, the kiln transformation effect is uncontrollable; the color-developing mechanism relying on empirical processes cannot achieve directional design of colors and patterns, limiting the space for innovation. Third, the glaze-body interface is weak; traditional glazes and bodies have insufficient interfacial interaction sites, making them prone to failure problems such as glaze layer peeling and cracking. Furthermore, research has revealed that a technical solution for deeply integrating metal-organic frameworks (MOFs) materials with ceramic glazes has not yet been developed, indicating a significant technological gap in this field. The technical solution of this application provides a metal-organic framework-based glaze, ceramic products and their preparation method. It aims to build a synergistic solution of "material-process-performance" through the functional design and process innovation of MOF materials, break through the limitations of the existing technology, and can be used to solve problems such as poor performance of traditional ceramic glazes, insufficient kiln transformation innovation or weak glaze-body bonding. It can also break through the limitations of the existing process, improve the quality of ceramics, enrich the kiln transformation effect, and meet the needs of high quality and personalization.

[0066] Unless otherwise stated, percentages, proportions or parts referred to herein are by mass.

[0067] In some embodiments of this application, a metal-organic framework-based glaze is provided, which includes: metal-organic framework (MOF) materials and a base glaze, wherein the base glaze includes the following raw material components: feldspar, quartz, calcite, wollastonite, copper ore, talc, bovine bone, and tin oxide.

[0068] This invention relates to the precise preparation of ceramic glazes through the cross-integration of traditional ceramic techniques and modern metal-organic framework (MOF) materials. It particularly relates to the research and development of ceramic glazes based on MOF materials and the corresponding ceramic firing processes, aiming to overcome the technical bottlenecks of insufficient color stability and the difficulty in synergistically optimizing mechanical properties and aesthetic texture in traditional ceramic glazes. The MOF glazes provided by this invention can be used in the preparation of high-performance MOF-glazed ceramics.

[0069] In the embodiments of this invention, the provided MOFs-based ceramic glaze, MOFs-based glazed ceramics, and their precise preparation process, through the molecular-level design of MOFs materials and the directional control of process parameters, achieve a significant improvement in the stability of ceramic glaze color, an innovative breakthrough in kiln transformation effects, and a leapfrog optimization of glaze-body bonding performance. Ultimately, it can meet the diversified needs of contemporary high-end ceramics for "aesthetic personalization, performance functionality, and quality standardization," and is suitable for promoting the transformation of traditional ceramics from "experience-driven processes" to "science-driven industries."

[0070] Specifically, in this embodiment of the invention, MOFs materials are added to metal-organic framework-based glazes, and MOFs are used as the core functional control unit, combined with specific basic glaze components such as feldspar, quartz, calcite, wollastonite, copper ore, tin oxide, talc and bovine bone to form a mineral composite system. Among them, feldspar serves as the core framework, providing a stable reaction carrier for MOFs. Its molten silicate network can interweave and anchor with the porous structure of MOFs, preventing MOFs from agglomerating and allowing metal ions to be uniformly embedded. The high hardness of quartz's silicon-oxygen bond structure, combined with the gloss-improving function of tin oxide, can form a hybrid bond network with the metal ions decomposed by MOFs, which not only strengthens the hardness and wear resistance of the glaze layer but also gives the glaze a warm and jade-like texture. The fluxing effect of calcite and the fluidity-regulating function of talc create a suitable melting environment for the diffusion of metal ions in MOFs. At the same time, MOFs adsorb CO2 bubbles decomposed by calcite, reducing glaze defects. The crack-resistant properties of wollastonite and the interfacial strengthening effect of phosphorus in bovine bone form a phosphosilicate transition layer with the decomposition products of MOFs, which greatly improves the bonding strength and crack resistance of the glaze body. The Cu ions of copper ore serve as auxiliary color-developing centers, working synergistically with the metal ions in MOFs to form a multi-dimensional color-developing system, enriching the kiln transformation layers. Furthermore, in some preferred embodiments, the present invention constructs an integrated technical system of "functional regulation, structural forming, and performance optimization" through a step-by-step preparation process of "precise raw material formulation - high-energy ball milling and slurry preparation - multi-dimensional uniform glazing - controlled atmosphere glazing firing".

[0071] This invention focuses on the designability of MOFs materials. Through the precise regulation mechanism of their metal nodes and organic ligands, it achieves directional control of the valence state and distribution of color-emitting ions within the glaze layer, fundamentally improving the stability of ceramic glaze color and its jade-like aesthetic texture. Simultaneously, during high-temperature sintering, MOFs materials can uniformly release metal ions to avoid agglomeration defects, and through the synergistic reaction of their decomposition products with the glaze matrix, they construct a dense crystalline network, significantly enhancing the mechanical properties of the glaze surface, such as hardness and wear resistance. This invention not only overcomes the industry pain points of "uncontrollable kiln transformation and difficulty in achieving balanced performance" in traditional ceramics, but also achieves a deep integration of modern materials science and traditional ceramic processes. It provides a new technological path for the industrial upgrading of high-end ceramic products and is of great significance for promoting the modernization and inheritance of traditional processes and the innovative development of high-performance ceramic materials.

[0072] More specifically, this invention achieves four core advantages through a breakthrough across the entire chain of "material design - process control - performance optimization": First, in terms of aesthetic performance, the molecular-level color regulation mechanism of MOFs materials breaks through the color limitations of traditional mineral color systems, enabling the directional formation of a new kiln-transformation effect with "dynamic optical effects and multi-dimensional color layers." Second, the porous structure of MOFs optimizes the melting uniformity of the glaze, giving the glaze an extremely smooth and delicate jade-like texture, solving the problems of poor color stability and significant batch-to-batch differences in traditional ceramic glazes. Third, in terms of mechanical performance, the metal ions uniformly released by MOFs at high temperatures react with the glaze matrix to form a dense crystalline network (such as a Zr-O-Si bonded network and an Fe-based spinel phase), which, in conjunction with phosphorus elements in the bovine bone, enhances the bonding energy between the glaze and the body. This can increase the hardness of the glaze layer by approximately 20% to 30%, the wear resistance by approximately 35% to 45%, and the bonding strength between the glaze and the body by more than 40%, effectively avoiding the failure risks of peeling and cracking of traditional ceramic glaze layers and extending the product's service life. Fourth, in terms of functional characteristics, the introduction of specific MOFs (such as Zr-based UiO-66 and rare earth Eu-MOF) enables ceramic glaze layers to have additional functions such as "photoluminescence, antibacterial properties, and resistance to acid and alkali corrosion". This can break through the limitations of the traditional ceramics' "single decorative attribute" and expand to diversified application scenarios such as high-end decorative and functional ceramics.

[0073] Meanwhile, in terms of the process system, the embodiments of the present invention construct a standardized process system of "multi-scale ball milling - precise glazing - dual atmosphere segmented temperature control" to replace the traditional empirical process, realize "controllable parameters and stable quality" in ceramic production, provide core technical support for the industrialization and high-end development of the ceramic industry, and provide a replicable technical paradigm for the cross-border integration of traditional porcelain making technology and modern materials science.

