CN112062573B - Sheet SiC-SiO2 composite material and preparation method thereof - Google Patents
Sheet SiC-SiO2 composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of material synthesis, and particularly relates to flaky SiC-SiO 2 A composite material and a method for preparing the same. The preparation method comprises the following steps: mixing SiO 2 And (3) alternately placing the coated SiC composite material and the graphite paper after oxidation treatment in a mould in sequence, tabletting, and performing microwave sintering to obtain the product. The method of the invention fully utilizes the core-shell structure formed by the microwave rapid heating effect and the good adsorption property of carbon in the graphite paper, and realizes the flaky SiC-SiO 2 And (3) rapidly synthesizing the composite material. The sheet SiC-SiO of the invention 2 The size of the composite material can be controlled by changing the size of the graphite paper in the preparation process, and the composite material has the advantages of short synthesis time, low energy consumption, suitability for large-scale rapid industrial production and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to flaky SiC-SiO 2 Composite materials and methods for making the same.
Background
The flaky SiC has good chemical stability, excellent high-temperature electrical property,The material has the characteristics of high thermal shock resistance and the like, becomes a material which is mainly concerned in the fields of high-end technologies and equipment, and has potential application value in the aspects of light emitters, sensors, solar cells and the like. The traditional method for producing the flaky SiC has the defects of complex preparation process, long production period, uncontrollable SiC size and the like, and the application of the flaky SiC is limited. SiO2 2 The composite material has good electrical insulation performance, low thermal expansion coefficient, excellent thermal shock resistance and excellent dielectric wave-transmitting performance, is widely applied to the fields of ceramics, electronic packaging, adhesives and the like, and limits the further development of the composite material due to low strength. Thus compounding the silicon dioxide and the silicon carbide to form SiC-SiO 2 The composite material has excellent performance, but the prior art has the defect of flaky SiC-SiO 2 Composite materials have been less studied.
Chinese patent application publication No. CN103539124A discloses a method for preparing silicon by microwave method, which comprises mixing silicon dioxide, silicon carbide and graphite powder, and then performing oxidation-reduction reaction by microwave irradiation under inert atmosphere to obtain silicon. The method can obtain a fused mass of silicon which is a product, and the flaky SiC-SiO can not be obtained 2 A composite material.
Disclosure of Invention
The invention aims to provide a flaky SiC-SiO 2 Preparation method of composite material, and SiC-SiO with sheet structure prepared by method 2 Composite material and controllable size.
The invention also aims to provide the flaky SiC-SiO prepared by the preparation method 2 A composite material having a dimensionally-controlled sheet-like structure.
In order to achieve the purpose, the invention adopts the technical scheme that:
flaky SiC-SiO 2 The preparation method of the composite material comprises the following steps: mixing SiO 2 The SiC-coated composite material and the graphite paper after oxidation treatment are sequentially and alternately placed in a die, pressed into sheets and subjected to microwave treatmentAnd sintering to obtain the material.
The preparation method has controllable size, fully utilizes the thermal effect and non-thermal effect of the microwave, efficiently utilizes the excellent adsorption performance of the graphite paper and realizes the flaky SiC-SiO 2 And (3) rapidly synthesizing the composite material. The tabletting can reduce the air content among the particles, increase the contact area among the particles and enhance the heat effect and the non-heat effect of microwave heating.
The preparation method of the invention utilizes graphite paper and SiO 2 The excellent microwave coupling capability of SiC in the coated SiC composite material and the plasma effect of the microwave excited gas product realize the SiC-SiO 2 The microwave rapid synthesis of the composite material greatly reduces the energy consumption (compared with the traditional industrial energy consumption, the energy consumption is reduced by more than 80 percent); and no harmful gas is generated in the reaction process, so that the pollution to the environment is reduced, and the method is suitable for large-scale rapid industrial production and has wide application prospect.
The SiO 2 The mass ratio of the coated SiC composite material to the graphite paper after oxidation treatment is (10-20): (5-15). SiO in the above ratio 2 The mixture of the coated SiC composite material and the graphite paper after oxidation treatment avoids SiO in the subsequent microwave sintering process 2 Is converted into Si.
