Cordierite-spinel ceramic material and preparation method thereof

Abstract

The invention relates to the technical field of ceramic material preparation, in particular to a preparation method of a cordierite-spinel ceramic material, which comprises the following steps: S1, uniformly mixing coal gangue powder, basic magnesium carbonate powder, alumina powder and epoxy resin powder to obtain a mixture, and compacting to obtain a ceramic base material; s2, putting the ceramic base material obtained in the step S1 into a cold isostatic press; s3, performing heat treatment on the ceramic base material treated in the step S2; s4, pressurizing and dipping the ceramic base material treated in the step S3 into a deoxidized acrylic acid solution; and S5, carrying out high-temperature calcination on the ceramic base material treated in the step S4 to obtain the cordierite-spinel ceramic material. According to the prepared ceramic material, a small amount of yttrium oxide powder, zinc borate powder and silicon nitride powder are dispersed into micropores of a ceramic base material through acrylic acid hydrogel, and formed ceramic is high in hardness.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic material preparation, and specifically 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 the industrial, aerospace, and electronic fields, 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 procedures, which not only increases production costs but also limits their applications. Therefore, the development of new composite ceramic materials has become one of the hotspots in current materials science research, especially the recycling and reuse of industrial waste. Coal gangue, as a solid waste generated during coal mining and washing, not only occupies land resources when piled up in large quantities but may also cause environmental pollution. Coal gangue contains abundant elements such as silicon, aluminum, and iron, and its utilization value is potential. In recent years, researchers have begun to explore the feasibility of using coal gangue as a raw material to prepare ceramic materials, aiming to reduce the production cost of ceramic materials while enabling 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 requirements. However, the cordierite-spinel ceramic materials used in traditional methods usually have relatively high requirements for the purity of raw materials, and the synthesis process is also relatively complex, which limits their production and application to a certain extent. For example, the patent technology of "Cordierite-Spinel Ceramic Material with High Infrared Emissivity and Its Preparation Method (Patent No. CN105198394B)" discloses a method for preparing cordierite-spinel ceramic materials using waste fly ash as a raw material, mainly relying on high-purity raw materials such as high-purity alumina and high-purity magnesia. This not only increases production costs but also hinders large-scale applications, with low mechanical strength and high porosity.

[0003] Therefore, the present invention aims to develop a cordierite-spinel ceramic material mainly using coal gangue, combined with basic magnesium carbonate and alumina, through a simple and effective process flow. By introducing raw materials such as silicon nitride powder, yttrium oxide powder, and zinc borate powder to enhance the performance, and the cold isostatic pressing process, the mechanical properties of the material are further optimized. In addition, during the introduction of a small amount of silicon nitride powder, yttrium oxide powder, and zinc borate powder in the present invention, the introduction method of silicon nitride powder, yttrium oxide powder, and zinc borate powder is optimized by using gelled acrylic acid as a carrier to improve their uniformity, providing 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-mentioned background technology.

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

[0006] A cordierite-spinel ceramic material includes a ceramic base material and an impregnating solution;

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

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

[0009] A preparation method of a cordierite-spinel ceramic material includes the following steps:

[0010] S1. Mix the coal gangue powder, basic magnesium carbonate powder, alumina powder and epoxy resin powder evenly to obtain a mixture, and put the mixture into a mold and compact it by a tablet press to obtain a ceramic base material;

[0011] S2. Put the ceramic base material obtained in step S1 into a cold isostatic press for treatment;

[0012] S3. Heat-treat the ceramic base material treated in step S2 at 200 °C for 3 h, and then raise the temperature to 600 °C and continue to treat for 1 h;

[0013] S4. Press-impregnate the ceramic base material treated in step S3 into a deoxygenated acrylic acid solution, and the acrylic acid solution further contains yttrium oxide powder, zinc borate powder, silicon nitride powder, ammonium persulfate, sodium dodecyl sulfate, N,N'-methylenebisacrylamide and glycerol, and crosslink at 75 °C for 2.5 h;

[0014] S5. Fire the ceramic base material treated in step S4 at 1200-1450 °C for 2-3 h, and cool it with the furnace to obtain the cordierite-spinel ceramic material.