[0074] In this embodiment of the invention, the MOFs-based glaze is composed of a core functional component and a basic glaze system. The core functional component is MOFs material, and the basic glaze system may include feldspar, quartz, calcite, wollastonite, copper ore, tin oxide, talc, and bovine bone.

[0075] The MOFs-based ceramic glaze provided in this invention adopts a synergistic design concept of "core functional phase (MOFs) - basic framework phase (mineral components)," with each component formulated in specific mass parts (or mass percentages) to achieve integrated fusion of function and structure. Specifically, in some embodiments, the metal-organic framework-based glaze includes the following raw material components in parts by mass: 0.1 to 10 parts of metal-organic framework material, 40 to 50 parts of feldspar, 5 to 12 parts of quartz, 10 to 17 parts of calcite, 5 to 8 parts of wollastonite, 1 to 5 parts of copper ore, 8 to 10 parts of talc, 2 to 4 parts of bovine bone, and 2 to 5 parts of tin oxide.

[0076] Preferably, in some embodiments, the metal-organic framework-based glaze comprises the following raw material components in parts by weight: The composition comprises 0.2 to 10 parts of metal-organic framework material, 44 to 46 parts of feldspar, 6 to 11 parts of quartz, 12 to 17 parts of calcite, 5 to 7 parts of wollastonite, 2 to 4 parts of copper ore, 8 to 10 parts of talc, 2.5 to 3 parts of bovine bone, and 3 to 4 parts of tin oxide; the sum of the mass parts of all raw material components is 100 parts.

[0077] Preferably, in some embodiments, the metal-organic framework-based glaze comprises the following raw material components in parts by weight: The composition comprises 0.5 to 2 parts metal-organic framework material, 44 to 45 parts feldspar, 7 to 10 parts quartz, 15 to 17 parts calcite, 5 to 7 parts wollastonite, 2.5 to 4 parts copper ore, 9 to 10 parts talc, 2.5 to 2.8 parts bovine bone, and 3 to 4 parts tin oxide; the total mass fraction of all raw material components is 100 parts. Under this formulation, the glaze's function and process compatibility are optimal.

[0078] In other words, in some preferred embodiments, with the total mass of the MOFs-based glaze being 100%, the mass percentages of each raw material component satisfy the following: metal-organic framework material 0.2%–10%, feldspar 44%–45%, quartz 7%–10%, calcite 15%–17%, wollastonite 5%–7%, copper ore 2%–4%, tin oxide 3%–4%, talc 8%–10%, and bovine bone 2.5%–3%, with the sum of the mass percentages of each component being 100%. Under this ratio, the glaze function and process adaptability can be optimally achieved.

[0079] In the raw material composition of the metal-organic framework-based glaze of this application embodiment, the mass fraction of the metal-organic framework material is 0.1 to 10 parts, preferably 0.2 to 10 parts, more preferably 0.5 to 2 parts, for example, 0.1, 0.2, 0.3, 0.5, 1, 2, 3, 5, 6, 8, 10 parts, etc. This metal-organic framework material can serve as a functional core phase in the glaze, alleviating problems such as the limited control of traditional ceramic glaze components, poor kiln transformation effects, easy peeling or cracking of the glaze layer, and difficulty in synergistically optimizing mechanical properties and aesthetic texture.

[0080] In the raw material composition of the metal-organic framework-based glaze of this application embodiment, the mass fraction of leucite is 40 to 50 parts, preferably 44 to 46 parts, more preferably 44 to 45 parts, for example, 40 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 ​​parts, 50 parts, etc. Leucite can act as a glaze skeleton forming agent in the glaze, providing support for the molten structure.

[0081] In the raw material composition of the metal-organic framework-based glaze of this application embodiment, the mass fraction of quartz is 5 to 12 parts, preferably 6 to 11 parts, more preferably 7 to 10 parts, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, etc. Quartz can be used as a glaze layer stability regulator in the glaze to improve chemical stability and hardness.

[0082] In the raw material composition of the metal-organic framework-based glaze of this application embodiment, the mass fraction of calcite is 10 to 17 parts, preferably 12 to 17 parts, more preferably 15 to 17 parts, for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, etc. Calcite can be used as a flux and bubble eliminator in the glaze to optimize the glaze's fluidity.

[0083] In the raw material composition of the metal-organic framework-based glaze of this application embodiment, the mass fraction of wollastonite is 5 to 8 parts, preferably 5 to 7 parts, for example, 5 parts, 6 parts, 7 parts, 8 parts, etc. Wollastonite can be used as a glaze surface smoothness improver in the glaze and can be used to inhibit glaze layer cracking.

[0084] In the raw material components of the metal-organic framework (MOF) based glaze of this application embodiment, the mass fraction of copper ore is 1 to 5 parts, preferably 2 to 4 parts, more preferably 2.5 to 4 parts, for example, it can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 5 parts, etc. Copper ore can be used as an auxiliary colorant in the glaze, and can be used to synergistically regulate color levels with MOFs.

[0085] In the raw material composition of the metal-organic framework-based glaze of this application embodiment, the mass fraction of talc is 8 to 10 parts, preferably 9 to 10 parts, for example, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, etc. Talc can be used as a glaze melting temperature regulator to improve firing adaptability.

[0086] In the raw material composition of the metal-organic framework-based glaze of this application embodiment, the mass fraction of bovine bone is 2 to 4 parts, preferably 2.5 to 3 parts, more preferably 2.5 to 2.8 parts, for example, 2 parts, 2.5 parts, 2.6 parts, 2.8 parts, 3 parts, 3.5 parts, 4 parts, etc. Bovine bone can serve as a phosphorus-based reinforcing phase in the glaze to enhance the interfacial bonding of the glaze body.

[0087] In the raw material components of the metal-organic framework-based glaze of this application embodiment, the mass fraction of tin oxide is 2 to 5 parts, preferably 3 to 4 parts, for example, 2 parts, 2.5 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 5 parts, etc. Tin oxide can be used as a glaze gloss enhancer in the glaze to improve the jade-like texture.

[0088] Therefore, by controlling the content of each raw material component in the above-mentioned metal-organic framework material-based glaze within the above-mentioned range, the ratio can be optimized, so that the function and process adaptability of the glaze can be optimized, which is conducive to achieving the best effect at a lower cost.

[0089] In some embodiments, the metal-organic framework-based glaze is made by mixing glaze powder and water, wherein the glaze powder includes the metal-organic framework material and the base glaze; the mass ratio of the glaze powder to water is glaze powder:water = 1:(1.1~1.5); for example, it can be 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, etc.

[0090] Preferably, in some embodiments, the mass ratio of glaze powder to water is glaze powder:water = 1:(1.2~1.3).

[0091] In some embodiments, the metal-organic framework material includes at least one of transition metal-based MOFs, rare earth metal-based MOFs, and their functionalized derivatives.

