Cordierite-spinel ceramic material and preparation method thereof

Abstract

The present invention relates to the technical field of ceramic material preparation, specifically a method for preparing a cordierite-spinel ceramic material, comprising the following steps: S1, uniformly mixing coal gangue powder, basic magnesium carbonate powder, aluminum oxide powder and epoxy resin powder to obtain a mixture, and compacting to obtain a ceramic base material; S2, placing the ceramic base material obtained in step S1 into a cold isostatic press; S3, heat-treating the ceramic base material treated in step S2; S4, pressurizing and impregnating the ceramic base material treated in step S3 into a deoxygenated acrylic acid solution; S5, high-temperature calcining the ceramic base material treated in step S4 to obtain a cordierite-spinel ceramic material. The ceramic material prepared by the present invention disperses a small amount of yttrium oxide powder, zinc borate powder and silicon nitride powder into the micropores of the ceramic base material through acrylic hydrogel, and the formed ceramic has high hardness.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic material preparation, in particular to a cordierite-spinel ceramic material and a preparation method thereof. Background Art

[0002] In the field of materials science, ceramic materials are widely used in industry, aerospace, and electronics, which is related to high-temperature stability, corrosion resistance and hardness. However, the preparation of traditional ceramic materials often relies on high-purity raw materials and complex process, which not only increases production costs, but also limits their applications. Therefore, the development of new composite ceramic materials has become one of the current hot spots in materials science research, especially the recycling and reuse of industrial waste. Gangue, as solid waste generated during coal mining and washing, not only occupies land resources, but also may pollute the environment when piled up in large quantities. Gangue is rich in silicon, aluminum, iron and other elements, and its utilization value is potential. In recent years, researchers have begun to explore the feasibility of using gangue as raw material to prepare ceramic materials, aiming to reduce the production cost of ceramic materials while making two common ceramic materials cordierite (Mg2Al4Si5O 18 ) and spinel (MgAl2O4) to obtain better thermal stability, chemical stability and mechanical properties. The composite treatment of cordierite and spinel can further optimize the material properties and meet a wider range of application needs. The cordierite-spinel ceramic materials used in traditional methods usually have high requirements on the purity of raw materials, and the synthesis process is also relatively complicated, which limits their production and application. For example, the patented technology of "Cordierite-spinel ceramic material with high infrared emissivity and preparation method thereof (patent number CN105198394B)" discloses a method of using waste fly ash as raw material, mainly relying on high-purity raw materials such as high-purity alumina and high-purity magnesium oxide to prepare cordierite-spinel ceramic materials. This not only increases the production cost, but also hinders large-scale application, has low mechanical strength, and has a high porosity.

[0003] Therefore, the present invention aims to develop a cordierite-spinel ceramic material using coal gangue as the main raw material, combined with basic magnesium carbonate and aluminum oxide, through a simple and effective process. The mechanical properties of the material are further optimized by introducing performance-enhancing raw materials such as silicon nitride powder, yttrium oxide powder, and zinc borate powder, and by using a cold isostatic pressing process. Furthermore, during the introduction of a small amount of silicon nitride powder, yttrium oxide powder, and zinc borate powder, the present invention uses gelled acrylic acid as a carrier to optimize the introduction method of the silicon nitride powder, yttrium oxide powder, and zinc borate powder, thereby improving their uniformity. This provides new ideas and technical support for the preparation and application of ceramic materials. Summary of the Invention

[0004] The object of the present invention is to provide a cordierite-spinel ceramic material and a preparation method thereof, so as to solve the problems raised in the above background technology.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] A cordierite-spinel ceramic material comprises a ceramic base material and an impregnation liquid;

[0007] The ceramic base material is composed of coal gangue powder, basic magnesium carbonate powder, aluminum oxide powder and epoxy resin powder;

[0008] The impregnation liquid is an acrylic acid solution, which further contains yttrium oxide powder, zinc borate powder, silicon nitride powder, ammonium persulfate, sodium lauryl sulfate, N,N'-methylenebisacrylamide and glycerol.

