CN108129151B - Graphene/silicon carbide nano composite structure monolithic ceramic and preparation method thereof - Google Patents
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Abstract
A graphene/silicon carbide nano composite structure monolithic ceramic and a preparation method thereof relate to the preparation of ceramic materials. 1) Precursor PCS (GO)x) Synthesizing; 2) monolithic ceramic SiC (rGO) with graphene/silicon carbide nano composite structurex) And (4) preparing. Precursor PCS (GO) is prepared by taking GO, VTES and PCS as raw materials through a chemical modification methodx) Powder is subjected to compression molding and high-temperature pyrolysis to obtain compact graphene/silicon carbide nano composite structure monolithic ceramic SiC (rGO)x). Wherein VTES has a bond of-Si-O-and-CH ═ CH2The group can compound GO and PCS into a new GO-VTES-PCS macromolecular structure. The GO is compounded into the silicon carbide ceramic, so that the cross-linking area of a precursor can be remarkably enlarged, the formation of SiC nanocrystals is inhibited, the sintering temperature is reduced, and the problems of difficult molding and poor compactness of the silicon carbide monolithic ceramic prepared by a precursor method are solved.
Description
Technical Field
The invention relates to preparation of ceramic materials, in particular to graphene/silicon carbide nano composite structure monolithic ceramic and a preparation method thereof.
Background
The silicon carbide ceramic not only has the advantages of corrosion resistance, wear resistance, high hardness, good chemical stability, low thermal expansion coefficient and the like at normal temperature, but also shows excellent mechanical properties at high temperature, is widely applied to the fields of electronics, machinery, nuclear energy and the like, and can be prepared by methods such as reaction sintering, hot-pressing sintering, normal-pressure sintering and the like at present. Patent ZL 200910020810.2 discloses a preparation method of silicon carbide-based reinforced composite ceramic, and the ceramic material with good strength and toughness is obtained after compression molding and siliconizing and sintering at 1450-1550 ℃. Patent ZL 200910098377.4 discloses a preparation method of normal pressure sintering silicon carbide ceramic, which is characterized in that graphite powder and boron carbide powder are used as sintering aids, and sintering is carried out under the protection of argon atmosphere at 2150-2200 ℃ after the steps of segmented ball milling, spray granulation, compression molding, segmented drying and the like, so that the corrosion-resistant silicon carbide ceramic with higher purity is prepared. Patent ZL 201410116797.1 discloses a method for preparing a large-scale self-bonding silicon carbide product by casting molding, which adopts a vibration casting molding technology, is sintered under the protection of 1300-1500 ℃ inert atmosphere, and can be applied to industries such as steel, nonferrous metals and the like. However, since the strong covalent bond of silicon carbide is not favorable for the densification, the conventional preparation method needs to add a sintering aid or provide a higher temperature in the sintering process of the silicon carbide ceramic, so that an impurity phase introduced by the sintering aid remains in the ceramic matrix, the mechanical property of the ceramic matrix is affected, and the production cost is higher.
The silicon carbide ceramic prepared by the precursor method has received much attention because of its excellent mechanical strength, corrosion resistance, thermal shock resistance, thermal stability, chemical stability and the like. Compared with the traditional silicon carbide ceramic preparation technology, the precursor method has high flexibility in design and forming, has low requirement on sintering temperature, does not need to add a sintering aid, and has great advantages. The high-purity light silicon carbide ceramic (amorphous, crystalline or nano composite material) can be prepared by a precursor method, and has potential application value in the aspect of preparing ceramic devices with complex shapes and structures. Patent ZL 201010280856.0 discloses a method for making continuous long silicon carbide fibers using Polycarbosilane (PCS) precursors. Patent ZL 200510031775.6 discloses a technology for preparing a compact silicon carbide ceramic coating by taking trichloromethylsilane as a precursor and adopting a chemical vapor deposition method, which is suitable for preparing a reflecting layer of an optical reflector. Patent US 6635215B 2 discloses a method for preparing carbon fiber reinforced silicon carbide composite material by impregnating silicon carbide fiber with a mixed precursor of polycarbosilane and polyvinylsilane and sintering, and the obtained product has high purity and excellent heat resistance. Patent ZL 201010152549.4 discloses a precursor method for preparing porous silicon carbide material, which uses silicon-resin core-shell structure powder as a precursor, and prepares a porous silicon carbide ceramic with high thermal shock resistance after pressure forming, carbonization and sintering. Although the silicon carbide prepared by the precursor method shows good performance in low-dimensional forms (fibers, films, coatings and the like), the preparation technology of three-dimensional ceramic materials such as silicon carbide monolithic ceramics, bulk ceramics, ceramic matrix composite materials and the like has some problems, such as high production cost, and the precipitation of a large amount of SiC nanocrystals in products, and the problem that the preparation of large-area silicon carbide monolithic ceramics is difficult to form is particularly prominent. In the process of pyrolysis of the precursor, a large amount of gaseous substances are slowly released, so that the defects of cracks, air holes and the like of single-chip ceramics and block ceramics can be caused, and the density of the product is seriously influenced, thereby limiting the application of the precursor method for preparing the silicon carbide ceramics in industry. In order to improve the forming capability of the precursor ceramic, prepare the silicon carbide monolithic ceramic with excellent performance and apply the silicon carbide monolithic ceramic to industrial production, the crosslinking of the high molecular weight solid precursor becomes a key process for preparing the silicon carbide ceramic.