The SiO 2 The coated SiC composite material is prepared by adopting a method comprising the following steps: uniformly mixing silicate ester and a solvent, adjusting the pH to 3-4, then adding SiC crystal seeds, uniformly mixing, and adjusting the pH to 9-11 to obtain the silicon-based catalyst. SiO can be formed by the above sol-gel method 2 Structures of coated SiC, in which SiO 2 Is amorphous silicon dioxide and SiO 2 The SiC surface is uniformly coated. The SiC seed crystal has the functions of: on one hand, the excellent wave-absorbing performance of the material is utilized to provide heat for the whole reaction process and reduce the reaction time, thereby reducing the energy consumption; on the other hand, the high temperature generated by absorbing the microwave is utilized to lead the SiO coated on the surface of the film 2 Melting to liquid, liquid SiO 2 Not only take part in the reaction to generate SiC crystals, but also bond the generated SiC crystals together, thereby realizing the SiC-SiO 2 And (3) preparing the composite material.
In order to fully hydrolyze silicate ester, the solvent is ethanol and water, and the volume ratio of the silicate ester to the ethanol to the water is (21-25): (34-38): (48 to 50). The hydrolysis rate of silicate ester can be adjusted by controlling the ratio of ethanol to water.
SiC seed crystals (0.5-1 g) are added to 100mL of silicate and solvent. Through experiments, when 0.5-1 g of SiC seed crystal is added into every 100mL of silicate and solvent, the obtained product is of a core-shell structure, and the core-shell structure cannot be formed in other proportions. If the core-shell structure can not be formed, the gas generated in the microwave sintering process directly enters the air, and finally the SiC-SiO with the sheet structure can not be formed 2 A composite material.
The oxidation treatment comprises the following steps: graphite paper is coated with KMnO 4 And H 2 SO 4 Soaking the mixture in the solution for 1.5-2 min, and then putting the mixture into H 2 O 2 Soaking in the solution for 3-8 min, taking out and drying to obtain the finished product. Through experiments, if the graphite paper is not subjected to the oxidation treatment, SiC-SiO with a sheet structure cannot be formed 2 A composite material. The surface of the graphite paper is oxidized into a lamellar layer by oxidation treatment, and the structure increases the graphite paper and SiO 2 Thereby realizing the SiC-SiO of a sheet structure 2 And (4) preparing the composite material.
And the microwave sintering is to embed the pressed sample into quartz sand for microwave sintering. The sample is embedded into the quartz sand for sintering, the quartz sand close to the sample can soften and flow in the sintering process, the quartz sand on the surface layer of the sample can be adsorbed to form a good core-shell structure by utilizing the adsorption performance of the graphite paper, the core-shell structure provides a high-temperature closed reaction zone with certain pressure for the chemical reaction of the sample inside the core-shell structure, the reaction zone not only prevents external air from directly contacting with the internal sample, thereby avoiding the influence of the external air on the SiC synthesis, achieving the purpose of reducing the energy consumption, and greatly reducing the synthesis of SiC-SiO 2 The time and temperature required by the composite material achieve the aim of low energy consumption.
The temperature of the microwave sintering is 1000-1300 ℃, and the SiC-SiO can be realized at the temperature 2 Composite materialIf the temperature is too high, the energy consumption is increased, and if the temperature is too low, the generation of SiC is affected.
In order to ensure that the reaction is fully carried out, the microwave sintering time is 1-4 h.
According to the sheet SiC-SiO 2 Preparation method of composite material for preparing flaky SiC-SiO 2 A composite material.