[0009] A method for preparing a cordierite-spinel ceramic material comprises the following steps:

[0010] S1. Evenly mixing coal gangue powder, basic magnesium carbonate powder, aluminum oxide powder and epoxy resin powder to obtain a mixture, placing the mixture into a mold and compacting it with a tablet press to obtain a ceramic base material;

[0011] S2, placing the ceramic base material obtained in step S1 into a cold isostatic press for processing;

[0012] S3, heating the ceramic base material treated in step S2 at 200° C. for 3 h, then heating to 600° C. for another 1 h;

[0013] S4, pressurizing and impregnating the ceramic base material treated in step S3 into a deoxygenated acrylic acid solution, wherein the acrylic acid solution also contains yttrium oxide powder, zinc borate powder, silicon nitride powder, ammonium persulfate, sodium lauryl sulfate, N,N'-methylenebisacrylamide, and glycerol, and crosslinking at 75° C. for 2.5 hours;

[0014] S5. Firing the ceramic base material processed in step S4 at 1200-1450° C. for 2-3 hours and cooling the furnace to obtain a cordierite-spinel ceramic material.

[0015] Furthermore, in step S1, the mass ratio of basic magnesium carbonate powder, alumina powder and coal gangue powder is 1:(0.8-2):(2.2-3.4), and the ratio of the mass of the epoxy resin powder to the total mass of basic magnesium carbonate powder, alumina powder and coal gangue powder is 1:15.

[0016] Furthermore, in step S1, the pressure of the tablet press is set to 8-12 MPa, and the holding time is 2-5 min.

[0017] Furthermore, in the step S2, the pressure applied during the isostatic press treatment is 150-200 MPa, and the holding time is 5-10 minutes.

[0018] Furthermore, the pressure of the pressurized impregnation in step S4 is 5-10 MPa, the mass ratio of N,N'-methylenebisacrylamide, sodium lauryl sulfate, ammonium persulfate, acrylic acid monomer and deionized water in the acrylic acid solution is 1:4:6:800:4000; the mass ratio of glycerol to acrylic acid monomer is 1:(3-5); the mass ratio of yttrium oxide powder, zinc borate powder and silicon nitride powder is 1:1:(0.5-3); the mass ratio of the total mass of yttrium oxide powder, zinc borate powder and silicon nitride powder to deionized water is 1:10.

[0019] Furthermore, the silicon nitride powder is thermally oxidized at 750° C. for 1.5 hours.

[0020] Furthermore, the particle size of the gangue powder, basic magnesium carbonate powder and alumina powder in step S1 is 25-40 μm; the particle size of the epoxy resin powder is 0.5-1 μm; and the particle size of the yttrium oxide powder, zinc borate powder and silicon nitride powder in step S3 is 30-50 nm.

[0021] A cordierite-spinel ceramic material is prepared by the above-mentioned method for preparing the cordierite-spinel ceramic material.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1. The ceramic material of the present invention significantly reduces the cost of raw materials, and the product has excellent performance. It can reduce environmental pollution and ecological damage, is low-cost, saves energy, has a simple process, and has a dense structure. By introducing silicon nitride powder, yttrium oxide powder, and zinc borate powder, the high-temperature strength and oxidation resistance of the ceramic material can be improved, and the stability and safety of the material in high-temperature environments can be enhanced. Its hardness is increased, and its wear resistance and impact resistance are greatly enhanced.