Disclosure of Invention
The invention aims to provide a graphene/silicon carbide nano composite structure monolithic ceramic with high hardness, low density and low linear shrinkage rate, aiming at the defects of the prior art.
The invention also aims to provide a preparation method of the graphene/silicon carbide nano composite structure monolithic ceramic, which is simple and economic and can be applied to industrial production.
The graphene/silicon carbide nano composite structure monolithic ceramic SiC (rGO) of the inventionx) Is composed of a PCS precursor (GO)x) Obtained by pyrolysis at high temperature, said PCS (GO)x) The structural general formula is as follows:
the preparation method of the graphene/silicon carbide nano composite structure monolithic ceramic comprises the following steps:
1) precursor PCS (GO)x) Synthesis of (2)
PCS and Karstedt catalyst are dissolved in organic solvent, Graphene Oxide (GO) powder is mixed into deionized water and ultrasonically dispersed, and then PCS/dimethylbenzene mixture is mixedAdding GO aqueous solution, adding Vinyltriethoxysilane (VTES) into the mixed solution, and adjusting the mixed solution to be acidic by using diluted hydrochloric acid; heating the mixed solution in water bath while magnetically stirring, standing, collecting supernatant, distilling under reduced pressure with rotary evaporator to obtain black solid, and grinding to obtain fine precursor PCS (GO)x) Powder products, wherein x is the mass ratio of PCS to GO;
2) monolithic ceramic SiC (rGO) with graphene/silicon carbide nano composite structurex) Preparation of
The PCS (GO) obtained in the step 1)x) Pressing the powder into green bodies, placing the green bodies on graphite paper, and pyrolyzing the green bodies under the protection of inert gas to obtain the graphene/silicon carbide nano composite structure monolithic ceramic SiC (rGO)x) (ii) a PCS is cracked at high temperature to generate silicon carbide (SiC), and GO is reduced into reduced graphene oxide (rGO) through high-temperature final burning.
In the step 1), the mass ratio of the PCS to the GO is preferably 10: 1-5, and the volume ratio of the Karstedt catalyst to the Vinyltriethoxysilane (VTES) is preferably 1: 2-4; the dosage of the dimethylbenzene is preferably 15-25 ml; the dosage of the deionized water is preferably 15-25 ml; the dosage of the dilute hydrochloric acid is preferably 5ml, and the pH value is preferably 2-4; the temperature of the water bath heating is preferably 70 ℃, and the time of the water bath heating is preferably 1 h; the magnetic stirring frequency is preferably 20 rpm.
In the step 2), the PCS (GO) obtained in the step 1) is usedx) Pressing the powder into green bodies, namely pressing PCS (GO) obtained in the step 1) by adopting an oil pressx) Pressing the powder into a green body in a steel model, wherein the using force of an oil press is preferably 100 MPa; the diameter of the steel model is preferably 10-20 mm; the inert gas is preferably high-purity argon, and the flow rate is controlled to be 150-250 ml/min; the pyrolysis temperature is preferably 1300-1500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 20-40 min.