[0092] Transition metal-based MOFs include, but are not limited to, at least one of Fe-based MOFs, Co-based MOFs, Cu-based MOFs, Zn-based MOFs, Cr-based MOFs, Zr-based MOFs, Mn-based MOFs, or Al-based MOFs. Rare earth metal-based MOFs include, but are not limited to, one or more of Eu-MOFs or Tb-MOFs; functionalized derivatives include composites of the above MOFs and MOF materials modified with functional groups. For example, Fe-based MOFs can be MIL-88A, MIL-100(Fe), MIL-101(Fe), etc.; Co-based MOFs can be ZIF-67, MOF-74, etc.; Cu-based MOFs can be HKUST-1, ZIF-68, etc.; Zn-based MOFs can be ZIF-8, MOF-5, etc.; Cr-based MOFs can be MIL-101(Cr), MIL-100(Cr), etc.; Zr-based MOFs can be UiO-66, UiO-67, etc.; Al-based MOFs can be MIL-53(Al), etc.; and Ni-based MOFs can be MOF-74(Ni), etc.

[0093] Typical, but not limiting, MOF materials include, but are not limited to, any one or a combination of at least two of ZIF-8, ZIF-67, ZIF-68, ZIF-9, ZIF-90, MOF-5, MOF-74 (Ni), MOF-808, MOF-525, MIL-53 (Cr / Al / Fe), MIL-100 (Fe / Cr), MIL-101 (Fe / Cr), MIL-125 (Ti), MIL-88A (Fe), MIL-88B (Fe), MIL-68 (Al / Fe), MIL-53 (Al), HKUST-1, UiO-66 (Zr), UiO-67 (Zr), and UiO-68 (Zr).

[0094] Preferably, metal-organic framework materials, i.e. MOFs, can be prepared by a green synthesis process, which includes, but is not limited to, at least one of room temperature stirring synthesis, water / solvent thermal synthesis, mechanical grinding synthesis, or microwave-assisted synthesis, and can achieve efficient utilization of raw materials and low environmental impact during the synthesis process.

[0095] In this embodiment, MOF materials such as MIL-88A(Fe), ZIF-8, and ZIF-67 can be prepared using a room temperature stirring method. The room temperature stirring method for preparing MOF materials provides mild synthesis conditions, is environmentally friendly, and is simple to operate, requiring no high-temperature, high-pressure containers or equipment.

[0096] It should be noted that this application does not limit the source or preparation of MOFs materials. They can be prepared by conventional methods known to those skilled in the art, or they can be obtained commercially.

[0097] Therefore, in the metal-organic framework-based glaze of this invention, MOFs can play a multifunctional precursor role: first, as molecularly dispersed color-regulating units, they achieve directional arrangement and state regulation of color-emitting ions through the synergy of the valence state of metal nodes and the optical properties of organic ligands; second, as a source of high-temperature active components, they uniformly release metal ions during firing (avoiding agglomeration defects) and react with the glaze matrix to form a dense reinforcing phase (such as spinel phase or silicate solid solution); third, as a regulator of glaze melting behavior and microstructure, their porous structure constructs a gradient pore network in the molten glaze, optimizing the glaze's fluidity and uniformity, and suppressing defects such as bubbles and pinholes.

[0098] Accordingly, in some embodiments, this application also provides a method for preparing the metal-organic framework-based glaze as described above, the method comprising: A metal-organic framework material, feldspar, quartz, calcite, wollastonite, copper ore, talc, bovine bone, and tin oxide are mixed to obtain a glaze powder. The glaze powder and water are added to a ball mill for ball milling and then sieved to obtain a metal-organic framework-based glaze.

[0099] The preparation method of this metal-organic framework-based glaze involves mixing MOF materials with a base glaze to obtain a glaze powder. Then, the glaze powder and water are added to a ball mill for ball milling. After sieving, the metal-organic framework-based glaze is obtained in slurry form, i.e., a glaze paste. This process is simple, easy to operate, and suitable for industrial-scale production.

[0100] It should be understood that the "method for preparing metal-organic framework-based glaze" and the aforementioned "metal-organic framework-based glaze" are based on the same inventive concept, and therefore have at least all the features and advantages of the aforementioned "metal-organic framework-based glaze", which will not be repeated here.

[0101] Accordingly, in some embodiments, this application also provides the application of the metal-organic framework-based glaze as described above in the ceramics field.

[0102] In some embodiments, a ceramic article is provided, the ceramic article comprising a ceramic body layer and a glaze layer in contact with the ceramic body layer; the glaze layer is made of the aforementioned metal-organic framework-based glaze and / or a metal-organic framework-based glaze prepared by the aforementioned preparation method.

[0103] Optionally, the glaze layer can be a top glaze layer, that is, the above-mentioned metal-organic framework-based glaze can be used as a top glaze.

[0104] The ceramic product provided in this embodiment is a MOFs glazed ceramic product. It is made by using the above-mentioned MOFs-based glaze as the raw material for the glaze layer and by high-temperature sintering process. The glaze layer has the synergistic effect of the unique functions given by MOFs materials and the traditional aesthetic characteristics of ceramic glaze.

[0105] The MOFs-based glazed ceramics provided in this embodiment are ceramic products that integrate traditional aesthetics and modern functions, prepared by using the above-mentioned MOFs-based ceramic glaze as the core raw material of the glaze layer and through the process of "precise glazing - uniform glazing - controlled firing". Its core features are that the glaze layer has the directional kiln transformation effect and high density jade-like texture given by MOFs, and the bonding strength of the glaze body interface, the mechanical properties (such as hardness and wear resistance) and chemical stability of the glaze layer are significantly better than those of traditional ceramics.

[0106] It should be understood that the raw materials for preparing the "ceramic product" include the aforementioned "metal-organic framework-based glaze", and therefore possess at least all the characteristics and advantages of the aforementioned "metal-organic framework-based glaze", which will not be elaborated here.

[0107] Accordingly, in some embodiments, this application also provides a method for preparing a ceramic article, the method comprising: We provide metal-organic framework-based glazes, which are made by mixing glaze powders and water. The glaze powders include metal-organic framework materials, feldspar, quartz, calcite, wollastonite, copper ore, talc, bovine bone, and tin oxide. A metal-organic framework-based glaze is applied to a ceramic green body to obtain a green body to be fired. The blank to be fired is sintered to obtain ceramic products.

[0108] The ceramic product preparation process in this embodiment mainly includes three steps: glaze preparation, body glazing, and precise temperature-controlled sintering. The ceramic product preparation process provided in this embodiment adopts a "multi-parameter synergistic control" approach. For example, it constructs a standardized process system of "multi-scale ball milling - precise glazing - dual-atmosphere segmented temperature control," which can replace traditional empirical processes, achieving "controllable parameters and stable quality" in ceramic production. This provides core technological support for the industrialization and high-end development of the ceramic industry, and also provides a replicable technological paradigm for the cross-disciplinary integration of traditional porcelain-making techniques and modern materials science.

[0109] Specifically, the preparation method of the ceramic product mainly includes the following steps S1 to S3.

[0110] S1. Glaze preparation: First, mix metal-organic framework materials, feldspar, quartz, calcite, wollastonite, copper ore, talc, bovine bone and tin oxide in a certain proportion to obtain glaze powder. Then, add the glaze powder and water to a ball mill such as a high-energy ball mill jar according to a preset ratio and perform constant temperature ball milling. After ball milling, filter to remove impurities to obtain a uniformly dispersed metal-organic framework-based glaze, which is also known as MOFs-based glaze slurry.

[0111] Optionally, the glaze powder and water are mixed in a mass ratio of 1:(1.1 to 1.5).