[0015] Further, the mass ratio between the basic magnesium carbonate powder, alumina powder and coal gangue powder in step S1 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 the basic magnesium carbonate powder, alumina powder and coal gangue powder is 1:15.

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

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

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

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

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

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

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:

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

[0024] 2. The incorporation amounts of the silicon nitride powder, yttrium oxide powder and zinc borate powder in the present invention are less. By impregnating the ceramic base material in the acrylic acid solution, it is convenient for the dispersion of a small amount of silicon nitride powder, yttrium oxide powder and zinc borate powder. Through the cross-linking of acrylic acid, a network structure is formed, enabling 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 melting and degreasing with the epoxy resin powder, improving the hardness of the sintered finished product. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0027] Figure 3 SEM images of cordierite-spinel ceramic materials prepared in Examples 1-4 of the present invention. Detailed implementation manners

[0028] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0029] Please refer to Figures 1 to 3 , the present invention provides:

[0030] Example 1

[0031] A preparation method of a cordierite-spinel ceramic material, comprising the following steps:

[0032] S1. Mix 9.2 g of coal gangue powder, 3.6 g of basic magnesium carbonate powder, 4.3 g of alumina powder and 1.14 g of epoxy resin powder evenly to obtain a mixture. The particle sizes of the coal gangue powder, basic magnesium carbonate powder and alumina powder are 40 μm, and the particle size of the epoxy resin powder is 0.8 μm. Put the mixture into a mold and compact it by a tablet press. The pressure set by the tablet press is 10 MPa, and the pressure holding time is 4 min to obtain a ceramic base material;

[0033] S2. Put the ceramic base material obtained in step S1 into an isostatic press, and the pressure applied during the isostatic press treatment is 180 MPa, and the pressure holding time is 8 min

[0034] S3. Heat-treat the ceramic base material treated in step S2 at 200 °C for 3 h, and then raise the temperature to 600 °C and continue to treat for 1 h;

[0035] S4. Pressurize and impregnate the ceramic base material treated in step S3 into a deoxygenated acrylic acid solution. The pressure of the pressurized impregnation is 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 dodecyl sulfate, 0.01 g of N,N'-methylenebisacrylamide and 2 g of glycerol, and crosslink at 75 °C for 2.5 h. The particle sizes of the yttrium oxide powder, zinc borate powder and silicon nitride powder are 50 nm;

[0036] S5. Bake the ceramic base material processed in step S4 at 1300 °C for 2.5 h and cool it with the furnace to obtain the cordierite-spinel ceramic material.

[0037] Example 2

[0038] A preparation method of a cordierite-spinel ceramic material includes the following steps:

[0039] S1. Mix 7.92 g of coal gangue powder, 3.6 g of basic magnesium carbonate powder, 2.88 g of alumina powder and 0.96 g of epoxy resin powder evenly to obtain a mixture. The particle sizes of the coal gangue powder, basic magnesium carbonate powder and alumina powder are 25 μm, and the particle size of the epoxy resin powder is 0.5 μm. Put the mixture into a mold and compact it with a tablet press. The pressure set by the tablet press is 8 MPa and the pressure holding time is 2 min to obtain a ceramic base material;

[0040] S2. Put the ceramic base material obtained in step S1 into an isostatic press. The pressure applied during the isostatic pressing process is 150 MPa and the pressure holding time is 5 min;

[0041] S3. Heat-treat the ceramic base material processed in step S2 at 200 °C for 3 h, and then raise the temperature to 600 °C and continue to treat for 1 h;

[0042] S4. Pressurize and impregnate the ceramic base material processed in step S3 into a deoxygenated acrylic acid solution. The pressure of the pressure impregnation is 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 of yttrium oxide powder, 1.6 g of zinc borate powder, 0.8 g of silicon nitride powder, 0.06 g of ammonium persulfate, 0.04 g of sodium dodecyl sulfate, 0.01 g of N,N'-methylenebisacrylamide and 2.67 g of glycerol. Crosslink at 75 °C for 2.5 h. The particle sizes of the yttrium oxide powder, zinc borate powder and silicon nitride powder are 30 nm;

[0043] S5. Bake the ceramic base material processed in step S4 at 1200 °C for 2 h and cool it with the furnace to obtain the cordierite-spinel ceramic material.