The sheet SiC-SiO of the invention 2 Composite material using SiO 2 The coated SiC composite material is synthesized by reacting with graphite paper, and the size can be controlled by changing the size of the graphite paper. In the microwave sintering process, SiO 2 The coated SiC crystal seed absorbs the microwave, becomes a hot spot and generates heat, and leads to the SiO coated around the crystal seed 2 Melting into liquid state, wherein part of the graphite paper after oxidation treatment and liquid SiO 2 The oxidation-reduction reaction occurs on the surface of the substrate to generate SiC and CO gas (formula (1)), and the other part of the oxidized graphite paper is mixed with solid SiO 2 The oxidation-reduction reaction (formula (2)) occurs on the surface of the substrate to generate CO gas and SiO gas, the CO gas and the SiO gas are accumulated on the surface of the graphite paper to generate the oxidation-reduction reaction to generate SiC (formula (3)), carbon in the graphite paper is consumed along with the extension of the heat preservation time, and unreacted liquid SiO gas is depleted 2 SiC generated by the reaction are adhered to each other, and finally the flake SiC-SiO with the size of the original graphite paper is synthesized 2 The composite material achieves the purpose of controlling the size. The redox reaction formulae (1) to (3) are:
C(s)+SiO 2 (l)SiC(s)+CO(g)(1)，
C(s)+SiO 2 (s)SiO(g)+CO(g)(2)，
CO(g)+SiO(g)SiC(s)+O 2 (g)(3)。
drawings
FIG. 1 is an SEM image of graphite paper after oxidation treatment;
FIG. 2 shows a sheet SiC-SiO of the present invention 2 Method for preparing composite Material flake SiC-SiO prepared in example 1 2 A core-shell structure diagram of the composite material;
FIG. 3 shows a sheet SiC-SiO of the present invention 2 Examples of composite materials1 sheet SiC-SiO 2 A visual representation of the composite;
FIG. 4 shows a sheet SiC-SiO of the present invention 2 Composite material sheet SiC-SiO of example 1 2 XRD pattern of the composite;
FIG. 5 shows a sheet-like SiC-SiO of the present invention 2 Composite material sheet SiC-SiO of example 1 2 SEM images of the composite;
FIG. 6 shows a sheet SiC-SiO of the present invention 2 Composite material sheet SiC-SiO of example 2 2 A visual representation of the composite;
FIG. 7 shows a sheet SiC-SiO of the present invention 2 Composite material sheet SiC-SiO of example 2 2 XRD pattern of the composite;
FIG. 8 shows a sheet-like SiC-SiO of the present invention 2 Composite material sheet SiC-SiO of example 2 2 SEM images of the composite;
FIG. 9 shows a sheet SiC-SiO of the present invention 2 Composite material sheet SiC-SiO of example 3 2 A visual representation of the composite;
FIG. 10 shows a sheet SiC-SiO of the present invention 2 Composite material sheet SiC-SiO of example 3 2 XRD pattern of the composite;
FIG. 11 shows a sheet-like SiC-SiO of the present invention 2 Composite material sheet SiC-SiO of example 3 2 SEM image of the composite material.
Detailed Description
The sheet SiC-SiO of the invention 2 The length and width of the graphite paper used in the preparation process of the composite material are 25mm multiplied by 25mm, and the thickness is 0.5 mm.
The sheet SiC-SiO of the invention 2 In the preparation process of the composite material, the tablet is an equiaxial pressed tablet, the equiaxial pressing pressure is 2-6 MPa, and the pressure maintaining time is 60-120 s. The pressed sheet is a cylindrical sheet with the diameter of 30mm and the thickness of 7-12 mm.
The sheet SiC-SiO of the invention 2 The microwave sintering of the composite material is carried out in an air atmosphere.
SiO of the invention 2 In the preparation of the coated SiC composite material, the methodThe mixing is carried out mechanically. The mechanical stirring is carried out for 1.5-2.5 h under the condition of 35-45 ℃ water bath.
SiO of the invention 2 In the preparation process of the coated SiC composite material, citric acid is used as a reagent for adjusting the pH to 3-4. And when the pH is adjusted to be 9-11, the used reagent is ammonia water, and the mass fraction of the ammonia water is 10-20%.
SiO of the invention 2 In the preparation process of the coated SiC composite material, the grain diameter of the used SiC seed crystal is 5 μm.
In the oxidation treatment process of the graphite paper, the KMnO is contained 4 And H 2 SO 4 The mass ratio of the two in the solution of (1): 16 to 20. Containing KMnO 4 And H 2 SO 4 Is prepared from KMnO 4 And concentrated sulfuric acid, wherein H in the concentrated sulfuric acid 2 SO 4 The mass fraction of (2) is 98%. The temperature of the oxidized graphite paper is 110 ℃ during drying, and the time is 3-4 h. The invention is further described with reference to the following specific embodiments and the accompanying drawings.