[0112] Furthermore, during the ball milling process, the mass ratio of glaze powder, water, and grinding media is glaze powder : water : grinding media = 1 : (1.1~1.5) : (2~3). The grinding media can be, for example, grinding stones.

[0113] Optionally, the filling rate of the grinding media (such as grinding stones) in the ball mill is 30% to 50%, further 35% to 45%, further 40% to 45%, and preferably 40%.

[0114] In step S1 of this embodiment, constant temperature ball milling is used for a time of 18h to 30h, more preferably 20h to 26h, and most preferably 24h; that is, ball milling is preferably performed using a 24h constant temperature ball milling method. Optionally, the rotation speed of the ball mill is 100 r / min to 500 r / min, more preferably 200 r / min to 400 r / min.

[0115] In some embodiments, in step S1, the grinding media used during ball milling include a first grinding media, a second grinding media, and a third grinding media, with the sizes of the first grinding media, the second grinding media, and the third grinding media increasing sequentially. That is, the sizes of the first grinding media, the second grinding media, and the third grinding media are different, with the first grinding media having the smallest size, the third grinding media having the largest size, and the size of the second grinding media falling between that of the first grinding media and the third grinding media.

[0116] Preferably, the size of the first abrasive media is 10mm to 20mm, for example, 10mm, 15mm, 20mm, etc.; the size of the second abrasive media is 30mm to 40mm, for example, 30mm, 35mm, 40mm, etc.; and the size of the third abrasive media is 50mm to 70mm, for example, 50mm, 60mm, 65mm, 70mm, etc. As an example, the size of the first abrasive media can be 10mm, the size of the second abrasive media can be 30mm, and the size of the third abrasive media can be 65mm.

[0117] Preferably, the mass ratio of the first grinding medium, the second grinding medium and the third grinding medium is (1.5~2):(1~1.5):1; for example, the mass ratio of the first grinding medium, the second grinding medium and the third grinding medium can be 2:1:1.

[0118] In this embodiment, a "multi-scale grinding media ratio" method is used during ball milling. For example, in 24-hour constant-temperature ball milling, the grinding media can have multiple sizes, such as 10 mm, 30 mm, and 65 mm, with a ratio of 2:1:1. Therefore, this method of ball milling achieves gradient grinding of coarse and fine particles, ensuring molecular-level dispersion of the glaze components.

[0119] In some embodiments, in step S1, the mesh size of the sieve is 100 to 300 mesh; or the pore size of the sieve is ≤100μm.

[0120] In this embodiment, after ball milling, a precision filter screen is used to remove impurities or filter materials within the desired particle size range.

[0121] In some embodiments, in step S1, the Baumé concentration of the metal-organic framework-based glaze, i.e., MOF-based glaze slurry, is 45–60 Baumé, for example, 45 Baumé, 48 Baumé, 50 Baumé, 55 Baumé, 60 Baumé, etc. At this concentration, the glaze slurry exhibits excellent fluidity and uniformity of application.

[0122] S2. Glazing the body: Apply the metal-organic framework-based glaze obtained in step S1 to the ceramic body to obtain the body to be fired.

[0123] In this embodiment, in step S2, the MOFs-based glaze is uniformly glazed. Optionally, during the glazing process, the metal-organic framework-based glaze is continuously stirred at a speed of 30 r / min to 60 r / min. Optionally, the glazing method includes immersion glazing, which includes immersing the surface-cleaned ceramic green body into the metal-organic framework-based glaze for immersion glazing.

[0124] As an example, in step S2, the MOFs-based glaze slurry obtained in step S1 is continuously and uniformly stirred at a speed of 30 r / min to 50 r / min to suppress the sedimentation and stratification of solid particles in the glaze slurry. The surface-cleaned ceramic green body is then immersed in the glaze slurry for immersion glazing. Optionally, the thickness of the glaze layer after glazing is precisely controlled to be 4 mm to 5 mm. At this glaze layer thickness, both the full release of MOF functionality and the aesthetic texture of the glaze surface can be ensured simultaneously.

[0125] S3. Precise temperature control sintering: The blank obtained in step S2 is sintered to obtain ceramic products.

[0126] In step S3, sintering is carried out in stages with temperature control, and the peak temperature of staged temperature control sintering is 1240℃~1300℃; the sintering atmosphere includes oxidizing atmosphere or reducing atmosphere.

[0127] In this embodiment, step S3 employs segmented firing under a controlled atmosphere. The glazed body is placed in a clean environment to air dry naturally (moisture content ≤0.5%), and then transferred to an electric kiln for segmented temperature-controlled sintering. For example, it is transferred to an intelligent electric kiln for "dual-atmosphere segmented temperature-controlled firing." During the sintering process, the spacing between the bodies is ensured to be uniform, and airflow circulation channels are reserved inside the kiln. Throughout the process, an oxidizing atmosphere sintering system or a reducing atmosphere sintering system is selected according to the functional requirements of the glaze layer. The peak sintering temperature can be controlled between 1240℃ and 1300℃, for example, it can be set to 1240℃, 1280℃, 1300℃, etc., preferably 1280℃. Under this temperature condition, the functional release of MOFs and the melting of the glaze reach the optimal equilibrium temperature.

[0128] In addition, during the firing process, the spacing between the green bodies is kept uniform (≥20 mm), and airflow circulation channels (orifice diameter ≥50 mm) are reserved inside the kiln.

[0129] Alternatively, when using an oxidizing atmosphere sintering system, the temperature rise curve of the electric kiln during firing is as follows: S10. Preheating stage (low temperature preheating stage): The temperature is increased to 300℃~400℃ at a heating rate of 10℃ / min~15℃ / min, and held in this temperature range for 2h~3h. The preheating stage utilizes the natural air in the kiln to maintain the oxidation state. That is, no deliberate oxygen control is performed in this stage, and the oxidation state is maintained by relying on the natural air environment in the kiln.

[0130] S20, Oxidation Stage (High-Temperature Oxidation Stage): First, the temperature is increased to 1140℃~1200℃ at a heating rate of 5℃ / min~10℃ / min, and held for 20min~30min. Then, the temperature is increased to 1240℃~1300℃ at a heating rate of 3℃ / min~5℃ / min, and held for 50min~60min. During this oxidation stage, clean air is introduced through the pre-set ventilation openings of the kiln to ensure sufficient oxygen in the kiln.

[0131] S30, Natural Cooling Stage: The kiln heating system is turned off, allowing the kiln temperature to naturally decrease from 1240℃~1300℃ to room temperature.

[0132] It should be noted that the embodiments of the present invention do not limit the specific temperature range of room temperature. For example, the room temperature can be 20℃~30℃.

[0133] Alternatively, when using a reducing atmosphere sintering system, the temperature rise curve of the electric kiln during firing is as follows: S10. Atmosphere transition stage: Close the kiln vents, start the gas control system, gradually introduce reducing gas into the kiln, control the gas flow rate, reduce the oxygen content in the kiln to below 1%, and maintain the reducing gas concentration in the kiln at 3% to 5%.

[0134] S20. Preheating stage (low temperature preheating stage): Heat to 300℃~400℃ at a heating rate of 10℃ / min~15℃ / min, and hold for 2h~3h.