[0044] Example 3

[0045] A preparation method of a cordierite-spinel ceramic material includes the following steps:

[0046] S1. Mix 7.48 g of coal gangue powder, 2.2 g of basic magnesium carbonate powder, 4.4 g of alumina powder and 0.94 g of epoxy resin powder evenly to obtain a mixture. The particle sizes of the coal gangue powder, basic magnesium carbonate powder and alumina powder are 40 μm, and the particle size of the epoxy resin powder is 1 μm. Put the mixture into a mold and compact it through a tablet press. The pressure set by the tablet press is 12 MPa, and the pressure holding time is 5 min to obtain a ceramic base material;

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

[0048] S3. Heat-treat the ceramic base material treated in step S2 at 200 °C for 3 h, and then raise the temperature to 600 °C and continue to treat for 1 h;

[0049] S4. Pressurize and impregnate the ceramic base material treated in step S3 into a deoxygenated acrylic acid solution. The pressure of the pressurized impregnation is 10 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 0.8 g of yttrium oxide powder, 0.8 g of zinc borate powder, 2.4 g of silicon nitride powder, 0.06 g of ammonium persulfate, 0.04 g of sodium dodecyl sulfate, 0.01 g of N,N'-methylenebisacrylamide and 1.6 g of glycerol. Crosslink at 75 °C for 2.5 h. The particle sizes of the yttrium oxide powder, zinc borate powder and silicon nitride powder are 50 nm;

[0050] S5. Fire the ceramic base material treated in step S4 at 1450 °C for 3 h and cool it with the furnace to obtain a cordierite-spinel ceramic material.

[0051] Example 4

[0052] A preparation method of a cordierite-spinel ceramic material, comprising the following steps:

[0053] S1. Mix 7.7 g of coal gangue powder, 2.8 g of basic magnesium carbonate powder, 3.9 g of alumina powder and 0.96 g of epoxy resin powder evenly to obtain a mixture. The particle sizes of the coal gangue powder, basic magnesium carbonate powder and alumina powder are 30 μm, and the particle size of the epoxy resin powder is 0.5 μm. Put the mixture into a mold and compact it through a tablet press. The pressure set by the tablet press is 10 MPa, and the pressure holding time is 4 min to obtain a ceramic base material;

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

[0055] S3. Heat-treat the ceramic base material treated in step S2 at 200 °C for 3 h, and then raise the temperature to 600 °C and continue to treat for 1 h;

[0056] S4. Impregnate the ceramic base material processed in step S3 into the deoxygenated acrylic acid solution under 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 dodecyl sulfate, 0.01 g of N,N'-methylenebisacrylamide, and 1.8 g of glycerol. Crosslink at 75 °C for 2.5 h. The particle sizes of the yttrium oxide powder, zinc borate powder, and silicon nitride powder are 40 nm.

[0057] S5. Fire the ceramic base material processed in step S4 at 1400 °C for 3 h and cool it with the furnace to obtain the cordierite-spinel ceramic material.

[0058] In the present invention, the silicon nitride powder is thermally oxidized at 750 °C for 1.5 h to improve the dispersion performance 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 the acrylic acid solution can be assisted by ultrasonic waves. The frequency of the ultrasonic waves is 40 KHz. In the above examples, the acrylic acid solution is sufficient for the ceramic base material.

[0060] In the present invention Figure 2 shows the XRD test results of the cordierite-spinel ceramic materials prepared in Examples 1-4. It can be concluded from the figure that the test results of the ceramic materials are mainly two phases of cordierite and spinel; Figure 3 shows the SEM images of Examples 1-4, Figure 3 in which (a), (b), (c), and (d) represent the SEM images of Examples 1, 2, 3, and 4 respectively. It can be further confirmed from the figure 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 in the present invention, the following comparative examples were 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 evenly with 9.2 g of coal gangue powder, 3.6 g of basic magnesium carbonate powder, and 4.3 g of alumina powder, then compacted by a tablet press, followed by isostatic pressing treatment, 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 alumina powder, then compacted by a tablet press, followed by isostatic pressing, 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 alumina powder, then compacted by a tablet press, followed by isostatic pressing, 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 is cancelled in the acrylic acid solution, and the remaining steps are exactly the same as those in Example 1.