Sheet SiC-SiO 2 Example 1 of the preparation of the composite Material
The sheet SiC-SiO of this example 2 The preparation method of the composite material comprises the following steps:
(1)SiO 2 preparing a SiC-coated seed crystal composite material:
placing the reaction vessel in a constant-temperature water bath kettle at 40 ℃, and taking the mixture of tetraethoxysilane, absolute ethyl alcohol and distilled water according to the volume ratio of 23: 35: 50 in a reactor (total 216mL), adjusting the pH value to 3 by using citric acid, and stirring for 2 hours at 40 ℃ to obtain a mixed solution A; adding SiC seed crystal with the particle size of 5 mu m into the mixed solution A, wherein the mass of the added seed crystal is 1.08g (which is 0.5 percent of the total volume of the tetraethoxysilane, the absolute ethyl alcohol and the water); stirring at 40 deg.C for 2h, adjusting pH to 10 with ammonia water, and stirring at 40 deg.C for 2h to obtain mixed solution B; drying the mixed solution B in a drying oven at the temperature of 80 ℃ for 10 hours to obtain SiO 2 A composite material coated with SiC seed crystal.
(2) Oxidation treatment of graphite paper
Taking industrial graphite paper as a carbon source, and mixing 10g of potassium permanganate and 183.05g of concentrated sulfuric acid (the mass fraction of the concentrated sulfuric acid is 98%) in a 250mL glass beaker to obtain a strong oxidation solution; then, the carbon source was immersed in a strongly oxidizing solution for 1.5min, rinsed 3 times with distilled water, and then immersed in a hydrogen peroxide solution (H) 2 O 2 30 percent of the mass fraction), rinsing the paper for 5 times by distilled water, and finally drying the carbon source in a drying box at 110 ℃ for 3 hours to obtain the graphite oxide paper. The surface of the graphite paper after oxidation treatment is in a lamellar shape, and the SEM thereof is shown in FIG. 1.
(3) Tabletting and microwave sintering
Firstly weighing 6g of the composite material prepared in the step (1) and putting the composite material into a cylindrical mold with the diameter of 30mm, then taking 20 layers (with the mass of 10g) of the graphite oxide paper prepared in the step (2) and putting the graphite oxide paper into the mold, and finally weighing 9g of the composite material prepared in the step (1) and putting the composite material into the mold. Placing the mold in an oil press, maintaining the pressure for 90s under 4MPa to obtain a cylindrical sheet with the diameter of 30mm and the thickness of 10mm, embedding the cylindrical sheet into quartz sand of an alumina crucible, placing the crucible in a multimode resonant cavity microwave oven with the frequency of 2.45GHz, adding a heat insulation structure (formed by filling alumina fiber cotton in a cavity formed by mullite), carrying out microwave sintering at 1300 ℃ for 1h in an air atmosphere, finally obtaining a product with a core-shell structure as shown in figure 2, removing a quartz sand shell on the surface, and obtaining the sheet SiC-SiO 2 A composite material.
Sheet SiC-SiO 2 Example 2 of the preparation of the composite Material
The sheet SiC-SiO of this example 2 The preparation method of the composite material comprises the following steps:
(1)SiO 2 preparing a wrapping SiC seed crystal composite material:
placing the reaction vessel in a constant-temperature water bath kettle at 35 ℃, and taking the mixture of tetraethoxysilane, absolute ethyl alcohol and distilled water according to the volume ratio of 21: 34: 48 (206 mL in total), adjusting the pH value to 3 with citric acid, and stirring at 35 ℃ for 1.5h to obtain a mixed solution A; 2.06g (as silicon carbide) of a SiC seed crystal having a particle size of 5 μm was added to the mixed solution AEthyl acetate, absolute ethanol and 1% of the total volume of water); stirring at 35 deg.C for 1.5h, adjusting pH to 11 with ammonia water, and stirring at 35 deg.C for 1.5h to obtain mixed solution B; drying the mixed solution B in a drying oven at 80 ℃ for 12h to obtain SiO 2 A composite material coated with SiC seed crystal.