[0135] S30, First reduction stage (weak reduction stage): Heat to 1050℃~1150℃ at a heating rate of 5℃ / min~10℃ / min, and hold for 1h~1.5h.

[0136] S40, Second reduction stage (strong reduction stage): Heat to 1150℃~1280℃ at a heating rate of 3℃ / min~5℃ / min, and hold for 2h~3h.

[0137] S50, Neutral holding stage: Reduce the concentration of reducing gas in the furnace to maintain a weak reducing atmosphere or a near-neutral reducing atmosphere; for example, reduce the concentration of reducing gas in the kiln to ≤1%, raise the temperature to 1280℃~1300℃ at a heating rate of 1℃ / min~3℃ / min, and hold for 0.5h~1h.

[0138] S60. In the stage of segmented cooling, the heating system of the kiln is turned off. The temperature is first reduced from 1280℃~1300℃ to 500℃~600℃ at a cooling rate of 10℃ / min~15℃ / min. If the temperature is reduced to about 600℃, the temperature inside the kiln is then reduced to room temperature through natural cooling. After that, the kiln can be opened and the products can be taken out.

[0139] To fully illustrate the properties of the metal-organic framework-based glazes, ceramic products, and their preparation methods provided in this application, and to facilitate understanding of the invention, multiple sets of experiments were conducted. The invention will be further described below with reference to specific embodiments and comparative examples.

[0140] Example 1 A method for preparing a ceramic product, comprising: (1) Providing MOFs materials: In this embodiment, iron-based metal-organic framework MIL-88A was selected as the functional component. MIL-88A was synthesized by room temperature stirring method and passed through a 200-mesh sieve to obtain uniform MIL-88A powder.

[0141] Figure 1The X-ray diffraction (XRD) pattern of the metal-organic framework material MIL-88A prepared in Example 1 is shown. Figure 2 A scanning electron microscope (SEM) image of the metal-organic framework material MIL-88A prepared in Example 1 is shown. Figure 1 The XRD pattern of MIL-88A shown shows that the MIL-88A synthesized using the room temperature stirring method matches the MIL-88A standard card without any impurity peaks, proving the purity of the crystal; as shown. Figure 2 The SEM image of MIL-88A shows that MIL-88A has a regular spindle shape with a particle size of 1-2 μm, which can meet the requirements for uniform dispersion in glaze.

[0142] (2) Glaze preparation: According to the mass fraction, 0.5 parts of MIL-88A, 45 parts of feldspar, 10 parts of quartz, 17 parts of calcite, 7 parts of wollastonite, 4 parts of copper ore, 4 parts of tin oxide, 10 parts of talc and 2.5 parts of bovine bone are mixed to obtain glaze powder; the glaze powder is placed in a ceramic ball mill jar (alumina is selected as the grinding stone to ensure that no impurities are introduced), deionized water is added at a material-to-liquid ratio of 1:1.2, and the mixture is ball-milled at 300 r / min for 24 h. After filtering with a 120-mesh filter, the Baume concentration of the glaze slurry is adjusted to 46 Baume degrees to obtain metal-organic framework-based glaze; and continuous stirring is carried out to prevent MIL-88A from precipitating.

[0143] (3) Glazing of the body: Select 150 mL kaolin Kung Fu tea cup blank (1100 ℃ bisque firing, water absorption rate ≤3%), polish with 400 grit sandpaper, rinse with deionized water and dry at 80 ℃ for 2 h, immerse the purified ceramic blank into metal organic framework base glaze for immersion glazing, for example, fix the glaze with stainless steel clamp for 15 s, lift at a uniform speed (5 cm / s) and drip naturally for 10 min to ensure that the glaze layer thickness is controlled at 5 mm ± 0.2 mm, and then air dry in a ventilated dust-free environment (25 ℃, humidity 50%) for 12 h.

[0144] (4) Precise temperature control sintering: The dried green body is placed in a box-type electric kiln (temperature control accuracy ±5℃) and fired according to the oxidizing atmosphere process, as follows: S10, Preheating Stage: Set the heating rate to 10℃ / min, the temperature to 350℃, and maintain for 3 hours. During this stage, oxygen is not deliberately controlled; the oxidation state is maintained by utilizing the natural air inside the kiln.

[0145] S20, Oxidation Stage: First, set the heating rate to 5℃ / min and the temperature to 1160℃, hold for 25 min; then set the heating rate to 3℃ / min and the temperature to 1280℃, hold for 60 min. During this stage, air is introduced through the ventilation openings reserved in the kiln to maintain sufficient oxygen.

[0146] S30, Cooling stage: Turn off the heating and allow the temperature to drop naturally from 1280℃ to room temperature to obtain the MIL-88A glazed Kung Fu tea cup (oxidation).

[0147] The actual object and optical microscope image of the MIL-88A glaze Kung Fu tea cup (oxidized) fired in Example 1 of this invention are shown below. Figure 3 and Figure 4 As shown, from Figure 3 and Figure 4 It can be seen that the fired teacups have a warm yellow-green hue, a restrained luster, and natural vine-like patterns on the glaze.

[0148] The sample was broken, and its glaze surface and fracture points were characterized by scanning electron microscopy. The results are as follows: Figure 5 and Figure 6 As shown. From Figure 5 and Figure 6 It can be seen that, under a scanning electron microscope, the texture of the MIL-88A glaze is formed by nano-iron-containing crystals with a dense structure, and further, through analysis of the cross-section ( Figure 6 Observations revealed that the body and glaze were tightly bonded.

[0149] Example 2 The ceramic product in this embodiment is prepared according to the method in Example 1, except that: (2) Glaze preparation: According to the mass fraction, 0.5 parts of MIL-88A, 45 parts of feldspar, 10 parts of quartz, 17 parts of calcite, 7 parts of wollastonite, 4 parts of copper ore, 4 parts of tin oxide, 10 parts of talc and 2.5 parts of bovine bone are mixed to obtain glaze powder; the glaze powder is placed in a ceramic ball mill jar (alumina is selected as the grinding stone to ensure that no impurities are introduced), and ball milled at 300 r / min for 24 h, and then passed through a 120-mesh standard sieve to obtain glaze powder with uniform particle size; deionized water is added to the glaze powder at a material-to-liquid ratio of 1:1.2, and stirred while adding until the glaze is fully dispersed and free of lumps, and the Baume concentration of the glaze slurry is adjusted to 46 Baume degrees (to ensure that the glaze layer is easy to adhere and the thickness is controllable when applying the glaze) to obtain metal-organic framework-based glaze; and stirring is continued to prevent MIL-88A from precipitating.

[0150] (3) Glazing of the body: Select 150 mL kaolin Kung Fu tea cup blank (1100 ℃ bisque firing, water absorption rate ≤3%), polish with 400 grit sandpaper, rinse with deionized water and dry at 80 ℃ for 2 h, immerse the purified ceramic blank into metal organic framework base glaze for immersion glazing, and ensure that the glaze layer thickness is controlled at 5 mm ± 0.2 mm by controlling the immersion time (about 15 s) and the glaze slurry stirring rate (50 r / min, to prevent MIL-88A precipitation). Then, let it air dry naturally for 12 h in a ventilated and dust-free environment (25℃, humidity 50%).