The invention takes GO, VTES and PCS as raw materials to prepare a precursor PCS (GO) by a chemical modification methodx) Powder is subjected to compression molding, high-temperature pyrolysis and other steps to obtain compact graphene/silicon carbide nano composite structure monolithic ceramic SiC (rGO)x). Wherein the VTES hasSi-O-bond and-CH ═ CH2The group can compound GO and PCS into a new GO-VTES-PCS macromolecular structure. The GO is compounded into the silicon carbide ceramic, so that the cross-linking area of a precursor can be remarkably enlarged, the formation of SiC nanocrystals is inhibited, the sintering temperature is reduced, and the problems of difficult molding and poor compactness of the silicon carbide monolithic ceramic prepared by a precursor method are effectively solved.
The invention has the following beneficial effects:
(1) high molecular weight PCS (GO)x) The application of the precursor is beneficial to the forming of silicon carbide monolithic ceramics, and can meet the process requirement of forming silicon carbide devices with complicated shape designs.
(2) Compared with the traditional precursor method, the preparation method is simple and feasible, and SiC (rGO) can be obtained by adjusting the raw material proportion, the process parameters and the like0.1-0.5) The monolithic ceramic has strong practicability, and promotes the industrial production of preparing the silicon carbide ceramic by a precursor method.
(3) The hardness of the synthesized product is 14-20 GPa and can be adjusted, and the density is about 2.0g/cm3The linear shrinkage was about 26%. The ceramic has good compactness and greatly improved performance compared with the traditional silicon carbide ceramic, and can be applied to devices working under various complex conditions.
Drawings
FIG. 1 shows PCS (GO)0.1) Precursor (left) and SiC (rGO)0.1) Graphene/silicon carbide nanocomposite structured monolithic ceramics (right).
FIG. 2 shows PCS, VTES, GO and green PCS (GO)0.1)、PCS(GO0.3)、PCS(GO0.5) Infrared (FTIR) spectrum of (a). The abscissa in FIG. 2 is the wave number (cm)-1)。
FIG. 3 is a graphene/silicon carbide nanocomposite monolithic ceramic SiC (rGO)0.1)、SiC(rGO0.3)、SiC(rGO0.5) X-ray diffraction (XRD) pattern of (a). The abscissa in fig. 3 is 2 θ (°).
FIG. 4 is a graphene/silicon carbide nanocomposite monolithic ceramic SiC (rGO)0.1)、SiC(rGO0.3)、SiC(rGO0.5) Raman (Raman) spectrum of (a). The abscissa in FIG. 4 is the wave number (cm)-1)。
FIG. 5 is a graphene/silicon carbide nanocomposite monolithic ceramic SiC (rGO)0.1)、SiC(rGO0.3)、SiC(rGO0.5) Hardness versus PCS/GO weight ratio. The ordinate in FIG. 5 is hardness (GPa) and the abscissa is the PCS/GO weight ratio.
FIG. 6 is a graphene/silicon carbide nanocomposite structured monolithic ceramic SiC (rGO)0.1)、SiC(rGO0.3)、SiC(rGO0.5) Density versus PCS/GO weight ratio and linear shrinkage versus PCS/GO weight ratio. The left ordinate in FIG. 5 is the density (g/cm)3) The right ordinate is the linear shrinkage (%) and the abscissa is the PCS/GO weight ratio.
Detailed Description
The above-described scheme will be further explained with reference to specific embodiments.
The graphene/silicon carbide nano composite structure monolithic ceramic SiC (rGO) of the inventionx) Is composed of a PCS precursor (GO)x) Obtained by pyrolysis at high temperature, said PCS (GO)x) The structural general formula is as follows:
the precursor PCS (GO)x) The Infrared (FTIR) spectrum has the following characteristics: at 2100cm-1A peak belonging to Si-H bond is formed, and the peak intensity is reduced along with the increase of the content of the GO serving as the raw material; at 780cm-1(assigned to Si-C bond) and 1410cm-1(ascribed to-CH)2-bonds) increase in peak strength with increasing GO content of the raw material; at 1610cm with increasing GO content of the raw material-1(assigned to aromatic ring C ═ C bond) and 1720cm-1The absorption strength (assigned to C ═ O bonds) also increases. The precursor PCS (GO)x) Grey in color and increasing with raw material GO content, PCS (GO)x) The darker the color of (a), the closer to black.