[0024] 2. The amount of silicon nitride powder, yttrium oxide powder, and zinc borate powder incorporated in the present invention is relatively small. By immersing the ceramic base material in an acrylic acid solution, the present invention facilitates the dispersion of a small amount of silicon nitride powder, yttrium oxide powder, and zinc borate powder. Through cross-linking with acrylic acid, a network structure is formed, allowing a small amount of silicon nitride powder, yttrium oxide powder, and zinc borate powder to be dispersed in the micropores of the ceramic base material. The micropores of the ceramic base material are formed after the epoxy resin powder is melted and degreased, thereby improving the hardness of the sintered product. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is a process flow chart of the present invention;

[0026] Figure 2XRD patterns of the cordierite-spinel ceramic materials prepared in Examples 1-4 of the present invention;

[0027] Figure 3 These are SEM images of the cordierite-spinel ceramic materials prepared in Examples 1-4 of the present invention. DETAILED DESCRIPTION

[0028] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0029] See also Figures 1 to 3 , the present invention provides:

[0030] Example 1

[0031] A method for preparing a cordierite-spinel ceramic material comprises the following steps:

[0032] S1, 9.2g of coal gangue powder, 3.6g of basic magnesium carbonate powder, 4.3g of aluminum oxide powder and 1.14g of epoxy resin powder are uniformly mixed to obtain a mixture, the particle size of the coal gangue powder, basic magnesium carbonate powder and aluminum oxide powder is 40um, and the particle size of the epoxy resin powder is 0.8um. ​​The mixture is placed in a mold and compacted by a tablet press. The pressure of the tablet press is set to 10MPa and the pressure holding time is 4min to obtain a ceramic base material;

[0033] S2. Place the ceramic base material obtained in step S1 into a cold isostatic press. The pressure applied during the isostatic press is 180 MPa and the holding time is 8 minutes.

[0034] S3, heating the ceramic base material treated in step S2 at 200° C. for 3 h, then heating to 600° C. for another 1 h;

[0035] S4. The ceramic base material treated in step S3 is pressurized and impregnated into a deoxygenated acrylic acid solution at a pressure of 8 MPa. The masses of deionized water and acrylic acid monomer in the acrylic acid solution are 40 g and 8 g, respectively. The acrylic acid solution also contains 1 g of yttrium oxide powder, 1 g of zinc borate powder, 2 g of silicon nitride powder, 0.06 g of ammonium persulfate, 0.04 g of sodium lauryl sulfate, 0.01 g of N,N'-methylenebisacrylamide, and 2 g of glycerol. The mixture is cross-linked at 75° C. for 2.5 h. The particle size of the yttrium oxide powder, zinc borate powder, and silicon nitride powder is 50 nm.

[0036] S5. Firing the ceramic base material processed in step S4 at 1300° C. for 2.5 hours and cooling the furnace to obtain a cordierite-spinel ceramic material.

[0037] Example 2

[0038] A method for preparing a cordierite-spinel ceramic material comprises the following steps:

[0039] S1, 7.92g of coal gangue powder, 3.6g of basic magnesium carbonate powder, 2.88g of aluminum oxide powder and 0.96g of epoxy resin powder were mixed to obtain a mixture, the particle size of the coal gangue powder, basic magnesium carbonate powder and aluminum oxide powder was 25um, and the particle size of the epoxy resin powder was 0.5um. The mixture was placed in a mold and compacted by a tablet press. The pressure of the tablet press was set to 8MPa and the pressure holding time was 2min to obtain a ceramic base material;

[0040] S2, placing the ceramic base material obtained in step S1 into a cold isostatic press, applying a pressure of 150 MPa during the isostatic press process, and holding the pressure for 5 minutes;

[0041] S3, heating the ceramic base material treated in step S2 at 200° C. for 3 h, then heating to 600° C. for another 1 h;

[0042] S4. The ceramic base material treated in step S3 is pressurized and impregnated into a deoxygenated acrylic acid solution at a pressure of 5 MPa. The masses of deionized water and acrylic acid monomer in the acrylic acid solution are 40 g and 8 g, respectively. The acrylic acid solution also contains 1.6 g yttrium oxide powder, 1.6 g zinc borate powder, 0.8 g silicon nitride powder, 0.06 g ammonium persulfate, 0.04 g sodium lauryl sulfate, 0.01 g N,N'-methylenebisacrylamide, and 2.67 g glycerol. The mixture is cross-linked at 75° C. for 2.5 h. The particle size of the yttrium oxide powder, zinc borate powder, and silicon nitride powder is 30 nm.