[0151] (4) Precise temperature control sintering: The dried green body is placed in a box-type electric kiln (temperature control accuracy ±5℃) and fired according to the reducing atmosphere gradient temperature rise process, as follows: S10, Atmosphere transition stage: Close the kiln vents, start the gas control system, gradually introduce reducing gas, control the gas flow rate, reduce the oxygen content in the furnace to below 1%, and ensure that the reducing gas concentration is maintained at 5%.

[0152] S20. Preheating stage: Set the heating rate to 10℃ / min, the temperature to 350℃, and maintain for 2 hours.

[0153] S30, Weak Reduction Stage: Set the heating rate to 5℃ / min, the temperature to 1050℃, and hold for 1 h.

[0154] S40, Strong Reduction Stage: Set the heating rate to 3℃ / min, the temperature to 1150℃, and hold for 2 h.

[0155] S50, Neutral Holding Stage: Reduce the concentration of reducing gases in the furnace to maintain a "weakly reducing" or near-moderately reducing atmosphere. Set the heating rate to 1℃ / min, the temperature to 1280℃, and hold for 1 hour.

[0156] S60, Cooling Stage: Turn off the heating system, set the cooling rate to 10℃ / min, and allow the temperature to drop from 1280℃ to 600℃ before allowing it to cool naturally until the kiln temperature reaches room temperature. Open the kiln to obtain a MIL-88A glazed Kung Fu tea cup (reduction).

[0157] The actual object and optical microscope image of the MIL-88A glaze Kung Fu tea cup (reduction) fired in Example 2 of this invention are shown below. Figure 7 and Figure 8 As shown, from Figure 7 and Figure 8 It can be seen that the MIL-88A glaze Kung Fu tea cup has a light sky blue color, with a uniform tone and no color deviation. The glaze is warm and subtle, and there are no defects such as glaze shrinkage or pinholes. The surface is delicate and smooth to the touch.

[0158] The sample was broken, and its glaze surface and fracture points were characterized by scanning electron microscopy. The results are as follows: Figure 9 and Figure 10 As shown. From Figure 9 and Figure 10 As can be seen from the scanning electron microscope, in terms of microscopic characterization, the SEM image of the glaze of the Kung Fu tea cup ( Figure 9 It can be observed that its glaze surface is smooth and flat, and the SEM image after the sample is broken ( Figure 10The results show that the transition at the junction of the body and glaze is continuous and uniform, with no obvious interface gaps, forming a dense bonding layer with a thickness of about 25μm, which is significantly better than traditional reduction glaze (bonding layer of about 12μm); the crystals inside the glaze layer are arranged in a regular manner with no obvious pores, which confirms the strengthening effect of the decomposition products of MIL-88A on the glaze structure.

[0159] Example 3 A method for preparing a ceramic product, comprising: (1) Providing MOFs materials: In this embodiment, iron-based metal-organic framework ZIF-67 was selected as the functional component. ZIF-67 was synthesized by room temperature stirring method and passed through a 200-mesh sieve to obtain uniform ZIF-67 powder.

[0160] Figure 11 The X-ray diffraction (XRD) pattern of the metal-organic framework material ZIF-67 prepared in Example 3 is shown. Figure 12 The image shows a scanning electron microscope (SEM) image of the metal-organic framework material ZIF-67 prepared in Example 3. Figure 11 The XRD pattern of ZIF-67 shown shows that the ZIF-67 synthesized using the room temperature stirring method matches the ZIF-67 standard card without any impurity peaks, proving the purity of the crystal; as shown. Figure 12 The SEM image of ZIF-67 shows that ZIF-67 has a regular dodecahedral morphology, a particle size of 0.5 ~ 1 μm, and good particle dispersibility, which can meet the requirements for uniform dispersion in glazes.

[0161] (2) Glaze preparation: According to the mass fraction, 1.0 part of ZIF-67, 47 parts of feldspar, 7 parts of quartz, 17 parts of calcite, 7 parts of wollastonite, 3.5 parts of copper ore, 5 parts of tin oxide, 10 parts of talc and 2.5 parts of bovine bone are mixed to obtain glaze powder; the glaze powder is placed in a ceramic ball mill jar (the ball mill stone is made of alumina material to ensure that no impurities are introduced). The size of the ball mill stone includes 10mm, 30mm and 65mm, the ratio is 2:1:1, and the filling rate is 40%; deionized water is added at a material-liquid ratio of 1:1.2, and the ball mill is run at 300 r / min for 24 h. Then, a 200 mesh standard sieve is used to remove the coarse particles that are not completely ground. Then, the glaze slurry concentration is adjusted while stirring, and the glaze slurry Baume concentration is adjusted to 45 Baume degrees to obtain metal-organic framework-based glaze; and the stirring is maintained at 50 r / min to prevent ZIF-67 particles from settling and separating.

[0162] (3) Glazing of the body: Select a 150 mL kaolin Kung Fu tea cup blank (fired at 1100 ℃, water absorption rate ≤3%). The pretreatment steps are as follows: lightly grind the burrs and impurities on the surface of the blank with 400 grit sandpaper, rinse it with deionized water, and dry it at 80 ℃ for 2 h (to remove surface moisture and avoid blistering of the glaze layer after glazing).

[0163] Static immersion glazing method is used: the unglazed body is fixed with stainless steel clamps and slowly immersed in continuously stirred glaze slurry, with the immersion time controlled at 20 s. The unglazed body is lifted at a uniform speed of 5 cm / s and allowed to drip naturally for 15 min. The glaze thickness is measured at 3 different positions on the cup body with vernier calipers to ensure uniform control within 5 mm ± 0.2 mm. After glazing, the unglazed body is placed in a ventilated and dust-free environment (temperature 25℃, humidity 50%) to air dry naturally for 12 h. It is ready for use when there are no obvious water stains on the glaze surface.

[0164] (4) Precise temperature control sintering: The dried green body is placed in a box-type electric kiln (temperature control accuracy ±5℃) and fired in an oxidizing atmosphere. The firing process is the same as in Example 1.

[0165] Upon opening the kiln, a ZIF-67 glazed Kung Fu tea cup (oxidized) was obtained.

[0166] The actual object and optical microscope image of the ZIF-67 glaze Kung Fu tea cup (oxidized) fired in Example 3 of this invention are shown below. Figure 13 and Figure 14 As shown, from Figure 13 and Figure 14 As can be seen, the ZIF-67 glaze in Example 3 is blue, with a uniform color distribution, a warm and lustrous surface, and visible fine spots and textures, presenting a unique textural effect.

[0167] The sample was broken, and its glaze surface and fracture points were characterized by scanning electron microscopy. The results are as follows: Figure 15 and Figure 16 As shown. Figure 15 As shown in the SEM image of the glaze on the Kung Fu tea cup, the glaze surface is smooth and flat. The sample was broken, and the fracture surface was characterized using scanning electron microscopy, as shown... Figure 16 As shown, the glaze-body interface is very dense, with no obvious interface.

[0168] Example 4 A method for preparing a ceramic product, comprising: Step (1) providing MOFs materials, step (2) glaze preparation, and step (3) glazing the body are the same as in Example 3.

