CN-122010414-A - Metal organic frame base glaze, ceramic product and preparation method thereof

CN122010414ACN 122010414 ACN122010414 ACN 122010414ACN-122010414-A

Abstract

The application discloses a Metal Organic Frameworks (MOFs) based glaze, a ceramic product and a preparation method thereof, and belongs to the technical field of ceramic materials. The metal organic frame base glaze comprises metal organic frame materials and basic glaze, wherein the basic glaze comprises white feldspar, quartz, calcite, wollastonite, copper ore, talcum, bovine bone and tin oxide. The metal organic frame base glaze adopts MOFs as a core function regulating unit, is matched with a specific weight percentage mineral composite system consisting of white feldspar, quartz, calcite, wollastonite, copper ore, tin oxide, talcum and bovine bone, and is constructed into an integrated technical system of function regulation, structure forming and performance optimization through a stepped preparation process of 'raw material precise proportioning-high-energy ball milling pulping-multi-dimensional uniform glazing-controllable atmosphere glaze firing', so that the problems of single component regulation dimension, uncontrollable kiln transformation effect, weak glaze interface combination and the like of the current ceramic glaze system can be alleviated.

Inventors

WANG CHONGCHEN
GAO YA
YI XIAOHONG
WANG FEI
WANG PENG

Assignees

北京建筑大学

Dates

Publication Date: 20260512
Application Date: 20260209

Claims (10)