[0043] S5. Firing the ceramic base material processed in step S4 at 1200° C. for 2 hours and cooling the furnace to obtain a cordierite-spinel ceramic material.

[0044] Example 3

[0045] A method for preparing a cordierite-spinel ceramic material comprises the following steps:

[0046] S1, 7.48g of coal gangue powder, 2.2g of basic magnesium carbonate powder, 4.4g of aluminum oxide powder and 0.94g of epoxy resin powder were mixed to obtain a mixture, the particle size of the coal gangue powder, basic magnesium carbonate powder and aluminum oxide powder was 40um, and the particle size of the epoxy resin powder was 1um. The mixture was placed in a mold and compacted by a tablet press. The pressure of the tablet press was set to 12MPa and the pressure was maintained for 5min to obtain a ceramic base material;

[0047] S2. Place the ceramic base material obtained in step S1 into a cold isostatic press. The pressure applied during the isostatic press is 200 MPa and the holding time is 10 min.

[0048] S3, heating the ceramic base material treated in step S2 at 200° C. for 3 h, then heating to 600° C. for another 1 h;

[0049] S4. The ceramic base material treated in step S3 is pressurized and impregnated into a deoxygenated acrylic acid solution at a pressure of 10 MPa. The mass of deionized water and acrylic acid monomer in the acrylic acid solution is 40 g and 8 g, respectively. The acrylic acid solution also contains 0.8 g yttrium oxide powder, 0.8 g zinc borate powder, 2.4 g silicon nitride powder, 0.06 g ammonium persulfate, 0.04 g sodium lauryl sulfate, 0.01 g N,N'-methylenebisacrylamide, and 1.6 g glycerol. The mixture is cross-linked at 75° C. for 2.5 h. The particle size of the yttrium oxide powder, zinc borate powder, and silicon nitride powder is 50 nm.

[0050] S5. Firing the ceramic base material processed in step S4 at 1450° C. for 3 hours and cooling the furnace to obtain a cordierite-spinel ceramic material.

[0051] Example 4

[0052] A method for preparing a cordierite-spinel ceramic material comprises the following steps:

[0053] S1, 7.7g of coal gangue powder, 2.8g of basic magnesium carbonate powder, 3.9g of aluminum oxide powder and 0.96g of epoxy resin powder were mixed to obtain a mixture, the particle size of the coal gangue powder, basic magnesium carbonate powder and aluminum oxide powder was 30um, and the particle size of the epoxy resin powder was 0.5um. The mixture was placed in a mold and compacted by a tablet press. The pressure of the tablet press was set to 10MPa and the pressure holding time was 4min to obtain a ceramic base material;

[0054] S2. Place the ceramic base material obtained in step S1 into a cold isostatic press. The pressure applied during the isostatic press is 190 MPa and the holding time is 9 minutes.

[0055] S3, heating the ceramic base material treated in step S2 at 200° C. for 3 h, then heating to 600° C. for another 1 h;

[0056] S4. The ceramic base material treated in step S3 is pressurized and impregnated into a deoxygenated acrylic acid solution at a pressure of 8 MPa. The masses of deionized water and acrylic acid monomer in the acrylic acid solution are 40 g and 8 g, respectively. The acrylic acid solution also contains 1 g of yttrium oxide powder, 1 g of zinc borate powder, 2 g of silicon nitride powder, 0.06 g of ammonium persulfate, 0.04 g of sodium lauryl sulfate, 0.01 g of N,N'-methylenebisacrylamide, and 1.8 g of glycerol. The mixture is cross-linked at 75° C. for 2.5 h. The particle size of the yttrium oxide powder, zinc borate powder, and silicon nitride powder is 40 nm.