[0169] (4) Precise temperature control sintering: The dried green body is placed in a box-type electric kiln (temperature control accuracy ±5℃) and fired in an oxidizing atmosphere. The firing process is the same as in Example 2.

[0170] Upon opening the kiln, a ZIF-67 glazed Kung Fu tea cup (restored) was obtained.

[0171] The actual object and optical microscope image of the ZIF-67 glaze Kung Fu tea cup (reduction) fired in Example 4 of this invention are shown below. Figure 17and Figure 18 As shown, from Figure 17 and Figure 18 As can be seen, compared with modern Co-containing glazes, the ZIF-67 glaze of Example 4 has a finer and denser texture, a more lustrous blue color, and presents a purer, more elegant, and textured glaze overall.

[0172] Figure 19 The SEM image of the sample obtained in Example 4 is shown; the sample was broken, and its glaze surface and fracture surface were characterized by scanning electron microscopy, with the results as follows. Figure 20 As shown. Figure 19 and Figure 20 As shown in the SEM image of the glaze of the Kung Fu tea cup, the glaze surface is smooth and flat; moreover, the glaze-body interface is very dense with no obvious interface.

[0173] Comparative Example 1 A method for preparing a ceramic product, comprising: (1) Provide MOFs and cobalt oxide materials: In this comparative example, cobalt-based metal-organic framework ZIF-67 and cobalt oxide were selected as functional components. The preparation method of ZIF-67 is the same as that in Example 3 or 4, and commercial copper oxide is used for cobalt oxide.

[0174] (2) Preparation of unglazed blanks: Select ceramic-specific kaolin + feldspar + quartz (mass ratio 6:3:1), add water and knead into clay (moisture content 18%~20%), press into 100mm×100mm×5mm sheet blanks with molds, air dry at room temperature for 24h, then bisque fire at 1100℃ for 2h (heating rate 5℃ / min), and obtain unglazed blank test pieces (water absorption ≤3%) after cooling.

[0175] (2) Glaze preparation: According to the mass fraction, 1.0 part of ZIF-67, 47 parts of feldspar, 7 parts of quartz, 17 parts of calcite, 7 parts of wollastonite, 3.5 parts of copper ore, 5 parts of tin oxide, 10 parts of talc, and 2.5 parts of bovine bone were mixed to obtain glaze powder; the glaze with cobalt oxide as the functional component was obtained by replacing 1.0 part of ZIF-67 with 1.0 part of cobalt oxide, while keeping the rest unchanged; the mass of cobalt metal in ZIF-67 and cobalt oxide was kept consistent; the glaze powder was placed in a ceramic ball mill jar (the grinding stone was made of alumina material to ensure no impurities were introduced), the size of the grinding stone included 10mm, 30mm, and 65mm, the ratio was 2:1:1, and the filling rate was 40%; deionized water was added at a material-to-liquid ratio of 1:1.2, and the mixture was ball milled at 300 r / min for 24 hours. h, then a 200-mesh standard sieve is used to remove coarse particles that are not fully ground. Then, while stirring, the glaze concentration is adjusted to 45 Baume degrees to obtain a metal-organic framework-based glaze. The stirring is maintained at 50 r / min to prevent ZIF-67 or cobalt oxide particles from precipitating and separating.

[0176] (3) Glazing of the body: Select a 100mm×100mm×5mm unglazed test piece. The pretreatment steps are as follows: lightly grind the burrs and impurities on the surface of the unglazed body with 400-grit sandpaper, rinse it with deionized water, and dry it in a forced-air drying at 80℃ for 2 hours (to remove surface moisture and avoid blistering of the glaze layer after glazing).

[0177] Static immersion glazing method was used: the unglazed test piece was glazed by hand dip immersion, slowly immersed in the continuously stirred glaze slurry, and the immersion time was controlled at 20 s. The test piece was lifted at a uniform speed of 5 cm / s and allowed to drip naturally for 5 min. The thickness was uniformly controlled at 5 mm ± 0.2 mm. After glazing, the test piece was placed in a ventilated and dust-free environment (temperature 25℃, humidity 50%) to air dry naturally for 12 h. It was ready for use when there were no obvious water stains on the surface of the glaze layer.

[0178] (4) Precise temperature control sintering: The dried green blank test piece is placed in a box-type electric kiln (temperature control accuracy ±5℃) and fired according to the oxidizing atmosphere process. The firing process is the same as in Example 1.

[0179] Upon opening the kiln, ZIF-67 glaze specimens (oxidized) and cobalt oxide glaze specimens (oxidized) were obtained.

[0180] The optical microscope images of the ZIF-67 glaze specimen (oxidation) and cobalt oxide glaze specimen (oxidation) fired in Comparative Example 1 of this invention are shown below. Figure 21 and Figure 22 As shown, from Figure 21 and Figure 22As can be seen, the ZIF-67 glaze in Comparative Example 1 exhibits a natural gradient from dark to light, a unique kiln-transformation effect brought about by MOFs as molecular-level color-developing precursors. In contrast, the blue of the cobalt oxide glaze, while uniform, appears somewhat flat and lacks dynamic color gradation. Furthermore, when MOFs decompose at high temperatures, their porous structure adsorbs CO2 bubbles generated during the glaze melting process, reducing pinholes on the glaze surface. The ZIF-67 glaze contains only a very small number of tiny impurities, while the cobalt oxide glaze shows numerous obvious bubble defects, indicating that MOFs are significantly effective in optimizing glaze density.

[0181] The embodiments of this application have been described above with reference to the accompanying drawings. However, this application is not limited to the specific embodiments described above. The specific embodiments described above are merely illustrative and not restrictive. Those skilled in the art can make many other forms under the guidance of this application without departing from the spirit and scope of the claims, and all of these forms are within the protection scope of this application.

Claims

1. A metal-organic framework-based glaze, characterized in that, The metal-organic framework-based glaze comprises: a metal-organic framework material and a base glaze, wherein the base glaze comprises the following components: White feldspar, quartz, calcite, wollastonite, copper ore, talc, cow bone, and tin oxide.

2. The metal-organic framework-based glaze according to claim 1, characterized in that, The metal-organic framework-based glaze is made by mixing glaze powder and water, wherein the glaze powder includes the metal-organic framework material and the base glaze; the mass ratio of the glaze powder to water is glaze powder:water = 1:(1.1~1.5), preferably glaze powder:water = 1:(1.2~1.3).

3. The metal-organic framework-based glaze according to claim 1, characterized in that, The metal-organic framework-based glaze comprises the following components in parts by weight: 0.1 to 10 parts of metal-organic framework material, 40 to 50 parts of feldspar, 5 to 12 parts of quartz, 10 to 17 parts of calcite, 5 to 8 parts of wollastonite, 1 to 5 parts of copper ore, 8 to 10 parts of talc, 2 to 4 parts of bovine bone, and 2 to 5 parts of tin oxide. Preferably, the metal-organic framework-based glaze comprises the following components in parts by weight: The composition includes 0.2 to 10 parts of metal-organic framework material, 44 to 46 parts of feldspar, 6 to 11 parts of quartz, 12 to 17 parts of calcite, 5 to 7 parts of wollastonite, 2 to 4 parts of copper ore, 8 to 10 parts of talc, 2.5 to 3 parts of bovine bone, and 3 to 4 parts of tin oxide. Preferably, the metal-organic framework-based glaze comprises the following components in parts by weight: The composition includes 0.5 to 2 parts of metal-organic framework material, 44 to 45 parts of feldspar, 7 to 10 parts of quartz, 15 to 17 parts of calcite, 5 to 7 parts of wollastonite, 2.5 to 4 parts of copper ore, 9 to 10 parts of talc, 2.5 to 2.8 parts of bovine bone, and 3 to 4 parts of tin oxide.