1. The metal organic frame base glaze is characterized by comprising a metal organic frame material and a basic glaze, wherein the basic glaze comprises the following components: White feldspar, quartz, calcite, wollastonite, copper ore, talc, bovine bone and tin oxide.
2. The metal organic frame base glaze according to claim 1, wherein the metal organic frame base glaze is prepared by mixing glaze powder and water, wherein the glaze powder comprises the metal organic frame material and the base glaze, and the mass ratio of the glaze powder to the water is (1.1-1.5) and preferably (1.2-1.3).
3. The metal organic frame base glaze according to claim 1, wherein the metal organic frame base glaze comprises the following components in parts by mass: 0.1 to 10 parts of metal organic frame material, 40 to 50 parts of white 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 talcum, 2 to 4 parts of beef bone and 2 to 5 parts of tin oxide; preferably, the metal organic frame base glaze comprises the following components in parts by mass: 0.2 to 10 parts of metal organic frame material, 44 to 46 parts of white 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 talcum, 2.5 to 3 parts of bovine bone and 3 to 4 parts of tin oxide; preferably, the metal organic frame base glaze comprises the following components in parts by mass: 0.5 to 2 parts of metal organic frame material, 44 to 45 parts of white 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 talcum, 2.5 to 2.8 parts of beef bone and 3 to 4 parts of tin oxide.
4. A metal organic frame based glaze according to any one of claims 1 to 3, wherein said metal organic frame material comprises at least one of transition metal based MOFs, rare earth metal based MOFs and functionalized derivatives thereof; Wherein the transition metal-based MOFs comprise 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 comprise 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 comprise Eu-MOF and/or Tb-MOF; the functional derivative comprises a compound of the MOFs and MOFs materials modified by functional groups; Preferably, the metal organic framework material is prepared by a green synthesis process comprising at least one of a room temperature stirred synthesis, a water/solvent thermal synthesis, a mechanical milling synthesis or a microwave assisted synthesis.
5. A method for preparing a metal organic framework-based glaze, the method comprising: Mixing a metal organic frame material, white feldspar, quartz, calcite, wollastonite, copper ore, talcum, bovine bone and tin oxide to obtain glaze powder; and adding the glaze powder and water into a ball mill for ball milling and sieving to obtain the metal organic frame base glaze.
6. The method of preparing a metal organic framework frit according to claim 5, wherein the method satisfies at least one of the following characteristics: (1) The mass ratio of the glaze powder to the water to the grinding medium is (1.1-1.5) to (2-3) that the glaze powder to the water to the grinding medium=1; and/or the filling rate of grinding media in the ball mill is 30% -50%; (2) The grinding media adopted in the ball milling process comprise a first grinding medium, a second grinding medium and a third grinding medium, and the sizes of the first grinding medium, the second grinding medium and the third grinding medium are sequentially increased; Preferably, the first grinding medium is 10 mm-20 mm in size, the second grinding medium is 30 mm-40 mm in size, and the third grinding medium is 50 mm-70 mm in size; preferably, the mass ratio of the first grinding medium to the second grinding medium to the third grinding medium is = (1.5-2): (1-1.5): 1; (3) The ball milling time is 18-30 h, and/or the rotating speed of the ball mill is 100 r-500 r/min; (4) The mesh number of the screened filter screen is 100-300 meshes; (5) The Baume concentration of the metal organic frame base glaze is 45-60 Baume degrees.
7. A 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 metal organic frame base glaze according to any one of claims 1 to 4 and/or the metal organic frame base glaze prepared by the preparation method according to any one of claims 5 to 6.
8. A method of making a ceramic article, the method comprising: Providing a metal organic frame-based glaze, wherein the metal organic frame-based glaze is prepared by mixing glaze powder and water, and the glaze powder comprises metal organic frame materials, white feldspar, quartz, calcite, wollastonite, copper ore, talcum, bovine bone and tin oxide; glazing the ceramic green body by adopting the metal organic frame base glaze to obtain a green body to be fired; And sintering the blank to be fired to obtain the ceramic product.
9. The method of making a ceramic article according to claim 8, wherein the method satisfies at least one of the following characteristics: (1) In the step of providing the metal organic frame base glaze, mixing and ball milling glaze powder and water according to the mass ratio of 1 (1.1-1.5), wherein the ball milling time is 18-30 hours, and the rotating speed of the ball mill is 100 r-500 r/min; preferably, the Baume concentration of the prepared metal organic frame base glaze is 45-60 Baume degrees; (2) Continuously stirring the metal organic frame base glaze in the glazing process, wherein the stirring speed is 30 r/min-60 r/min; Preferably, the glazing method comprises immersion glazing, wherein the immersion glazing comprises immersing a ceramic green body subjected to surface purification treatment into a metal organic frame-based glaze for immersion glazing; (3) The thickness of the glaze layer obtained after glazing is 4 mm-5 mm; (4) The sintering adopts staged temperature-controlled sintering, and the peak temperature of the staged temperature-controlled sintering is 1240-1300 ℃; The atmosphere for sintering includes an oxidizing atmosphere or a reducing atmosphere.
10. The method of preparing a ceramic article according to claim 9, wherein the oxidizing atmosphere sintering process comprises: S10, a preheating stage, wherein the temperature is raised to 300-400 ℃ at a temperature rising rate of 10-15 ℃ per minute, and the temperature is kept for 2-3 hours; S20, in an oxidation stage, firstly, heating to 1140-1200 ℃ at a heating rate of 5-10 ℃ per minute, preserving heat for 20-30 min, and then heating to 1240-1300 ℃ at a heating rate of 3-5 ℃ per minute, preserving heat for 50-60 min, wherein air is introduced into the oxidation stage through a kiln preset vent so as to ensure sufficient oxygen in the kiln; S30, in the cooling stage, a heating system of the kiln is closed, so that the temperature in the kiln is reduced from 1240 ℃ to 1300 ℃ to room temperature; And/or, the sintering process of the reducing atmosphere comprises the following steps: S10, in an atmosphere conversion stage, introducing reducing gas into the kiln, controlling the gas flow, reducing the oxygen content in the kiln to below 1%, and maintaining the concentration of the reducing gas in the kiln to 3% -5%; S20, in a preheating stage, heating to 300-400 ℃ at a heating rate of 10-15 ℃ per minute, and preserving heat for 2-3 hours; S30, in a first reduction stage, heating to 1050-1150 ℃ at a heating rate of 5-10 ℃ per min, and preserving heat for 1-1.5 h; s40, in a second reduction stage, heating to 1150-1280 ℃ at a heating rate of 3-5 ℃ per minute, and preserving heat for 2-3 hours; S50, in a neutral heat preservation stage, the concentration of the reducing gas in the kiln is increased to be less than or equal to 1%, the temperature is increased to 1280-1300 ℃ at the temperature increasing rate of 1-3 ℃ per minute, and the heat is preserved for 0.5-1 h; s60, in a stage of sectional cooling, a heating system of the kiln is closed, the temperature is firstly reduced from 1280-1300 ℃ to 500-600 ℃ at a cooling rate of 10-15 ℃ per minute, and then the temperature in the kiln is reduced to the room temperature through natural cooling.