[0057] S5. Firing the ceramic base material processed in step S4 at 1400° C. for 3 hours and cooling the furnace to obtain a cordierite-spinel ceramic material.

[0058] In the present invention, the silicon nitride powder is subjected to thermal oxidation treatment at 750° C. for 1.5 hours to improve the dispersibility of the silicon nitride powder in the acrylic acid solution; the model of the epoxy resin powder is E-12.

[0059] In the present invention, the dispersion of yttrium oxide powder, zinc borate powder and silicon nitride powder in acrylic acid solution can be assisted by ultrasound, and the frequency of ultrasound is 40KHz. In the above embodiments, the amount of acrylic acid solution is sufficient for the ceramic base material.

[0060] In the present invention Figure 2 The XRD test results of the cordierite-spinel ceramic materials prepared in Examples 1-4 are shown. From the figure, it can be concluded that the test results of the ceramic materials are mainly cordierite and spinel phases; Figure 3 SEM images of Examples 1-4 are shown. Figure 3 (a), (b), (c) and (d) represent the SEM images of Examples 1, 2, 3 and 4, respectively. It can be further confirmed from the figures that the cordierite phase presents a columnar structure, while the spinel phase presents a regular tetrahedral structure.

[0061] Furthermore, in order to verify the performance of the cordierite-spinel ceramic material prepared by the present invention, the following comparative example was set up.

[0062] Comparative Example 1

[0063] The difference between Comparative Example 1 and Example 1 is that 0.2 g of yttrium oxide powder, 0.2 g of zinc borate powder and 0.4 g of silicon nitride powder are directly mixed with 9.2 g of coal gangue powder, 3.6 g of basic magnesium carbonate powder and 4.3 g of aluminum oxide powder, and then compacted by a tablet press, isostatically pressed, and finally sintered. The pressure parameters, sintering temperature, and time parameters are exactly the same as those in Example 1.

[0064] Comparative Example 2

[0065] The difference between Comparative Example 2 and Example 1 is that 0.14 g of yttrium oxide powder, 0.14 g of zinc borate powder and 0.28 g of silicon nitride powder are directly mixed with 9.2 g of coal gangue powder, 3.6 g of basic magnesium carbonate powder and 4.3 g of aluminum oxide powder, and then compacted by a tablet press, isostatically pressed, and finally sintered. The pressure parameters, sintering temperature, and time parameters are exactly the same as those in Example 1.

[0066] Comparative Example 3

[0067] The difference between Comparative Example 2 and Example 1 is that 0.08 g of yttrium oxide powder, 0.08 g of zinc borate powder and 0.16 g of silicon nitride powder are directly mixed with 9.2 g of coal gangue powder, 3.6 g of basic magnesium carbonate powder and 4.3 g of aluminum oxide powder, and then compacted by a tablet press, isostatically pressed, and finally sintered. The pressure parameters, sintering temperature, and time parameters are exactly the same as those in Example 1.

[0068] Comparative Example 4

[0069] The difference between Comparative Example 4 and Example 1 is that the addition of yttrium oxide powder, zinc borate powder and silicon nitride powder to the acrylic acid solution is omitted, and the remaining steps are exactly the same as those in Example 1.

[0070] The cordierite-spinel ceramic materials prepared in Examples 1-4 and the cordierite-spinel ceramic materials prepared in Comparative Examples 1-3 were subjected to hardness tests. The test results are shown in Table 1 below:

[0071] Table 1: Hardness test table of cordierite-spinel ceramic materials prepared in Examples 1-4 and Comparative Examples 1-3

[0072]

[0073]

[0074] It can be seen from the data of Comparative Examples 1-3 in the above table that the ceramic material sintered with the addition of yttrium oxide powder, zinc borate powder and silicon nitride powder in the mass of Example 2 has the highest hardness. Compared with the sintered hardness of the ceramic material of Example 1, the hardness of the ceramic material is weaker, proving that the effect of dispersing yttrium oxide powder, zinc borate powder and silicon nitride powder is better; it can be seen from the comparison of Comparative Example 4 with Example 1 that the addition of a small amount of yttrium oxide powder, zinc borate powder and silicon nitride powder can improve the hardness of the sintered ceramic.