The graphene/silicon carbide nano composite structure monolithic ceramic SiC (rGO) of the inventionx) The following features are present in the X-ray diffraction (XRD) pattern: the peak assigned to rGO is at 21.947 degrees 2 theta, and the peak increases with the GO content in the raw materialThe 2 theta (35.827 DEG/60.141 DEG/71.285 DEG) has a peak belonging to β -SiC crystal, and the peak values of the three peaks are gradually reduced along with the increase of the content of the raw material GOx) The following features are found in the Raman (Raman) spectrum: at 1335cm-1(peak D) and 1600cm-1(G Peak) has two distinct peaks, and as the content of GO in the raw material increases, the value of D Peak to G Peak (I)D/IG) And is increased. The graphene/silicon carbide nano composite structure monolithic ceramic SiC (rGO)x) The device is also characterized in that: with the increase of the content of GO serving as a raw material, the hardness, the density and the linear shrinkage rate of the ceramic are all reduced; the SiC (rGO)x) The ceramic is black.
Specific preparation method examples are given below.
Example 1
1. 1g of PCS with a relative molecular weight of 1426g/mol and 0.5ml of Karstedt catalyst were dissolved in 20ml of xylene to give a clear solution;
2. mixing 0.1g of GO powder into 20ml of deionized water, and then carrying out ultrasonic dispersion for 30 min;
3. and slowly adding the PCS/xylene mixture into the GO aqueous solution, adding 1ml of VTES into the mixed solution, and adjusting the pH value of the mixed solution to 2-4 by using 5ml of dilute hydrochloric acid.
4. The mixed solution was heated in a water bath to 70 ℃ and held for 1h while magnetic stirring was performed at a rate of 20 rpm.
5. And (4) standing the mixed solution obtained in the step (4) for 5min, and taking the supernatant to perform reduced pressure distillation through a rotary evaporator to obtain a black solid.
6. Grinding the black solid obtained in step 5 to obtain fine PCS (GO)0.1) And (3) obtaining a powder product.
7. Using an oil press to mix the PCS (GO) obtained in the step 60.1) Pressing the powder into a green body in a steel model with the diameter of 17mm, placing the green body on graphite paper, pyrolyzing the green body under the protection of high-purity argon with the flow of 200ml/min, wherein the heating rate is 5 ℃/min, the pyrolysis temperature is 1400 ℃, and the temperature is kept for 30min to finally obtain SiC (rGO)0.1) Monolithic ceramic.
8. For step 7Obtaining SiC (rGO)0.1) The monolithic ceramic is subjected to performance test, the Vickers hardness of the monolithic ceramic is 19.49GPa measured by a microhardness instrument, and the density of the monolithic ceramic is 2.18g/cm measured according to the Archimedes principle3The linear shrinkage was calculated to be 26.88%.
Example 2
1. 1g of PCS with a relative molecular weight of 1426g/mol and 0.5ml of Karstedt catalyst were dissolved in 20ml of xylene to give a clear solution;
2. mixing 0.3g of GO powder into 20ml of deionized water, and then carrying out ultrasonic dispersion for 30 min;
3. and slowly adding the PCS/xylene mixture into the GO aqueous solution, adding 1.4ml of VTES into the mixed solution, and adjusting the pH value of the mixed solution to 2-4 by using 5ml of dilute hydrochloric acid.
4. The mixed solution was heated in a water bath to 70 ℃ and held for 1h while magnetic stirring was performed at a rate of 20 rpm.
5. And (4) standing the mixed solution obtained in the step (4) for 5min, and taking the supernatant to perform reduced pressure distillation through a rotary evaporator to obtain a black solid.
6. Grinding the black solid obtained in step 5 to obtain fine PCS (GO)0.3) And (3) obtaining a powder product.
7. Using an oil press to mix the PCS (GO) obtained in the step 60.3) Pressing the powder into a green body in a steel model with the diameter of 17mm, placing the green body on graphite paper, pyrolyzing the green body under the protection of high-purity argon with the flow of 200ml/min, wherein the heating rate is 5 ℃/min, the pyrolysis temperature is 1400 ℃, and the temperature is kept for 30min to finally obtain SiC (rGO)0.3) Monolithic ceramic.
8. For SiC (rGO) obtained in step 70.3) The monolithic ceramic is subjected to performance test, the Vickers hardness of the monolithic ceramic is 15.41GPa as measured by a microhardness instrument, and the density of the monolithic ceramic is 2.01g/cm as measured according to the Archimedes principle3The linear shrinkage was calculated to be 25.88%.