4. The metal-organic framework-based glaze according to any one of claims 1 to 3, characterized in that, The metal-organic framework material includes at least one of transition metal-based MOFs, rare earth metal-based MOFs, and their functionalized derivatives. The transition metal-based MOFs include at least one of Fe-based MOFs, Co-based MOFs, Cu-based MOFs, Zn-based MOFs, Cr-based MOFs, Zr-based MOFs, Mn-based MOFs, or Al-based MOFs; preferably, the transition metal-based MOFs include at least one of MIL-88A, MIL-100 (Fe), MIL-101 (Fe), ZIF-67, MOF-74 (Ni), HKUST-1 (Cu), ZIF-68, ZIF-8, MOF-5, MIL-101 (Cr), MIL-100 (Cr), UiO-66 (Zr), UiO-67 (Zr), or MIL-53 (Al); The rare earth metal-based MOFs include Eu-MOF and / or Tb-MOF; the functionalized derivatives include complexes of the above MOFs and MOF materials modified with functional groups. Preferably, the metal-organic framework material is prepared by a green synthesis process, which includes at least one of room temperature stirring synthesis, hydrothermal synthesis, mechanical grinding synthesis, or microwave-assisted synthesis.

5. A method for preparing a metal-organic framework-based glaze, characterized in that, The method includes: A metal-organic framework material, feldspar, quartz, calcite, wollastonite, copper ore, talc, bovine bone, and tin oxide are mixed to obtain a glaze powder. The glaze powder and water are added to a ball mill for ball milling and then sieved to obtain a metal-organic framework-based glaze.

6. The method for preparing the metal-organic framework-based glaze according to claim 5, characterized in that, The method satisfies at least one of the following characteristics: (1) The mass ratio of the glaze powder, water and grinding media is glaze powder: water: grinding media = 1: (1.1~1.5): (2~3); And / or, the filling rate of the grinding media in the ball mill is 30% to 50%; (2) The grinding media used in the ball milling includes a first grinding media, a second grinding media and a third grinding media, wherein the size of the first grinding media, the second grinding media and the third grinding media increases sequentially; Preferably, the size of the first grinding media is 10mm to 20mm, the size of the second grinding media is 30mm to 40mm, and the size of the third grinding media is 50mm to 70mm. Preferably, the mass ratio of the first grinding medium, the second grinding medium, and the third grinding medium is (1.5~2):(1~1.5):1; (3) The ball milling time is 18h to 30h; and / or the ball mill speed is 100 r / min to 500 r / min; (4) The mesh size of the sieve is 100 to 300 mesh; (5) The Baumé concentration of the metal-organic framework-based glaze is 45 to 60 Baumé degrees.

7. A ceramic product, characterized in that, The ceramic product includes a ceramic body layer and a glaze layer in contact with the ceramic body layer; The glaze layer is made of the metal-organic framework-based glaze according to any one of claims 1 to 4 and / or the metal-organic framework-based glaze prepared by the preparation method according to any one of claims 5 to 6.

8. A method for preparing a ceramic product, characterized in that, The method includes: A metal-organic framework-based glaze is provided, which is made by mixing glaze powder and water. The glaze powder includes metal-organic framework materials, feldspar, quartz, calcite, wollastonite, copper ore, talc, bovine bone, and tin oxide. The metal-organic framework-based glaze is applied to a ceramic green body to obtain a green body to be fired. The blank to be fired is sintered to obtain the ceramic product.

9. The method for preparing ceramic products according to claim 8, characterized in that, The method satisfies at least one of the following characteristics: (1) In the step of providing metal-organic framework-based glaze, the glaze powder and water are mixed and ball-milled in a mass ratio of 1: (1.1 to 1.5) for 18 to 30 hours and the ball mill speed is 100 to 500 r / min; and then the mixture is sieved through a 100 to 300 mesh filter. Preferably, the Baumé concentration of the prepared metal-organic framework-based glaze is 45–60 Baumé degrees; (2) During the glazing process, the metal-organic framework-based glaze is continuously stirred at a speed of 30 r / min to 60 r / min. Preferably, the glazing method includes immersion glazing, which includes: immersing a surface-cleaned ceramic blank into a metal-organic framework-based glaze for immersion glazing; (3) The thickness of the glaze layer obtained after glazing is 4mm to 5mm; (4) The sintering adopts staged temperature-controlled sintering, and the peak temperature of the staged temperature-controlled sintering is 1240℃~1300℃; The sintering atmosphere includes an oxidizing atmosphere or a reducing atmosphere.

10. The method for preparing ceramic products according to claim 9, characterized in that, The sintering process in the oxidizing atmosphere includes: S10. Preheating stage: The temperature is increased to 300℃ to 400℃ at a heating rate of 10℃ / min to 15℃ / min, and held for 2h to 3h; the preheating stage utilizes natural air inside the kiln to maintain the oxidation state. S20, Oxidation Stage: First, the temperature is increased to 1140℃~1200℃ at a heating rate of 5℃ / min~10℃ / min, and held for 20min~30min. Then, the temperature is increased to 1240℃~1300℃ at a heating rate of 3℃ / min~5℃ / min, and held for 50min~60min. During the oxidation stage, air is introduced through the pre-set ventilation openings of the kiln to ensure sufficient oxygen in the kiln. S30, Cooling stage: Turn off the heating system of the kiln to reduce the temperature inside the kiln from 1240℃~1300℃ to room temperature; And / or, the sintering process in the reducing atmosphere includes: S10, Atmosphere transition stage: Reducing gas is introduced into the kiln, and the gas flow rate is controlled to reduce the oxygen content in the kiln to below 1% and maintain the reducing gas concentration in the kiln at 3% to 5%. S20. During the preheating stage, the temperature is increased to 300℃ to 400℃ at a heating rate of 10℃ / min to 15℃ / min, and held for 2h to 3h. S30, First reduction stage: Heat to 1050℃~1150℃ at a heating rate of 5℃ / min~10℃ / min, and hold for 1h~1.5h; S40, Second reduction stage: Heat to 1150℃~1280℃ at a heating rate of 3℃ / min~5℃ / min, and hold for 2h~3h; S50, Neutral heat preservation stage: reduce the concentration of reducing gas in the kiln to ≤1%, raise the temperature to 1280℃~1300℃ at a heating rate of 1℃ / min~3℃ / min, and keep it at that temperature for 0.5h~1h. S60. In the stage of segmented cooling, the heating system of the kiln is turned off. The temperature is first reduced from 1280℃~1300℃ to 500℃~600℃ at a cooling rate of 10℃ / min~15℃ / min. Then, the temperature inside the kiln is reduced to room temperature through natural cooling.

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