Description

Metal organic frame base glaze, ceramic product and preparation method thereof Technical Field The application belongs to the technical field of ceramic materials, and particularly relates to a metal organic frame base glaze, a ceramic product and a preparation method thereof. Background The ceramic is taken as an important material carrier of the excellent traditional culture of China, is a peak pattern integrating process complexity, glaze color artistry and culture symbolism in a traditional ceramic manufacturing process system, has unique kiln transformation phenomenon and rich glaze color layers, not only bears the technical spirit of thousands of years of ceramic civilization, but also forms the core content of the activation inheritance of the current cultural heritage. The traditional ceramic firing process is characterized by being characterized by empirically made of mineral formula and uncontrollable kiln transformation process, and can form unique aesthetic effects by relying on compatibility of specific mineral components and complicated kiln atmosphere regulation and control, but along with upgrading of requirements of modern society on ceramic high-end, functional and personalized, the technical bottleneck of a traditional system is increasingly highlighted, on one hand, the traditional glaze takes natural minerals as a main component, the component regulation and control space is limited, the glaze color stability is poor, the batch difference is obvious, and mechanical properties such as glaze hardness and wear resistance and the aesthetic texture of jade luster are difficult to cooperatively optimize, on the other hand, the kiln transformation effect depends on empirical process parameters, directional design cannot be realized, the requirements of diversified application scenes such as modern high-end decoration and functional ceramics are difficult to meet, and the cross-boundary development of ceramics from 'cultural artware' to 'high-function products' is restricted. Currently, research in the ceramic field is still focused on the traditional paradigm of traditional glaze component fine adjustment and firing process parameter optimization, and the improvement means is limited to local adjustment of mineral proportion or small modification of kiln temperature curve, and cannot break through the inherent framework of mineral combination-process parameter, so that the spanning improvement of performance and aesthetics is difficult to realize from the material essence level. Disclosure of Invention In view of the above-described problems, the present invention aims to solve, at least to some extent, one of the technical problems in the related art. Therefore, the metal organic frame-based glaze, the ceramic product and the preparation method thereof can solve the technical problems of single component regulation dimension, poor ceramic glaze performance, poor kiln transformation effect, weak glaze blank combination and the like of the current ceramic glaze system, and can overcome the defects in the prior art. In order to solve the technical problems, the application is realized as follows: According to a first aspect of the application, an embodiment of the application provides a metal organic frame-based glaze comprising a metal organic frame material and a base glaze comprising the following components white feldspar, quartz, calcite, wollastonite, copper ore, talc, bovine bone and tin oxide. In some embodiments, the metal organic frame base glaze is prepared by mixing glaze powder and water, wherein the glaze powder comprises the metal organic frame material and the base glaze, and the mass ratio of the glaze powder to the water is (1.1-1.5) of the glaze powder to the water=1. In some embodiments, the mass ratio of the glaze powder to the water is (1.2-1.3) that the glaze powder and the water are in a ratio of (1). In some embodiments, the metal organic frame based glaze comprises the following components in parts by mass: 0.1-10 parts of metal organic frame material, 40-50 parts of white feldspar, 5-12 parts of quartz, 10-17 parts of calcite, 5-8 parts of wollastonite, 1-5 parts of copper ore, 8-10 parts of talcum, 2-4 parts of beef bone and 2-5 parts of tin oxide. In some embodiments, the metal organic frame based glaze comprises the following components in parts by mass: 0.2 to 10 parts of metal organic frame material, 44 to 46 parts of white 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 talcum, 2.5 to 3 parts of beef bone and 3 to 4 parts of tin oxide. In some embodiments, the metal organic frame based glaze comprises the following components in parts by mass: 0.5 to 2 parts of metal organic frame material, 44 to 45 parts of white 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 talcum, 2.5 to 2.8 parts