[0070] The hardness of the cordierite-spinel ceramic materials prepared in Examples 1-4 and the cordierite-spinel ceramic materials prepared in Comparative Examples 1-3 was tested, and 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] From the data of Comparative Examples 1-3 in the above table, it can be seen that the hardness of the ceramic material sintered with the amounts of yttrium oxide powder, zinc borate powder and silicon nitride powder in Example 2 is the highest. Compared with the sintering hardness of the ceramic material in Example 1, the hardness of the ceramic material is weaker, which proves that the effect of dispersing yttrium oxide powder, zinc borate powder and silicon nitride powder is better; from the comparison between Comparative Example 4 and Example 1, it can be seen that adding a small amount of yttrium oxide powder, zinc borate powder and silicon nitride powder can improve the hardness of the sintered ceramic.

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

Claims

1. A cordierite-spinel ceramic material, characterized in that, It includes a ceramic base material and an impregnating solution; The ceramic base material is composed of coal gangue powder, basic magnesium carbonate powder, alumina powder and epoxy resin powder; The impregnating solution is an acrylic acid solution, and the acrylic acid solution also contains yttrium oxide powder, zinc borate powder, silicon nitride powder, ammonium persulfate, sodium dodecyl sulfate, N,N'-methylenebisacrylamide and glycerol.

2. A method for preparing a cordierite-spinel ceramic material as described in claim 1, characterized in that, It includes the following steps: S1. Mix the coal gangue powder, basic magnesium carbonate powder, alumina powder and epoxy resin powder evenly to obtain a mixture, put the mixture into a mold and compact it by a tablet press to obtain the ceramic base material; S2. Put the ceramic base material obtained in step S1 into a cold isostatic press for treatment; S3. Heat-treat the ceramic base material treated in step S2 at 200 °C for 3 h, and then raise the temperature to 600 °C and continue to treat for 1 h; S4. Press-impregnate the ceramic base material treated in step S3 into the deoxygenated acrylic acid solution. The acrylic acid solution also contains yttrium oxide powder, zinc borate powder, silicon nitride powder, ammonium persulfate, sodium dodecyl sulfate, N,N'-methylenebisacrylamide and glycerol, and crosslink at 75 °C for 2.5 h; S5. Fire the ceramic base material treated in step S4 at 1200 - 1450 °C for 2 - 3 h, and cool it with the furnace to obtain the cordierite-spinel ceramic material.

3. The preparation method of the cordierite-spinel ceramic material according to claim 2, characterized in that, In step S1, the mass ratio between the 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 the basic magnesium carbonate powder, alumina powder and coal gangue powder is 1:

15.

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

5. The preparation method of the cordierite-spinel ceramic material according to claim 2, characterized in that, In step S2, the pressure applied during the isostatic press treatment is 150 - 200 MPa, and the pressure holding time is 5 - 10 min.

6. The preparation method of the cordierite-spinel ceramic material according to claim 2, characterized in that, In step S4, the pressure of the press-impregnation is 5 - 10 MPa. The mass ratio between N,N'-methylenebisacrylamide, sodium dodecyl sulfate, ammonium persulfate, acrylic acid monomer and deionized water in the acrylic acid solution is 1:4:6:800:4000; the mass ratio between glycerol and the acrylic acid monomer is 1:(3 - 5); the mass ratio between the yttrium oxide powder, zinc borate powder and silicon nitride powder is 1:1:(0.5 - 3); the mass ratio between the total mass of the yttrium oxide powder, zinc borate powder and silicon nitride powder and deionized water is 1:

10.

7. The preparation method of the cordierite-spinel ceramic material according to claim 2, wherein The silicon nitride powder is thermally oxidized at 750 °C for 1.5 h.

8. The preparation method of the cordierite-spinel ceramic material according to claim 2, wherein In step S1, the particle sizes of the coal gangue powder, basic magnesium carbonate powder and alumina powder are 25 - 40 μm; the particle size of the epoxy resin powder is 0.5 - 1 μm; in step S3, the particle sizes of the yttrium oxide powder, zinc borate powder and silicon nitride powder are 30 - 50 nm.

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