[0075] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A cordierite-spinel ceramic material, characterized in that: including a ceramic base material and an impregnation solution; The ceramic base material is composed of coal gangue powder, basic magnesium carbonate powder, aluminum oxide powder and epoxy resin powder; The impregnation liquid is an acrylic acid solution, which further contains yttrium oxide powder, zinc borate powder, silicon nitride powder, ammonium persulfate, sodium lauryl sulfate, N,N'-methylenebisacrylamide and glycerol; The preparation method of the above-mentioned cordierite-spinel ceramic material comprises the following steps: S1. Evenly mixing coal gangue powder, basic magnesium carbonate powder, aluminum oxide powder and epoxy resin powder to obtain a mixture, placing the mixture into a mold and compacting it with a tablet press to obtain a ceramic base material; S2, placing the ceramic base material obtained in step S1 into a cold isostatic press for processing; S3, heating the ceramic base material treated in step S2 at 200° C. for 3 h, then heating to 600° C. for another 1 h; S4, pressurizing and impregnating the ceramic base material treated in step S3 into a deoxygenated acrylic acid solution, wherein the acrylic acid solution also contains yttrium oxide powder, zinc borate powder, silicon nitride powder, ammonium persulfate, sodium lauryl sulfate, N,N'-methylenebisacrylamide, and glycerol, and crosslinking at 75° C. for 2.5 hours; S5. Firing the ceramic base material processed in step S4 at 1200-1450° C. for 2-3 hours and cooling the furnace to obtain a cordierite-spinel ceramic material.

2. The cordierite-spinel ceramic material according to claim 1, characterized in that In step S1, the mass ratio of basic magnesium carbonate powder, aluminum oxide powder and coal gangue powder is 1:(0.8-2):(2.2-3.4), and the ratio of the mass of the epoxy resin powder to the total mass of basic magnesium carbonate powder, aluminum oxide powder and coal gangue powder is 1:

15.

3. The cordierite-spinel ceramic material according to claim 1, characterized in that: In step S1, the pressure of the tablet press is set to 8-12 MPa, and the holding time is 2-5 min.

4. The cordierite-spinel ceramic material according to claim 1, characterized in that: In the step S2, the pressure applied in the isostatic press is 150-200 MPa, and the holding time is 5-10 minutes.

5. The cordierite-spinel ceramic material according to claim 1, characterized in that: The pressure of the pressurized impregnation in step S4 is 5-10 MPa, the mass ratio of N,N'-methylenebisacrylamide, sodium lauryl sulfate, ammonium persulfate, acrylic acid monomer and deionized water in the acrylic acid solution is 1:4:6:800:4000; the mass ratio of glycerol to acrylic acid monomer is 1:(3-5); the mass ratio of yttrium oxide powder, zinc borate powder and silicon nitride powder is 1:1:(0.5-3); and the mass ratio of the total mass of the yttrium oxide powder, zinc borate powder and silicon nitride powder to deionized water is 1:

10.

6. The cordierite-spinel ceramic material according to claim 1, characterized in that: The silicon nitride powder was thermally oxidized at 750° C. for 1.5 hours.

7. The cordierite-spinel ceramic material according to claim 1, characterized in that: The particle size of the coal gangue powder, basic magnesium carbonate powder and aluminum oxide powder in step S1 is 25-40 μm; the particle size of the epoxy resin powder is 0.5-1 μm; and the particle size of the yttrium oxide powder, zinc borate powder and silicon nitride powder in step S3 is 30-50 nm.

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