(2) Oxidation treatment of graphite paper
Taking industrial graphite paper as a carbon source, and mixing 10g of potassium permanganate and 160g (mass fraction is 98%) of concentrated sulfuric acid in a 250mL glass beaker to obtain a strong oxidation solution; and then, soaking the carbon source in a strong oxidation solution for 2min, rinsing with distilled water for 5 times, soaking the carbon source in a hydrogen peroxide (with the mass fraction of 30%) solution for 3min, rinsing with distilled water for 3 times, and finally drying the carbon source in a drying oven at the temperature of 110 ℃ for 4h to obtain the graphite oxide paper.
(3) Tabletting and microwave sintering
Weighing 4g of the composite material prepared in the step (1) and putting the composite material into a cylindrical mold with the diameter of 30mm, then weighing 10 layers (with the mass of 5g) of the graphite oxide paper prepared in the step (2) and putting the graphite oxide paper into the mold, and finally weighing 6g of the composite material prepared in the step (1) and putting the composite material into the mold. Placing the mold in an oil press, maintaining the pressure for 120s under 2MPa to obtain a cylindrical sheet with the diameter of 30mm and the thickness of 7mm, embedding the cylindrical sheet into quartz sand of an alumina crucible, placing the crucible in a multi-mode resonant cavity microwave oven with the frequency of 2.45GHz, adding a heat preservation structure (formed by filling alumina fiber cotton in a cavity formed by mullite), preserving the heat for 2h at 1300 ℃ in an air atmosphere for microwave sintering, finally obtaining a product with a core-shell structure, removing the quartz sand shell on the surface, and obtaining the sheet SiC-SiO 2 A composite material.
Sheet-like SiC-SiO 2 Example 3 of the preparation method of the composite Material
The sheet SiC-SiO of this example 2 The preparation method of the composite material comprises the following steps:
(1)SiO 2 preparing a SiC-coated seed crystal composite material:
placing the reaction vessel in a constant-temperature water bath kettle at 45 ℃, and taking tetraethoxysilane, absolute ethyl alcohol andthe volume ratio of the distilled water is 25: 38: mixing the three solutions (226 mL in total) in a reactor according to the proportion of 50, adjusting the pH value to 4 by using citric acid, and stirring for 2.5 hours at the temperature of 45 ℃ to obtain a mixed solution A; 113g of SiC seed crystal (which is 0.5 percent of the total volume of the ethyl orthosilicate, the absolute ethyl alcohol and the water) with the particle size of 5 mu m is added into the mixed solution A; stirring at 45 deg.C for 2.5h, adjusting pH to 9 with ammonia water, and stirring at 45 deg.C for 2.5h to obtain mixed solution B; drying the mixed solution B in a drying oven at 80 ℃ for 11h to obtain SiO 2 A composite material coated with SiC seed crystal.
(2) Oxidation treatment of graphite paper
Taking industrial graphite paper as a carbon source, and mixing 10g of potassium permanganate and 200g (mass fraction is 98%) of concentrated sulfuric acid in a 250mL glass beaker to obtain a strong oxidation solution; and then, soaking the carbon source in a strong oxidation solution for 2min, rinsing with distilled water for 3 times, soaking the carbon source in a hydrogen peroxide solution (the mass fraction is 30%) for 8min, rinsing with distilled water for 3 times, and finally drying the carbon source in a drying oven at 110 ℃ for 3h to obtain the graphite oxide paper.
(3) Tabletting and microwave sintering
Firstly weighing 8g of the composite material prepared in the step (1) and putting the composite material into a cylindrical mould with the diameter of 30mm, then taking 30 layers (with the mass of 15g) of the graphite oxide paper prepared in the step (2) and putting the graphite oxide paper into the mould, and finally weighing 12g of the composite material prepared in the step (1) and putting the composite material into the mould. Placing the mould in an oil press, maintaining the pressure for 60s under 6MPa to obtain a cylindrical sheet with the diameter of 30mm and the thickness of 12mm, embedding the cylindrical sheet into quartz sand of an alumina crucible, placing the crucible in a multi-mode resonant cavity microwave oven with the frequency of 2.45GHz, adding a heat preservation structure (formed by filling alumina fiber cotton in a cavity formed by mullite), preserving the heat for 4h at the temperature of 1000 ℃ in an air atmosphere, carrying out microwave sintering, finally obtaining a product with a core-shell structure, removing a quartz sand shell on the surface, and obtaining the sheet SiC-SiO 2 A composite material.