Example 3
1. 1g of PCS with a relative molecular weight of 1426g/mol and 0.5ml of Karstedt catalyst were dissolved in 20ml of xylene to give a clear solution;
2. mixing 0.5g of GO powder into 20ml of deionized water, and then carrying out ultrasonic dispersion for 30 min;
3. and slowly adding the PCS/xylene mixture into the GO aqueous solution, adding 1.8ml of VTES into the mixed solution, and adjusting the pH value of the mixed solution to 2-4 by using 5ml of dilute hydrochloric acid.
4. The mixed solution was heated in a water bath to 70 ℃ and held for 1h while magnetic stirring was performed at a rate of 20 rpm.
5. And (4) standing the mixed solution obtained in the step (4) for 5min, and taking the supernatant to perform reduced pressure distillation through a rotary evaporator to obtain a black solid.
6. Grinding the black solid obtained in step 5 to obtain fine PCS (GO)0.5) And (3) obtaining a powder product.
7. Using an oil press to mix the PCS (GO) obtained in the step 60.5) Pressing the powder into a green body in a steel model with the diameter of 17mm, placing the green body on graphite paper, pyrolyzing the green body under the protection of high-purity argon with the flow of 200ml/min, wherein the heating rate is 5 ℃/min, the pyrolysis temperature is 1400 ℃, and the temperature is kept for 30min to finally obtain SiC (rGO)0.5) Monolithic ceramic.
8. For SiC (rGO) obtained in step 70.5) The monolithic ceramic is subjected to performance test, the Vickers hardness of the monolithic ceramic is 14.29GPa as measured by a microhardness instrument, and the density of the monolithic ceramic is 1.77g/cm as measured according to the Archimedes principle3The linear shrinkage was calculated to be 23.88%.
FIG. 1 shows PCS (GO)0.1) Precursor (left) and SiC (rGO)0.1) Graphene/silicon carbide nanocomposite structured monolithic ceramics (right).
FIG. 2 shows PCS, VTES, GO and green PCS (GO)0.1)、PCS(GO0.3)、PCS(GO0.5) Infrared (FTIR) spectrum of (a). The abscissa in FIG. 2 is the wave number (cm)-1)。
FIG. 3 is a graphene/silicon carbide nanocomposite monolithic ceramic SiC (rGO)0.1)、SiC(rGO0.3)、SiC(rGO0.5) X-ray diffraction (XRD) pattern of (a). The abscissa in fig. 3 is 2 θ (°).
FIG. 4 is a graphene/silicon carbide nanocomposite monolithic ceramic SiC (rGO)0.1)、SiC(rGO0.3)、SiC(rGO0.5) Raman (Raman) spectrum of (a). In the cross section of FIG. 4The coordinates are wave number (cm)-1)。
FIG. 5 is a graphene/silicon carbide nanocomposite monolithic ceramic SiC (rGO)0.1)、SiC(rGO0.3)、SiC(rGO0.5) Hardness versus PCS/GO weight ratio. The ordinate in FIG. 5 is hardness (GPa) and the abscissa is the PCS/GO weight ratio.
FIG. 6 is a graphene/silicon carbide nanocomposite structured monolithic ceramic SiC (rGO)0.1)、SiC(rGO0.3)、SiC(rGO0.5) Density versus PCS/GO weight ratio and linear shrinkage versus PCS/GO weight ratio. The left ordinate in FIG. 5 is the density (g/cm)3) The right ordinate is the linear shrinkage (%) and the abscissa is the PCS/GO weight ratio. The graphene/silicon carbide nano composite structure monolithic ceramic obtained by the method has excellent physical properties, and the physical properties of the monolithic ceramic are not greatly influenced by the addition proportion of GO.
The invention designs a simple graphene oxide-vinyl triethoxysilane-polycarbosilane (GO-VTES-PCS named as PCS (GO)x) ) preparing the graphene/silicon carbide nano composite structure monolithic ceramic by high-temperature pyrolysis of the precursor. The novel process solves the problem of difficult molding of the silicon carbide precursor ceramic, can meet the ceramic preparation requirement of complex structural design, effectively improves the physical performance of the silicon carbide monolithic ceramic, reduces the production cost, and is beneficial to mass production and wide application.
Claims (10)
1. A preparation method of graphene/silicon carbide nano composite structure monolithic ceramic is characterized by comprising the following steps:
1) precursor PCS (GO)x) Synthesis of (2)
Mixing GO powder into deionized water and performing ultrasonic dispersion, dissolving PCS and Karstedt catalyst into a xylene organic solvent, adding a PCS/xylene mixture into a GO aqueous solution, adding VTES into the mixed solution, and adjusting the mixed solution to be acidic by using dilute hydrochloric acid; heating the mixed solution in water bath while magnetically stirring, standing, collecting supernatant, distilling under reduced pressure with rotary evaporator to obtain black solid, and grinding to obtain fine precursor PCS(GOx) Powder products, wherein x is the mass ratio of PCS to GO;
2) monolithic ceramic SiC (rGO) with graphene/silicon carbide nano composite structurex) Preparation of
The PCS (GO) obtained in the step 1)x) Pressing the powder into green bodies, placing the green bodies on graphite paper, and pyrolyzing the green bodies under the protection of inert gas to obtain the graphene/silicon carbide nano composite structure monolithic ceramic SiC (rGO)x) (ii) a And the PCS is cracked at high temperature to generate SiC, and GO is reduced into rGO through high-temperature final burning.
2. The method for preparing the graphene/silicon carbide nano composite structure monolithic ceramic of claim 1, wherein in the step 1), the mass ratio of the PCS to the GO is 10: 1-5, and the volume ratio of the Karstedt catalyst to the VTES is 1: 2-4.
3. The method for preparing the graphene/silicon carbide nanocomposite structure monolithic ceramic according to claim 1, wherein in the step 1), the amount of the xylene is 15 to 25 mL; the using amount of the deionized water is 15-25 mL; the dosage of the dilute hydrochloric acid is 5mL, so that the pH value is 2-4.
4. The method for preparing the graphene/silicon carbide nanocomposite structure monolithic ceramic according to claim 1, wherein in the step 1), the water bath heating temperature is 70 ℃, and the water bath heating time is 1 h.
5. The method for preparing graphene/silicon carbide nanocomposite structure monolithic ceramic according to claim 1, wherein in the step 1), the frequency of the magnetic stirring is 20 rpm.
6. The method for preparing graphene/silicon carbide nanocomposite structure monolithic ceramic according to claim 1, wherein in the step 2), the PCS (GO) obtained in the step 1) is usedx) Pressing the powder into a green body, and adopting an oil press to press the PCS (GO) obtained in the step 1)x) Pressing the powder in a steel mouldAnd (4) green pressing.
7. The method according to claim 6, wherein the oil press working force is 100 MPa; the diameter of the steel model is 10-20 mm.
8. The method for preparing the graphene/silicon carbide nanocomposite structure monolithic ceramic according to claim 1, wherein in the step 2), the inert gas is argon, and the flow rate is controlled to be 150-250 mL/min.
9. The method for preparing the graphene/silicon carbide nanocomposite structure monolithic ceramic according to claim 1, wherein in the step 2), the pyrolysis temperature is 1300-1500 ℃, the heating rate is 5 ℃/min, and the holding time is 20-40 min.
10. The graphene/silicon carbide nanocomposite monolithic ceramic prepared by the method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201711494377.7A CN108129151B (en) | 2017-12-31 | 2017-12-31 | Graphene/silicon carbide nano composite structure monolithic ceramic and preparation method thereof |
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| CN110467467B (en) * | 2019-09-03 | 2020-10-02 | 厦门大学 | Bulk silicon carbide polymer precursor ceramic and blending and cracking preparation method |
| CN110922191B (en) * | 2019-12-20 | 2020-12-01 | 厦门大学 | Silicon carbide polymer precursor ceramic defect healing method |
| CN111454061B (en) * | 2020-04-07 | 2021-10-01 | 厦门大学 | Polycarbosilane non-melting pretreatment and cracking conversion method for three-dimensional ceramic |
| CN111848172B (en) * | 2020-07-24 | 2021-09-28 | 厦门大学 | Molybdenum disilicide/silicon carbide three-dimensional polymer precursor ceramic and preparation method thereof |
| CN115465856A (en) * | 2021-06-10 | 2022-12-13 | 中国科学院上海微系统与信息技术研究所 | Preparation method of patterned graphene |
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