Sheet-like SiC-SiO 2 Example 1 of composite Material
The sheet SiC-SiO of this example 2 The composite material is made of SiC-SiO 2 Of composite materialsPreparation method the preparation method of example 1 was followed to obtain, as shown in FIG. 3, SiC-SiO 2 The length and width dimensions of the composite material were 25mm x 25mm, the thickness was 0.5mm, and were almost identical to the original graphite paper dimensions, and the missing corners were mainly due to the removal of the quartz sand shell.
Sheet SiC-SiO 2 Example 2 of composite Material
The sheet SiC-SiO of this example 2 The composite material is made of SiC-SiO 2 Preparation of composite material prepared by the method of example 2, as shown in fig. 6.
Sheet SiC-SiO 2 Example 3 of composite Material
Sheet-like SiC-SiO of the present example 2 The composite material is made of SiC-SiO 2 Method of making a composite material prepared as in example 3, is shown in fig. 9.
Test example 1
Mixing SiC-SiO 2 Composite Material sheet SiC-SiO of examples 1 to 3 2 XRD testing was performed on the composite material, and the results are shown in FIG. 4, FIG. 7 and FIG. 10, respectively. As can be seen from FIGS. 4, 7 and 10, the product obtained by the production method of the present invention is SiC-SiO 2 The composite material can increase the crystallinity of SiC in the product by prolonging the heat preservation time or increasing the temperature.
Test example 2
Mixing SiC-SiO 2 Composite Material examples 1 to 3 of sheet-shaped SiC-SiO 2 The composite material was subjected to SEM test, and the test results are shown in fig. 5, fig. 8, and fig. 11, respectively. As can be seen from FIGS. 5, 8 and 11, the composite material is mainly composed of SiO 2 Wrapping and adhering SiC crystals, and gradually increasing the densification degree of the product along with the prolonging of the heat preservation time or the increase of the temperature.
Claims (6)
1. Flaky SiC-SiO 2 The preparation method of the composite material is characterized by comprising the following steps: mixing SiO 2 Alternately placing the coated SiC composite material and the oxidized graphite paper in a die in sequence, tabletting and microwave sintering to obtain the product; the SiO 2 Coated SiC composite materialThe mass ratio of the graphite paper to the graphite paper after oxidation treatment is (10-20) to (5-15); the SiO 2 The coated SiC composite material is prepared by adopting a method comprising the following steps: uniformly mixing silicate ester and a solvent, adjusting the pH to 3-4, then adding SiC crystal seeds, uniformly mixing, and adjusting the pH to 9-11 to obtain the silicon-based catalyst; adding 0.5-1 g of SiC seed crystal into each 100mL of silicate ester and solvent; the solvent is ethanol and water, and the volume ratio of the silicate ester to the ethanol to the water is (21-25): (34-38): (48-50).
2. The sheet form SiC-SiO of claim 1 2 The preparation method of the composite material is characterized in that the oxidation treatment comprises the following steps: graphite paper is coated with KMnO 4 And H 2 SO 4 Soaking in the solution for 1.5-2 min, and then putting into H 2 O 2 And soaking in the solution for 3-8 min, taking out and drying to obtain the product.
3. The sheet form SiC-SiO of claim 1 2 The preparation method of the composite material is characterized in that the microwave sintering is to embed the pressed sample into quartz sand for microwave sintering.
4. Flake SiC-SiO according to claim 1 or 3 2 The preparation method of the composite material is characterized in that the temperature of the microwave sintering is 1000-1300 ℃.
5. Flake SiC-SiO according to claim 1 or 3 2 The preparation method of the composite material is characterized in that the microwave sintering time is 1-4 h.
6. The sheet-like SiC-SiO of claim 1 2 Preparation method of composite material for preparing flaky SiC-SiO 2 A composite material.
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